copolymers of 2,4‐dichlorophenyl methacrylate with styrene: synthesis, thermal properties, and...

15
This article was downloaded by: [Eindhoven Technical University] On: 22 November 2014, At: 05:03 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Journal of Macromolecular Science, Part A: Pure and Applied Chemistry Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/lmsa20 Copolymers of 2,4Dichlorophenyl Methacrylate with Styrene: Synthesis, Thermal Properties, and Antimicrobial Activity Jatin N. Patel a , Milan V. Patel a & Rajni M. Patel a a Department of Chemistry , Sardar Patel University , Vallabh Vidyanagar, 388120, Gujarat, India Published online: 22 Aug 2007. To cite this article: Jatin N. Patel , Milan V. Patel & Rajni M. Patel (2005) Copolymers of 2,4Dichlorophenyl Methacrylate with Styrene: Synthesis, Thermal Properties, and Antimicrobial Activity, Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 42:1, 71-83, DOI: 10.1081/MA-200040970 To link to this article: http://dx.doi.org/10.1081/MA-200040970 PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

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This article was downloaded by [Eindhoven Technical University]On 22 November 2014 At 0503Publisher Taylor amp FrancisInforma Ltd Registered in England and Wales Registered Number 1072954 Registeredoffice Mortimer House 37-41 Mortimer Street London W1T 3JH UK

Journal of Macromolecular Science PartA Pure and Applied ChemistryPublication details including instructions for authors andsubscription informationhttpwwwtandfonlinecomloilmsa20

Copolymers of 24‐DichlorophenylMethacrylate with Styrene SynthesisThermal Properties and AntimicrobialActivityJatin N Patel a Milan V Patel a amp Rajni M Patel aa Department of Chemistry Sardar Patel University VallabhVidyanagar 388120 Gujarat IndiaPublished online 22 Aug 2007

To cite this article Jatin N Patel Milan V Patel amp Rajni M Patel (2005) Copolymers of24‐Dichlorophenyl Methacrylate with Styrene Synthesis Thermal Properties and AntimicrobialActivity Journal of Macromolecular Science Part A Pure and Applied Chemistry 421 71-83 DOI101081MA-200040970

To link to this article httpdxdoiorg101081MA-200040970

PLEASE SCROLL DOWN FOR ARTICLE

Taylor amp Francis makes every effort to ensure the accuracy of all the information (theldquoContentrdquo) contained in the publications on our platform However Taylor amp Francisour agents and our licensors make no representations or warranties whatsoever as tothe accuracy completeness or suitability for any purpose of the Content Any opinionsand views expressed in this publication are the opinions and views of the authorsand are not the views of or endorsed by Taylor amp Francis The accuracy of the Contentshould not be relied upon and should be independently verified with primary sourcesof information Taylor and Francis shall not be liable for any losses actions claimsproceedings demands costs expenses damages and other liabilities whatsoever orhowsoever caused arising directly or indirectly in connection with in relation to or arisingout of the use of the Content

This article may be used for research teaching and private study purposes Anysubstantial or systematic reproduction redistribution reselling loan sub-licensingsystematic supply or distribution in any form to anyone is expressly forbidden Terms amp

Conditions of access and use can be found at httpwwwtandfonlinecompageterms-and-conditions

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Copolymers of 24-Dichlorophenyl Methacrylatewith Styrene Synthesis Thermal Properties

and Antimicrobial Activity

JATIN N PATEL MILAN V PATELAND RAJNI M PATEL

Department of Chemistry Sardar Patel University Gujarat India

The methacrylate monomer 24-dichlorophenyl methacrylate (24-DMA) was syn-thesized by reacting 24-dichlorophenol (24-D) with methacryloyl chloride Thefree-radical initiated copolymerization of 24-DMA with styrene was carried out in atoluene solution at 708C using 220-azobisisobutyronitrile (AIBN) as an initiator withdifferent monomer feed ratios The monomer 24-DMA and the copolymers werecharacterized by Fourier transform infrared spectral studies Copolymer compositionwas determined by UV-spectroscopy The reactivity ratio of the monomers wasobtained employing the conventional linearization method of FinemanndashRoss Themolecular weights (Mw Mn) and polydispersity index of the polymers were determinedusing gel permeation chromatography Thermogravimetric analysis (TGA) of thepolymers was carried out in nitrogen atmosphere Antimicrobial effects of the homo-and copolymers were also investigated for various microorganisms

Keywords copolymer reactivity ratio thermal analysis antimicrobial activity

Introduction

Copolymerization is one of the most successful and powerful methods for affecting sys-

tematic changes in polymer properties[1] The incorporation of two different monomers

having different physical andor chemical properties in the same polymer molecule in

varying properties leads to the formation of new materials with great scientific and com-

mercial importance[2] Currently a strong demand exists for functional polymers with very

specific properties In recent years some comprehensive work has been published on func-

tional monomer and their polymers[3ndash5]

Because of their excellent biocompatibility and long term stability the polymeric

systems based on acrylic derivatives are increasingly being used as biomaterials for

clinical applications[6]

Acrylate and methacrylate vinyl esters are readily polymerized by freemdashradical

polymerization to form linear branched or network polymers[7] Thermogravimetric

analysis (TGA) has been widely used to investigate the thermal decomposition of these

Received February 2004 Accepted May 2004Address correspondence to Jatin N Patel Department of Chemistry Sardar Patel University

Vallabh Vidyanagar 388120 Gujarat India E-mail jatspatel11979yahoocoin

Journal of Macromolecular SciencewPart AmdashPure and Applied Chemistry 4271ndash83 2005

Copyright Taylor amp Francis Inc

ISSN 1060-1325 print1520-5738 online

DOI 101081MA-200040970

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polymers[8ndash10] The polymers having antimicrobial properties are suitable in a variety of

applications such as film packaging materials foodstuffs sanitary application and many

others[1112]

The presence of chlorine has been suggested to impart an antimicrobial property to a

compound[1314] Many acrylic polymers containing chlorine and possessing an antimicro-

bial property have been reported[1516] Recently the acrylic polymers derived from 24-

dichlorophenyl methacrylate (24-DMA) and MMA are reported from this laboratory[17]

and these are found to be antimicrobial agents It was thought appropriate to replace

MMA by styrene to form copolymers with 24-DMA and examine the antimicrobial

property so that the role of MMA in inhibiting the growth of microorganisms could be

examined

Here we report the synthesis and characterization of monomer 24-DMA as well as

homo- and copolymers of 24-DMA with styrene obtained by using different monomer

feed ratio The copolymer composition was obtained by UV-spectroscopy and

molecular weight was determined by gel permeation chromatography Thermal analyses

of polymers are also included here The homo- and copolymers have been used to

screen their antimicrobial activity against microorganisms such as bacteria (Escherichia

coli Bacillus subtilis and Staphylococcus citreus) fungi (Aspergillus niger Sporotrichum

pulverulentum and Trichoderma lignorum) and yeast (Candida utilis Saccharomyces

cerevisiae and Pichia stipitis) These organisms were chosen because of their ready

availability

Experimental

Materials

Methacryloyl chloride (Fluka) was used as received Styrene was freed from the inhibitor

by washing with 5 NaOH solution followed by distilled water and after drying over

anhydrous sodium sulfate it was distilled under vacuum 220-Azobisisobutyronitrile

(AIBN) was recrystallized from ethanol All other chemicals were of analytical grade

products obtained from Chiti Chem Baroda India and they were used without any

further purification

Synthesis of 24-Dichlorophenyl Methacrylate

Methacryloyl chloride was prepared by reacting methacrylic acid with benzoyl

chloride[18] The esterification was performed with methacryloyl chloride and 24-dichloro-

phenol (24-D)

Absolute alcohol (400mL) and NaOH (02mol 809 g) were added to a three-necked

flask equipped with stirrer condenser and thermometer and placed in a water bath and the

contents were stirred until all the NaOH dissolved and 24-D (02mol 326 g) was added

to this The reaction mixture was heated to 608C for 30min with stirring then cooled to

room temperature and then to 0ndash58C by ice Freshly prepared methacryloyl chloride

(021mol 205mL) was added to the cooled reaction mixture and stirred for 90min It

was then poured into a crushed icendashwater mixture when a cream colored product

separated out It was filtered out washed thoroughly with cold water dried at 358C in

vacuum and recrystallized from petroleum ether

J N Patel M V Patel and R M Patel72

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Copolymerization

Homo- and copolymerizations were carried out in toluene using AIBN as an initiator Pre-

determined quantities of 24-DMA styrene toluene and AIBN were mixed in a round

bottom flask equipped with mechanical stirrer and reflux condenser The reaction

mixture was heated at 708C for 5 hr with constant stirring After that it was cooled to

room temperature and slowly poured into a large excess of methanol used as a non-

solvent with constant stirring A solid polymer was purified by repeated precipitation by

methanol from solution in toluene and finally dried under vacuum

Characterization

Infrared spectra of solid samples in the KBr pellets were recorded with a NICOLET-400DFT-IR spectrophotometer A Shimadzu-160A recording UV-visible spectrophotometer

was used to determine copolymer composition and reactivity ratio Molecular weights

of the polymers were determined by gel permeation chromatography (Water 600E)

equipped with a 410-RI detectors calibrated with polystyrene standard TGA was

performed with DuPont-951 thermal analyzer at a heating rate of 108Cmin21 in static

air atmosphere A differential thermal analysis (DTA) trace was obtained with a

DuPont-9900 differential thermal analyzer at a heating rate of 108Cmin21 in nitrogen

atmosphere

Antimicrobial Activity

The homo- and copolymers thus obtained were tested against different microorganisms

which are commonly employed for biodegradability tests bacterial strains (B subtilis

E coli and S citreus) fungi (A niger S pulverulentum and T lignorum) and yeast

(C utilis S cerevisiae and P stipitis) were grown in Nutrient broth (N-broth) and Sabour-

andrsquos dextrose broth medium

Screening of Acrylic Copolymers for Antibacterial Activity A 5 (vv) inoculum of

bacterial culture was used to inoculate a 100mL solution of N-broth (control ie it

does not contain polymer) and test media (100mL solution of N-broththorn 50mg

polymer sample) and incubated on rotary shaker (200 rpm) at room temperature A

05mL liquid was withdrawn at specified time intervals (24ndash48 hr) from test-media and

after suitable dilution with 35-dinitrosalicylic acid (DNS) reagent[19] and distilled

water optical density was measured at 660 nm The analysis was carried out using a

DNS reagent of the following compositions DNS (104 g) NaOH (198 g) NaK-

tartarate (306 g) phenol (76 g) sodiummetabisulfate (83 g) distilled water (1416mL)

The activity was calculated as optical density per milliliter (ie growth) This method

is based on the principle that as growth proceeds cell number increases which lead to

increase in optical density of medium

Screening of Acrylic Copolymers for Antifungal Activity Since fungal culture shows fila-

mentous growth an optical method cannot be used to monitor the growth Gravimetric

analysis was carried out to determine the dry cell mass A 10 (vv) inoculum was

added to the sterile control medium (without polymer) and test medium (100mL

controlthorn 50mg polymer sample) Flasks were incubated at room temperature on a

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 73

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rotary shaker (200 rpm) for 48 hr Contents of the flasks were filtered using cheese cloth

and cell pellets were dried to content weight

Screening of Acrylic Copolymers on Yeast A 5 (vv) inoculum of yeast culture was

added to both sterile control medium and test medium (100mL controlthorn 50mg polymer

sample) and the same procedure as mentioned in antibacterial activity was followed

Results and Discussion

The copolymerization of 24-DMA with styrene in toluene solution was studied in a wide

composition interval with a mole fraction of 24-DMA ranging from 02 to 08 in the feed

The reaction time was selected to give conversion less than 10 wt in order to satisfy the

differential copolymerization equation

The peaks due to IR spectrum (Fig 1) of the monomer are IR (cm21) 2925 (nCH3)

1743 (nC55o) 1642 (nC55C) 1333 (nCndashO) 1232 and 1160 (nCndashOndashC) 890 (ndashCH bending

mode of vinyl group) 720 (rocking mode of vinyl group) 670 (nCndashCl) 1590 and 1488

(bands due to phenyl ring)

The proton NMR peaks (Fig 2) are 1H-NMR (ppm) (60MHz) 2080 (3H) (methyl

proton) 6416 (1H) and 5811 (1H) (non-equivalent methylene protons) 7383ndash7471

(1H) (aromatic proton) 7031ndash7236 (2H) (aromatic proton)

Figure 1 IR spectra of 24-DMA

J N Patel M V Patel and R M Patel74

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The spectral data agree well with the results reported for the monomer 24-DMA[20]

The IR spectra (Fig 3) confirmed the structure of copolymers A band at 2969ndash

2800 cm21 is attributed to CndashH stretching vibration of methyl and methylene group

The bands at 1380 and 1460 cm21 are assigned to the CndashH bending vibrations of

methyl and methylene groups The strong absorption at 1770 cm21 is due to C55O stretch-

ing vibration in ester group whereas the strong absorption at 1300 cm21 could be attrib-

uted to predominantly CndashO stretching The bands at 750 cm21 may have contributions

from CndashH out-of-plane bending vibration of monosubstituted aromatic ring[21] In the

copolymers as the styrene content decreases the intensity of 750 cm21 band also

decreases The band at 680 cm21 is attributed to CndashCl stretching[22] The disappearance

of the band at 1642 cm21 indicates the formation of polymers

Copolymer Composition and Reactivity Ratios

The synthesis of copolymer is presented in Fig 4 The average composition of

each copolymer sample was determined from the corresponding UV-spectrum The

assignment of the absorption in the UV-spectrum allows for the accurate determination

of the content of each kind of monomeric unit incorporated into the copolymer

chains The reactivity ratios of 24-DMA and styrene were determined by the

FinemanndashRoss (FndashR) method[23] and presented in Table 1 The value of reactivity

ratios for 24-DMA (r1) and styrene (r2) from FndashR plot is 035 and 09 respectively

When r1 and r2 values are less than 1 the system gives rise to azeotropic

Figure 2 1H-NMR spectra of 24-DMA

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 75

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polymerization at a particular composition of the monomer which is calculated using

the equation[24]

N1 frac141 r2

2 r1 r2

frac14 0133

where N1 is the mole fraction of 24-DMA in the feed

Figure 3 IR spectra of homo- and copolymers of 24-DMA with styrene

J N Patel M V Patel and R M Patel76

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When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

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Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

J N Patel M V Patel and R M Patel78

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Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

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All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

J N Patel M V Patel and R M Patel80

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Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

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Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

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18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

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Conditions of access and use can be found at httpwwwtandfonlinecompageterms-and-conditions

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Copolymers of 24-Dichlorophenyl Methacrylatewith Styrene Synthesis Thermal Properties

and Antimicrobial Activity

JATIN N PATEL MILAN V PATELAND RAJNI M PATEL

Department of Chemistry Sardar Patel University Gujarat India

The methacrylate monomer 24-dichlorophenyl methacrylate (24-DMA) was syn-thesized by reacting 24-dichlorophenol (24-D) with methacryloyl chloride Thefree-radical initiated copolymerization of 24-DMA with styrene was carried out in atoluene solution at 708C using 220-azobisisobutyronitrile (AIBN) as an initiator withdifferent monomer feed ratios The monomer 24-DMA and the copolymers werecharacterized by Fourier transform infrared spectral studies Copolymer compositionwas determined by UV-spectroscopy The reactivity ratio of the monomers wasobtained employing the conventional linearization method of FinemanndashRoss Themolecular weights (Mw Mn) and polydispersity index of the polymers were determinedusing gel permeation chromatography Thermogravimetric analysis (TGA) of thepolymers was carried out in nitrogen atmosphere Antimicrobial effects of the homo-and copolymers were also investigated for various microorganisms

Keywords copolymer reactivity ratio thermal analysis antimicrobial activity

Introduction

Copolymerization is one of the most successful and powerful methods for affecting sys-

tematic changes in polymer properties[1] The incorporation of two different monomers

having different physical andor chemical properties in the same polymer molecule in

varying properties leads to the formation of new materials with great scientific and com-

mercial importance[2] Currently a strong demand exists for functional polymers with very

specific properties In recent years some comprehensive work has been published on func-

tional monomer and their polymers[3ndash5]

Because of their excellent biocompatibility and long term stability the polymeric

systems based on acrylic derivatives are increasingly being used as biomaterials for

clinical applications[6]

Acrylate and methacrylate vinyl esters are readily polymerized by freemdashradical

polymerization to form linear branched or network polymers[7] Thermogravimetric

analysis (TGA) has been widely used to investigate the thermal decomposition of these

Received February 2004 Accepted May 2004Address correspondence to Jatin N Patel Department of Chemistry Sardar Patel University

Vallabh Vidyanagar 388120 Gujarat India E-mail jatspatel11979yahoocoin

Journal of Macromolecular SciencewPart AmdashPure and Applied Chemistry 4271ndash83 2005

Copyright Taylor amp Francis Inc

ISSN 1060-1325 print1520-5738 online

DOI 101081MA-200040970

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polymers[8ndash10] The polymers having antimicrobial properties are suitable in a variety of

applications such as film packaging materials foodstuffs sanitary application and many

others[1112]

The presence of chlorine has been suggested to impart an antimicrobial property to a

compound[1314] Many acrylic polymers containing chlorine and possessing an antimicro-

bial property have been reported[1516] Recently the acrylic polymers derived from 24-

dichlorophenyl methacrylate (24-DMA) and MMA are reported from this laboratory[17]

and these are found to be antimicrobial agents It was thought appropriate to replace

MMA by styrene to form copolymers with 24-DMA and examine the antimicrobial

property so that the role of MMA in inhibiting the growth of microorganisms could be

examined

Here we report the synthesis and characterization of monomer 24-DMA as well as

homo- and copolymers of 24-DMA with styrene obtained by using different monomer

feed ratio The copolymer composition was obtained by UV-spectroscopy and

molecular weight was determined by gel permeation chromatography Thermal analyses

of polymers are also included here The homo- and copolymers have been used to

screen their antimicrobial activity against microorganisms such as bacteria (Escherichia

coli Bacillus subtilis and Staphylococcus citreus) fungi (Aspergillus niger Sporotrichum

pulverulentum and Trichoderma lignorum) and yeast (Candida utilis Saccharomyces

cerevisiae and Pichia stipitis) These organisms were chosen because of their ready

availability

Experimental

Materials

Methacryloyl chloride (Fluka) was used as received Styrene was freed from the inhibitor

by washing with 5 NaOH solution followed by distilled water and after drying over

anhydrous sodium sulfate it was distilled under vacuum 220-Azobisisobutyronitrile

(AIBN) was recrystallized from ethanol All other chemicals were of analytical grade

products obtained from Chiti Chem Baroda India and they were used without any

further purification

Synthesis of 24-Dichlorophenyl Methacrylate

Methacryloyl chloride was prepared by reacting methacrylic acid with benzoyl

chloride[18] The esterification was performed with methacryloyl chloride and 24-dichloro-

phenol (24-D)

Absolute alcohol (400mL) and NaOH (02mol 809 g) were added to a three-necked

flask equipped with stirrer condenser and thermometer and placed in a water bath and the

contents were stirred until all the NaOH dissolved and 24-D (02mol 326 g) was added

to this The reaction mixture was heated to 608C for 30min with stirring then cooled to

room temperature and then to 0ndash58C by ice Freshly prepared methacryloyl chloride

(021mol 205mL) was added to the cooled reaction mixture and stirred for 90min It

was then poured into a crushed icendashwater mixture when a cream colored product

separated out It was filtered out washed thoroughly with cold water dried at 358C in

vacuum and recrystallized from petroleum ether

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Copolymerization

Homo- and copolymerizations were carried out in toluene using AIBN as an initiator Pre-

determined quantities of 24-DMA styrene toluene and AIBN were mixed in a round

bottom flask equipped with mechanical stirrer and reflux condenser The reaction

mixture was heated at 708C for 5 hr with constant stirring After that it was cooled to

room temperature and slowly poured into a large excess of methanol used as a non-

solvent with constant stirring A solid polymer was purified by repeated precipitation by

methanol from solution in toluene and finally dried under vacuum

Characterization

Infrared spectra of solid samples in the KBr pellets were recorded with a NICOLET-400DFT-IR spectrophotometer A Shimadzu-160A recording UV-visible spectrophotometer

was used to determine copolymer composition and reactivity ratio Molecular weights

of the polymers were determined by gel permeation chromatography (Water 600E)

equipped with a 410-RI detectors calibrated with polystyrene standard TGA was

performed with DuPont-951 thermal analyzer at a heating rate of 108Cmin21 in static

air atmosphere A differential thermal analysis (DTA) trace was obtained with a

DuPont-9900 differential thermal analyzer at a heating rate of 108Cmin21 in nitrogen

atmosphere

Antimicrobial Activity

The homo- and copolymers thus obtained were tested against different microorganisms

which are commonly employed for biodegradability tests bacterial strains (B subtilis

E coli and S citreus) fungi (A niger S pulverulentum and T lignorum) and yeast

(C utilis S cerevisiae and P stipitis) were grown in Nutrient broth (N-broth) and Sabour-

andrsquos dextrose broth medium

Screening of Acrylic Copolymers for Antibacterial Activity A 5 (vv) inoculum of

bacterial culture was used to inoculate a 100mL solution of N-broth (control ie it

does not contain polymer) and test media (100mL solution of N-broththorn 50mg

polymer sample) and incubated on rotary shaker (200 rpm) at room temperature A

05mL liquid was withdrawn at specified time intervals (24ndash48 hr) from test-media and

after suitable dilution with 35-dinitrosalicylic acid (DNS) reagent[19] and distilled

water optical density was measured at 660 nm The analysis was carried out using a

DNS reagent of the following compositions DNS (104 g) NaOH (198 g) NaK-

tartarate (306 g) phenol (76 g) sodiummetabisulfate (83 g) distilled water (1416mL)

The activity was calculated as optical density per milliliter (ie growth) This method

is based on the principle that as growth proceeds cell number increases which lead to

increase in optical density of medium

Screening of Acrylic Copolymers for Antifungal Activity Since fungal culture shows fila-

mentous growth an optical method cannot be used to monitor the growth Gravimetric

analysis was carried out to determine the dry cell mass A 10 (vv) inoculum was

added to the sterile control medium (without polymer) and test medium (100mL

controlthorn 50mg polymer sample) Flasks were incubated at room temperature on a

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 73

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rotary shaker (200 rpm) for 48 hr Contents of the flasks were filtered using cheese cloth

and cell pellets were dried to content weight

Screening of Acrylic Copolymers on Yeast A 5 (vv) inoculum of yeast culture was

added to both sterile control medium and test medium (100mL controlthorn 50mg polymer

sample) and the same procedure as mentioned in antibacterial activity was followed

Results and Discussion

The copolymerization of 24-DMA with styrene in toluene solution was studied in a wide

composition interval with a mole fraction of 24-DMA ranging from 02 to 08 in the feed

The reaction time was selected to give conversion less than 10 wt in order to satisfy the

differential copolymerization equation

The peaks due to IR spectrum (Fig 1) of the monomer are IR (cm21) 2925 (nCH3)

1743 (nC55o) 1642 (nC55C) 1333 (nCndashO) 1232 and 1160 (nCndashOndashC) 890 (ndashCH bending

mode of vinyl group) 720 (rocking mode of vinyl group) 670 (nCndashCl) 1590 and 1488

(bands due to phenyl ring)

The proton NMR peaks (Fig 2) are 1H-NMR (ppm) (60MHz) 2080 (3H) (methyl

proton) 6416 (1H) and 5811 (1H) (non-equivalent methylene protons) 7383ndash7471

(1H) (aromatic proton) 7031ndash7236 (2H) (aromatic proton)

Figure 1 IR spectra of 24-DMA

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The spectral data agree well with the results reported for the monomer 24-DMA[20]

The IR spectra (Fig 3) confirmed the structure of copolymers A band at 2969ndash

2800 cm21 is attributed to CndashH stretching vibration of methyl and methylene group

The bands at 1380 and 1460 cm21 are assigned to the CndashH bending vibrations of

methyl and methylene groups The strong absorption at 1770 cm21 is due to C55O stretch-

ing vibration in ester group whereas the strong absorption at 1300 cm21 could be attrib-

uted to predominantly CndashO stretching The bands at 750 cm21 may have contributions

from CndashH out-of-plane bending vibration of monosubstituted aromatic ring[21] In the

copolymers as the styrene content decreases the intensity of 750 cm21 band also

decreases The band at 680 cm21 is attributed to CndashCl stretching[22] The disappearance

of the band at 1642 cm21 indicates the formation of polymers

Copolymer Composition and Reactivity Ratios

The synthesis of copolymer is presented in Fig 4 The average composition of

each copolymer sample was determined from the corresponding UV-spectrum The

assignment of the absorption in the UV-spectrum allows for the accurate determination

of the content of each kind of monomeric unit incorporated into the copolymer

chains The reactivity ratios of 24-DMA and styrene were determined by the

FinemanndashRoss (FndashR) method[23] and presented in Table 1 The value of reactivity

ratios for 24-DMA (r1) and styrene (r2) from FndashR plot is 035 and 09 respectively

When r1 and r2 values are less than 1 the system gives rise to azeotropic

Figure 2 1H-NMR spectra of 24-DMA

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 75

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polymerization at a particular composition of the monomer which is calculated using

the equation[24]

N1 frac141 r2

2 r1 r2

frac14 0133

where N1 is the mole fraction of 24-DMA in the feed

Figure 3 IR spectra of homo- and copolymers of 24-DMA with styrene

J N Patel M V Patel and R M Patel76

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When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

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Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

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Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

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All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

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Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

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Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

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18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

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Copolymers of 24-Dichlorophenyl Methacrylatewith Styrene Synthesis Thermal Properties

and Antimicrobial Activity

JATIN N PATEL MILAN V PATELAND RAJNI M PATEL

Department of Chemistry Sardar Patel University Gujarat India

The methacrylate monomer 24-dichlorophenyl methacrylate (24-DMA) was syn-thesized by reacting 24-dichlorophenol (24-D) with methacryloyl chloride Thefree-radical initiated copolymerization of 24-DMA with styrene was carried out in atoluene solution at 708C using 220-azobisisobutyronitrile (AIBN) as an initiator withdifferent monomer feed ratios The monomer 24-DMA and the copolymers werecharacterized by Fourier transform infrared spectral studies Copolymer compositionwas determined by UV-spectroscopy The reactivity ratio of the monomers wasobtained employing the conventional linearization method of FinemanndashRoss Themolecular weights (Mw Mn) and polydispersity index of the polymers were determinedusing gel permeation chromatography Thermogravimetric analysis (TGA) of thepolymers was carried out in nitrogen atmosphere Antimicrobial effects of the homo-and copolymers were also investigated for various microorganisms

Keywords copolymer reactivity ratio thermal analysis antimicrobial activity

Introduction

Copolymerization is one of the most successful and powerful methods for affecting sys-

tematic changes in polymer properties[1] The incorporation of two different monomers

having different physical andor chemical properties in the same polymer molecule in

varying properties leads to the formation of new materials with great scientific and com-

mercial importance[2] Currently a strong demand exists for functional polymers with very

specific properties In recent years some comprehensive work has been published on func-

tional monomer and their polymers[3ndash5]

Because of their excellent biocompatibility and long term stability the polymeric

systems based on acrylic derivatives are increasingly being used as biomaterials for

clinical applications[6]

Acrylate and methacrylate vinyl esters are readily polymerized by freemdashradical

polymerization to form linear branched or network polymers[7] Thermogravimetric

analysis (TGA) has been widely used to investigate the thermal decomposition of these

Received February 2004 Accepted May 2004Address correspondence to Jatin N Patel Department of Chemistry Sardar Patel University

Vallabh Vidyanagar 388120 Gujarat India E-mail jatspatel11979yahoocoin

Journal of Macromolecular SciencewPart AmdashPure and Applied Chemistry 4271ndash83 2005

Copyright Taylor amp Francis Inc

ISSN 1060-1325 print1520-5738 online

DOI 101081MA-200040970

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polymers[8ndash10] The polymers having antimicrobial properties are suitable in a variety of

applications such as film packaging materials foodstuffs sanitary application and many

others[1112]

The presence of chlorine has been suggested to impart an antimicrobial property to a

compound[1314] Many acrylic polymers containing chlorine and possessing an antimicro-

bial property have been reported[1516] Recently the acrylic polymers derived from 24-

dichlorophenyl methacrylate (24-DMA) and MMA are reported from this laboratory[17]

and these are found to be antimicrobial agents It was thought appropriate to replace

MMA by styrene to form copolymers with 24-DMA and examine the antimicrobial

property so that the role of MMA in inhibiting the growth of microorganisms could be

examined

Here we report the synthesis and characterization of monomer 24-DMA as well as

homo- and copolymers of 24-DMA with styrene obtained by using different monomer

feed ratio The copolymer composition was obtained by UV-spectroscopy and

molecular weight was determined by gel permeation chromatography Thermal analyses

of polymers are also included here The homo- and copolymers have been used to

screen their antimicrobial activity against microorganisms such as bacteria (Escherichia

coli Bacillus subtilis and Staphylococcus citreus) fungi (Aspergillus niger Sporotrichum

pulverulentum and Trichoderma lignorum) and yeast (Candida utilis Saccharomyces

cerevisiae and Pichia stipitis) These organisms were chosen because of their ready

availability

Experimental

Materials

Methacryloyl chloride (Fluka) was used as received Styrene was freed from the inhibitor

by washing with 5 NaOH solution followed by distilled water and after drying over

anhydrous sodium sulfate it was distilled under vacuum 220-Azobisisobutyronitrile

(AIBN) was recrystallized from ethanol All other chemicals were of analytical grade

products obtained from Chiti Chem Baroda India and they were used without any

further purification

Synthesis of 24-Dichlorophenyl Methacrylate

Methacryloyl chloride was prepared by reacting methacrylic acid with benzoyl

chloride[18] The esterification was performed with methacryloyl chloride and 24-dichloro-

phenol (24-D)

Absolute alcohol (400mL) and NaOH (02mol 809 g) were added to a three-necked

flask equipped with stirrer condenser and thermometer and placed in a water bath and the

contents were stirred until all the NaOH dissolved and 24-D (02mol 326 g) was added

to this The reaction mixture was heated to 608C for 30min with stirring then cooled to

room temperature and then to 0ndash58C by ice Freshly prepared methacryloyl chloride

(021mol 205mL) was added to the cooled reaction mixture and stirred for 90min It

was then poured into a crushed icendashwater mixture when a cream colored product

separated out It was filtered out washed thoroughly with cold water dried at 358C in

vacuum and recrystallized from petroleum ether

J N Patel M V Patel and R M Patel72

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Copolymerization

Homo- and copolymerizations were carried out in toluene using AIBN as an initiator Pre-

determined quantities of 24-DMA styrene toluene and AIBN were mixed in a round

bottom flask equipped with mechanical stirrer and reflux condenser The reaction

mixture was heated at 708C for 5 hr with constant stirring After that it was cooled to

room temperature and slowly poured into a large excess of methanol used as a non-

solvent with constant stirring A solid polymer was purified by repeated precipitation by

methanol from solution in toluene and finally dried under vacuum

Characterization

Infrared spectra of solid samples in the KBr pellets were recorded with a NICOLET-400DFT-IR spectrophotometer A Shimadzu-160A recording UV-visible spectrophotometer

was used to determine copolymer composition and reactivity ratio Molecular weights

of the polymers were determined by gel permeation chromatography (Water 600E)

equipped with a 410-RI detectors calibrated with polystyrene standard TGA was

performed with DuPont-951 thermal analyzer at a heating rate of 108Cmin21 in static

air atmosphere A differential thermal analysis (DTA) trace was obtained with a

DuPont-9900 differential thermal analyzer at a heating rate of 108Cmin21 in nitrogen

atmosphere

Antimicrobial Activity

The homo- and copolymers thus obtained were tested against different microorganisms

which are commonly employed for biodegradability tests bacterial strains (B subtilis

E coli and S citreus) fungi (A niger S pulverulentum and T lignorum) and yeast

(C utilis S cerevisiae and P stipitis) were grown in Nutrient broth (N-broth) and Sabour-

andrsquos dextrose broth medium

Screening of Acrylic Copolymers for Antibacterial Activity A 5 (vv) inoculum of

bacterial culture was used to inoculate a 100mL solution of N-broth (control ie it

does not contain polymer) and test media (100mL solution of N-broththorn 50mg

polymer sample) and incubated on rotary shaker (200 rpm) at room temperature A

05mL liquid was withdrawn at specified time intervals (24ndash48 hr) from test-media and

after suitable dilution with 35-dinitrosalicylic acid (DNS) reagent[19] and distilled

water optical density was measured at 660 nm The analysis was carried out using a

DNS reagent of the following compositions DNS (104 g) NaOH (198 g) NaK-

tartarate (306 g) phenol (76 g) sodiummetabisulfate (83 g) distilled water (1416mL)

The activity was calculated as optical density per milliliter (ie growth) This method

is based on the principle that as growth proceeds cell number increases which lead to

increase in optical density of medium

Screening of Acrylic Copolymers for Antifungal Activity Since fungal culture shows fila-

mentous growth an optical method cannot be used to monitor the growth Gravimetric

analysis was carried out to determine the dry cell mass A 10 (vv) inoculum was

added to the sterile control medium (without polymer) and test medium (100mL

controlthorn 50mg polymer sample) Flasks were incubated at room temperature on a

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 73

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rotary shaker (200 rpm) for 48 hr Contents of the flasks were filtered using cheese cloth

and cell pellets were dried to content weight

Screening of Acrylic Copolymers on Yeast A 5 (vv) inoculum of yeast culture was

added to both sterile control medium and test medium (100mL controlthorn 50mg polymer

sample) and the same procedure as mentioned in antibacterial activity was followed

Results and Discussion

The copolymerization of 24-DMA with styrene in toluene solution was studied in a wide

composition interval with a mole fraction of 24-DMA ranging from 02 to 08 in the feed

The reaction time was selected to give conversion less than 10 wt in order to satisfy the

differential copolymerization equation

The peaks due to IR spectrum (Fig 1) of the monomer are IR (cm21) 2925 (nCH3)

1743 (nC55o) 1642 (nC55C) 1333 (nCndashO) 1232 and 1160 (nCndashOndashC) 890 (ndashCH bending

mode of vinyl group) 720 (rocking mode of vinyl group) 670 (nCndashCl) 1590 and 1488

(bands due to phenyl ring)

The proton NMR peaks (Fig 2) are 1H-NMR (ppm) (60MHz) 2080 (3H) (methyl

proton) 6416 (1H) and 5811 (1H) (non-equivalent methylene protons) 7383ndash7471

(1H) (aromatic proton) 7031ndash7236 (2H) (aromatic proton)

Figure 1 IR spectra of 24-DMA

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The spectral data agree well with the results reported for the monomer 24-DMA[20]

The IR spectra (Fig 3) confirmed the structure of copolymers A band at 2969ndash

2800 cm21 is attributed to CndashH stretching vibration of methyl and methylene group

The bands at 1380 and 1460 cm21 are assigned to the CndashH bending vibrations of

methyl and methylene groups The strong absorption at 1770 cm21 is due to C55O stretch-

ing vibration in ester group whereas the strong absorption at 1300 cm21 could be attrib-

uted to predominantly CndashO stretching The bands at 750 cm21 may have contributions

from CndashH out-of-plane bending vibration of monosubstituted aromatic ring[21] In the

copolymers as the styrene content decreases the intensity of 750 cm21 band also

decreases The band at 680 cm21 is attributed to CndashCl stretching[22] The disappearance

of the band at 1642 cm21 indicates the formation of polymers

Copolymer Composition and Reactivity Ratios

The synthesis of copolymer is presented in Fig 4 The average composition of

each copolymer sample was determined from the corresponding UV-spectrum The

assignment of the absorption in the UV-spectrum allows for the accurate determination

of the content of each kind of monomeric unit incorporated into the copolymer

chains The reactivity ratios of 24-DMA and styrene were determined by the

FinemanndashRoss (FndashR) method[23] and presented in Table 1 The value of reactivity

ratios for 24-DMA (r1) and styrene (r2) from FndashR plot is 035 and 09 respectively

When r1 and r2 values are less than 1 the system gives rise to azeotropic

Figure 2 1H-NMR spectra of 24-DMA

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 75

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polymerization at a particular composition of the monomer which is calculated using

the equation[24]

N1 frac141 r2

2 r1 r2

frac14 0133

where N1 is the mole fraction of 24-DMA in the feed

Figure 3 IR spectra of homo- and copolymers of 24-DMA with styrene

J N Patel M V Patel and R M Patel76

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When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

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Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

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Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

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All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

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Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

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Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

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18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

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polymers[8ndash10] The polymers having antimicrobial properties are suitable in a variety of

applications such as film packaging materials foodstuffs sanitary application and many

others[1112]

The presence of chlorine has been suggested to impart an antimicrobial property to a

compound[1314] Many acrylic polymers containing chlorine and possessing an antimicro-

bial property have been reported[1516] Recently the acrylic polymers derived from 24-

dichlorophenyl methacrylate (24-DMA) and MMA are reported from this laboratory[17]

and these are found to be antimicrobial agents It was thought appropriate to replace

MMA by styrene to form copolymers with 24-DMA and examine the antimicrobial

property so that the role of MMA in inhibiting the growth of microorganisms could be

examined

Here we report the synthesis and characterization of monomer 24-DMA as well as

homo- and copolymers of 24-DMA with styrene obtained by using different monomer

feed ratio The copolymer composition was obtained by UV-spectroscopy and

molecular weight was determined by gel permeation chromatography Thermal analyses

of polymers are also included here The homo- and copolymers have been used to

screen their antimicrobial activity against microorganisms such as bacteria (Escherichia

coli Bacillus subtilis and Staphylococcus citreus) fungi (Aspergillus niger Sporotrichum

pulverulentum and Trichoderma lignorum) and yeast (Candida utilis Saccharomyces

cerevisiae and Pichia stipitis) These organisms were chosen because of their ready

availability

Experimental

Materials

Methacryloyl chloride (Fluka) was used as received Styrene was freed from the inhibitor

by washing with 5 NaOH solution followed by distilled water and after drying over

anhydrous sodium sulfate it was distilled under vacuum 220-Azobisisobutyronitrile

(AIBN) was recrystallized from ethanol All other chemicals were of analytical grade

products obtained from Chiti Chem Baroda India and they were used without any

further purification

Synthesis of 24-Dichlorophenyl Methacrylate

Methacryloyl chloride was prepared by reacting methacrylic acid with benzoyl

chloride[18] The esterification was performed with methacryloyl chloride and 24-dichloro-

phenol (24-D)

Absolute alcohol (400mL) and NaOH (02mol 809 g) were added to a three-necked

flask equipped with stirrer condenser and thermometer and placed in a water bath and the

contents were stirred until all the NaOH dissolved and 24-D (02mol 326 g) was added

to this The reaction mixture was heated to 608C for 30min with stirring then cooled to

room temperature and then to 0ndash58C by ice Freshly prepared methacryloyl chloride

(021mol 205mL) was added to the cooled reaction mixture and stirred for 90min It

was then poured into a crushed icendashwater mixture when a cream colored product

separated out It was filtered out washed thoroughly with cold water dried at 358C in

vacuum and recrystallized from petroleum ether

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Copolymerization

Homo- and copolymerizations were carried out in toluene using AIBN as an initiator Pre-

determined quantities of 24-DMA styrene toluene and AIBN were mixed in a round

bottom flask equipped with mechanical stirrer and reflux condenser The reaction

mixture was heated at 708C for 5 hr with constant stirring After that it was cooled to

room temperature and slowly poured into a large excess of methanol used as a non-

solvent with constant stirring A solid polymer was purified by repeated precipitation by

methanol from solution in toluene and finally dried under vacuum

Characterization

Infrared spectra of solid samples in the KBr pellets were recorded with a NICOLET-400DFT-IR spectrophotometer A Shimadzu-160A recording UV-visible spectrophotometer

was used to determine copolymer composition and reactivity ratio Molecular weights

of the polymers were determined by gel permeation chromatography (Water 600E)

equipped with a 410-RI detectors calibrated with polystyrene standard TGA was

performed with DuPont-951 thermal analyzer at a heating rate of 108Cmin21 in static

air atmosphere A differential thermal analysis (DTA) trace was obtained with a

DuPont-9900 differential thermal analyzer at a heating rate of 108Cmin21 in nitrogen

atmosphere

Antimicrobial Activity

The homo- and copolymers thus obtained were tested against different microorganisms

which are commonly employed for biodegradability tests bacterial strains (B subtilis

E coli and S citreus) fungi (A niger S pulverulentum and T lignorum) and yeast

(C utilis S cerevisiae and P stipitis) were grown in Nutrient broth (N-broth) and Sabour-

andrsquos dextrose broth medium

Screening of Acrylic Copolymers for Antibacterial Activity A 5 (vv) inoculum of

bacterial culture was used to inoculate a 100mL solution of N-broth (control ie it

does not contain polymer) and test media (100mL solution of N-broththorn 50mg

polymer sample) and incubated on rotary shaker (200 rpm) at room temperature A

05mL liquid was withdrawn at specified time intervals (24ndash48 hr) from test-media and

after suitable dilution with 35-dinitrosalicylic acid (DNS) reagent[19] and distilled

water optical density was measured at 660 nm The analysis was carried out using a

DNS reagent of the following compositions DNS (104 g) NaOH (198 g) NaK-

tartarate (306 g) phenol (76 g) sodiummetabisulfate (83 g) distilled water (1416mL)

The activity was calculated as optical density per milliliter (ie growth) This method

is based on the principle that as growth proceeds cell number increases which lead to

increase in optical density of medium

Screening of Acrylic Copolymers for Antifungal Activity Since fungal culture shows fila-

mentous growth an optical method cannot be used to monitor the growth Gravimetric

analysis was carried out to determine the dry cell mass A 10 (vv) inoculum was

added to the sterile control medium (without polymer) and test medium (100mL

controlthorn 50mg polymer sample) Flasks were incubated at room temperature on a

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 73

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rotary shaker (200 rpm) for 48 hr Contents of the flasks were filtered using cheese cloth

and cell pellets were dried to content weight

Screening of Acrylic Copolymers on Yeast A 5 (vv) inoculum of yeast culture was

added to both sterile control medium and test medium (100mL controlthorn 50mg polymer

sample) and the same procedure as mentioned in antibacterial activity was followed

Results and Discussion

The copolymerization of 24-DMA with styrene in toluene solution was studied in a wide

composition interval with a mole fraction of 24-DMA ranging from 02 to 08 in the feed

The reaction time was selected to give conversion less than 10 wt in order to satisfy the

differential copolymerization equation

The peaks due to IR spectrum (Fig 1) of the monomer are IR (cm21) 2925 (nCH3)

1743 (nC55o) 1642 (nC55C) 1333 (nCndashO) 1232 and 1160 (nCndashOndashC) 890 (ndashCH bending

mode of vinyl group) 720 (rocking mode of vinyl group) 670 (nCndashCl) 1590 and 1488

(bands due to phenyl ring)

The proton NMR peaks (Fig 2) are 1H-NMR (ppm) (60MHz) 2080 (3H) (methyl

proton) 6416 (1H) and 5811 (1H) (non-equivalent methylene protons) 7383ndash7471

(1H) (aromatic proton) 7031ndash7236 (2H) (aromatic proton)

Figure 1 IR spectra of 24-DMA

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The spectral data agree well with the results reported for the monomer 24-DMA[20]

The IR spectra (Fig 3) confirmed the structure of copolymers A band at 2969ndash

2800 cm21 is attributed to CndashH stretching vibration of methyl and methylene group

The bands at 1380 and 1460 cm21 are assigned to the CndashH bending vibrations of

methyl and methylene groups The strong absorption at 1770 cm21 is due to C55O stretch-

ing vibration in ester group whereas the strong absorption at 1300 cm21 could be attrib-

uted to predominantly CndashO stretching The bands at 750 cm21 may have contributions

from CndashH out-of-plane bending vibration of monosubstituted aromatic ring[21] In the

copolymers as the styrene content decreases the intensity of 750 cm21 band also

decreases The band at 680 cm21 is attributed to CndashCl stretching[22] The disappearance

of the band at 1642 cm21 indicates the formation of polymers

Copolymer Composition and Reactivity Ratios

The synthesis of copolymer is presented in Fig 4 The average composition of

each copolymer sample was determined from the corresponding UV-spectrum The

assignment of the absorption in the UV-spectrum allows for the accurate determination

of the content of each kind of monomeric unit incorporated into the copolymer

chains The reactivity ratios of 24-DMA and styrene were determined by the

FinemanndashRoss (FndashR) method[23] and presented in Table 1 The value of reactivity

ratios for 24-DMA (r1) and styrene (r2) from FndashR plot is 035 and 09 respectively

When r1 and r2 values are less than 1 the system gives rise to azeotropic

Figure 2 1H-NMR spectra of 24-DMA

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 75

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polymerization at a particular composition of the monomer which is calculated using

the equation[24]

N1 frac141 r2

2 r1 r2

frac14 0133

where N1 is the mole fraction of 24-DMA in the feed

Figure 3 IR spectra of homo- and copolymers of 24-DMA with styrene

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When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

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Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

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Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

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All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

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Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

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Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

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18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

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embe

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Copolymerization

Homo- and copolymerizations were carried out in toluene using AIBN as an initiator Pre-

determined quantities of 24-DMA styrene toluene and AIBN were mixed in a round

bottom flask equipped with mechanical stirrer and reflux condenser The reaction

mixture was heated at 708C for 5 hr with constant stirring After that it was cooled to

room temperature and slowly poured into a large excess of methanol used as a non-

solvent with constant stirring A solid polymer was purified by repeated precipitation by

methanol from solution in toluene and finally dried under vacuum

Characterization

Infrared spectra of solid samples in the KBr pellets were recorded with a NICOLET-400DFT-IR spectrophotometer A Shimadzu-160A recording UV-visible spectrophotometer

was used to determine copolymer composition and reactivity ratio Molecular weights

of the polymers were determined by gel permeation chromatography (Water 600E)

equipped with a 410-RI detectors calibrated with polystyrene standard TGA was

performed with DuPont-951 thermal analyzer at a heating rate of 108Cmin21 in static

air atmosphere A differential thermal analysis (DTA) trace was obtained with a

DuPont-9900 differential thermal analyzer at a heating rate of 108Cmin21 in nitrogen

atmosphere

Antimicrobial Activity

The homo- and copolymers thus obtained were tested against different microorganisms

which are commonly employed for biodegradability tests bacterial strains (B subtilis

E coli and S citreus) fungi (A niger S pulverulentum and T lignorum) and yeast

(C utilis S cerevisiae and P stipitis) were grown in Nutrient broth (N-broth) and Sabour-

andrsquos dextrose broth medium

Screening of Acrylic Copolymers for Antibacterial Activity A 5 (vv) inoculum of

bacterial culture was used to inoculate a 100mL solution of N-broth (control ie it

does not contain polymer) and test media (100mL solution of N-broththorn 50mg

polymer sample) and incubated on rotary shaker (200 rpm) at room temperature A

05mL liquid was withdrawn at specified time intervals (24ndash48 hr) from test-media and

after suitable dilution with 35-dinitrosalicylic acid (DNS) reagent[19] and distilled

water optical density was measured at 660 nm The analysis was carried out using a

DNS reagent of the following compositions DNS (104 g) NaOH (198 g) NaK-

tartarate (306 g) phenol (76 g) sodiummetabisulfate (83 g) distilled water (1416mL)

The activity was calculated as optical density per milliliter (ie growth) This method

is based on the principle that as growth proceeds cell number increases which lead to

increase in optical density of medium

Screening of Acrylic Copolymers for Antifungal Activity Since fungal culture shows fila-

mentous growth an optical method cannot be used to monitor the growth Gravimetric

analysis was carried out to determine the dry cell mass A 10 (vv) inoculum was

added to the sterile control medium (without polymer) and test medium (100mL

controlthorn 50mg polymer sample) Flasks were incubated at room temperature on a

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 73

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rotary shaker (200 rpm) for 48 hr Contents of the flasks were filtered using cheese cloth

and cell pellets were dried to content weight

Screening of Acrylic Copolymers on Yeast A 5 (vv) inoculum of yeast culture was

added to both sterile control medium and test medium (100mL controlthorn 50mg polymer

sample) and the same procedure as mentioned in antibacterial activity was followed

Results and Discussion

The copolymerization of 24-DMA with styrene in toluene solution was studied in a wide

composition interval with a mole fraction of 24-DMA ranging from 02 to 08 in the feed

The reaction time was selected to give conversion less than 10 wt in order to satisfy the

differential copolymerization equation

The peaks due to IR spectrum (Fig 1) of the monomer are IR (cm21) 2925 (nCH3)

1743 (nC55o) 1642 (nC55C) 1333 (nCndashO) 1232 and 1160 (nCndashOndashC) 890 (ndashCH bending

mode of vinyl group) 720 (rocking mode of vinyl group) 670 (nCndashCl) 1590 and 1488

(bands due to phenyl ring)

The proton NMR peaks (Fig 2) are 1H-NMR (ppm) (60MHz) 2080 (3H) (methyl

proton) 6416 (1H) and 5811 (1H) (non-equivalent methylene protons) 7383ndash7471

(1H) (aromatic proton) 7031ndash7236 (2H) (aromatic proton)

Figure 1 IR spectra of 24-DMA

J N Patel M V Patel and R M Patel74

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The spectral data agree well with the results reported for the monomer 24-DMA[20]

The IR spectra (Fig 3) confirmed the structure of copolymers A band at 2969ndash

2800 cm21 is attributed to CndashH stretching vibration of methyl and methylene group

The bands at 1380 and 1460 cm21 are assigned to the CndashH bending vibrations of

methyl and methylene groups The strong absorption at 1770 cm21 is due to C55O stretch-

ing vibration in ester group whereas the strong absorption at 1300 cm21 could be attrib-

uted to predominantly CndashO stretching The bands at 750 cm21 may have contributions

from CndashH out-of-plane bending vibration of monosubstituted aromatic ring[21] In the

copolymers as the styrene content decreases the intensity of 750 cm21 band also

decreases The band at 680 cm21 is attributed to CndashCl stretching[22] The disappearance

of the band at 1642 cm21 indicates the formation of polymers

Copolymer Composition and Reactivity Ratios

The synthesis of copolymer is presented in Fig 4 The average composition of

each copolymer sample was determined from the corresponding UV-spectrum The

assignment of the absorption in the UV-spectrum allows for the accurate determination

of the content of each kind of monomeric unit incorporated into the copolymer

chains The reactivity ratios of 24-DMA and styrene were determined by the

FinemanndashRoss (FndashR) method[23] and presented in Table 1 The value of reactivity

ratios for 24-DMA (r1) and styrene (r2) from FndashR plot is 035 and 09 respectively

When r1 and r2 values are less than 1 the system gives rise to azeotropic

Figure 2 1H-NMR spectra of 24-DMA

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 75

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polymerization at a particular composition of the monomer which is calculated using

the equation[24]

N1 frac141 r2

2 r1 r2

frac14 0133

where N1 is the mole fraction of 24-DMA in the feed

Figure 3 IR spectra of homo- and copolymers of 24-DMA with styrene

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When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

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Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

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Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

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All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

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Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

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Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

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18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

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rotary shaker (200 rpm) for 48 hr Contents of the flasks were filtered using cheese cloth

and cell pellets were dried to content weight

Screening of Acrylic Copolymers on Yeast A 5 (vv) inoculum of yeast culture was

added to both sterile control medium and test medium (100mL controlthorn 50mg polymer

sample) and the same procedure as mentioned in antibacterial activity was followed

Results and Discussion

The copolymerization of 24-DMA with styrene in toluene solution was studied in a wide

composition interval with a mole fraction of 24-DMA ranging from 02 to 08 in the feed

The reaction time was selected to give conversion less than 10 wt in order to satisfy the

differential copolymerization equation

The peaks due to IR spectrum (Fig 1) of the monomer are IR (cm21) 2925 (nCH3)

1743 (nC55o) 1642 (nC55C) 1333 (nCndashO) 1232 and 1160 (nCndashOndashC) 890 (ndashCH bending

mode of vinyl group) 720 (rocking mode of vinyl group) 670 (nCndashCl) 1590 and 1488

(bands due to phenyl ring)

The proton NMR peaks (Fig 2) are 1H-NMR (ppm) (60MHz) 2080 (3H) (methyl

proton) 6416 (1H) and 5811 (1H) (non-equivalent methylene protons) 7383ndash7471

(1H) (aromatic proton) 7031ndash7236 (2H) (aromatic proton)

Figure 1 IR spectra of 24-DMA

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The spectral data agree well with the results reported for the monomer 24-DMA[20]

The IR spectra (Fig 3) confirmed the structure of copolymers A band at 2969ndash

2800 cm21 is attributed to CndashH stretching vibration of methyl and methylene group

The bands at 1380 and 1460 cm21 are assigned to the CndashH bending vibrations of

methyl and methylene groups The strong absorption at 1770 cm21 is due to C55O stretch-

ing vibration in ester group whereas the strong absorption at 1300 cm21 could be attrib-

uted to predominantly CndashO stretching The bands at 750 cm21 may have contributions

from CndashH out-of-plane bending vibration of monosubstituted aromatic ring[21] In the

copolymers as the styrene content decreases the intensity of 750 cm21 band also

decreases The band at 680 cm21 is attributed to CndashCl stretching[22] The disappearance

of the band at 1642 cm21 indicates the formation of polymers

Copolymer Composition and Reactivity Ratios

The synthesis of copolymer is presented in Fig 4 The average composition of

each copolymer sample was determined from the corresponding UV-spectrum The

assignment of the absorption in the UV-spectrum allows for the accurate determination

of the content of each kind of monomeric unit incorporated into the copolymer

chains The reactivity ratios of 24-DMA and styrene were determined by the

FinemanndashRoss (FndashR) method[23] and presented in Table 1 The value of reactivity

ratios for 24-DMA (r1) and styrene (r2) from FndashR plot is 035 and 09 respectively

When r1 and r2 values are less than 1 the system gives rise to azeotropic

Figure 2 1H-NMR spectra of 24-DMA

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 75

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polymerization at a particular composition of the monomer which is calculated using

the equation[24]

N1 frac141 r2

2 r1 r2

frac14 0133

where N1 is the mole fraction of 24-DMA in the feed

Figure 3 IR spectra of homo- and copolymers of 24-DMA with styrene

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When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

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Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

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Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

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All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

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Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

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ical

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14

Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

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ded

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ical

Uni

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ity]

at 0

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22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

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The spectral data agree well with the results reported for the monomer 24-DMA[20]

The IR spectra (Fig 3) confirmed the structure of copolymers A band at 2969ndash

2800 cm21 is attributed to CndashH stretching vibration of methyl and methylene group

The bands at 1380 and 1460 cm21 are assigned to the CndashH bending vibrations of

methyl and methylene groups The strong absorption at 1770 cm21 is due to C55O stretch-

ing vibration in ester group whereas the strong absorption at 1300 cm21 could be attrib-

uted to predominantly CndashO stretching The bands at 750 cm21 may have contributions

from CndashH out-of-plane bending vibration of monosubstituted aromatic ring[21] In the

copolymers as the styrene content decreases the intensity of 750 cm21 band also

decreases The band at 680 cm21 is attributed to CndashCl stretching[22] The disappearance

of the band at 1642 cm21 indicates the formation of polymers

Copolymer Composition and Reactivity Ratios

The synthesis of copolymer is presented in Fig 4 The average composition of

each copolymer sample was determined from the corresponding UV-spectrum The

assignment of the absorption in the UV-spectrum allows for the accurate determination

of the content of each kind of monomeric unit incorporated into the copolymer

chains The reactivity ratios of 24-DMA and styrene were determined by the

FinemanndashRoss (FndashR) method[23] and presented in Table 1 The value of reactivity

ratios for 24-DMA (r1) and styrene (r2) from FndashR plot is 035 and 09 respectively

When r1 and r2 values are less than 1 the system gives rise to azeotropic

Figure 2 1H-NMR spectra of 24-DMA

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 75

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polymerization at a particular composition of the monomer which is calculated using

the equation[24]

N1 frac141 r2

2 r1 r2

frac14 0133

where N1 is the mole fraction of 24-DMA in the feed

Figure 3 IR spectra of homo- and copolymers of 24-DMA with styrene

J N Patel M V Patel and R M Patel76

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When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

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Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

J N Patel M V Patel and R M Patel78

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Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

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All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

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Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

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ical

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503

22

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Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

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ical

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ity]

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22

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r 20

14

polymerization at a particular composition of the monomer which is calculated using

the equation[24]

N1 frac141 r2

2 r1 r2

frac14 0133

where N1 is the mole fraction of 24-DMA in the feed

Figure 3 IR spectra of homo- and copolymers of 24-DMA with styrene

J N Patel M V Patel and R M Patel76

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When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

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Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

J N Patel M V Patel and R M Patel78

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Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

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All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

J N Patel M V Patel and R M Patel80

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

When the mole fraction of the monomer 24-DMA in the feed is 0133 the copolymer

formed will have the same composition as that of the feed When the mole fraction of the

feed is less than 0133 with respect to 24-DMA the copolymer is relatively richer in this

monomeric unit than the feed When the mole fraction of the monomeric 24-DMA in the

feed is above 0133 the copolymer is relatively richer in the styrene monomeric unit

Molecular Weights and Viscosity Measurement

The number average and weight average molecular weights (Mw Mn) and the polydisper-

sity index of homopolymers as well as copolymer samples were determined by gel per-

meation chromatography The values of number average and weight average molecular

weights range from 4612 to 5739 and 10046 to 29126 respectively The polydispersity

index of homo- and copolymers varies in the range of 217ndash277 Intrinsic viscosity lies in

the range 0012ndash0018 dL g21 (Table 2)

Figure 4 Reaction scheme of poly(24-DMA-co-styrene)

Table 1Copolymer compositions data and reactivity ratios of copolymers of 24-DMA and

styrene

Sample

code

no

Monomer feed

compositions

Conversion

()

Composition of

24-DMA in the

copolymer [m1]

Reactivity

ratio

24-DMA

[M1] (mol)

Styrene

[M2] (mol) r1 r2

S-1 10 mdash mdash mdash

S-2 02 08 86 0168

S-3 04 06 91 0375

S-4 05 05 94 0414 035 090

S-5 06 04 89 0560

S-6 08 02 90 0758

S-7 mdash 10 mdash mdash

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 77

Dow

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ded

by [

Ein

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en T

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ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

J N Patel M V Patel and R M Patel78

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

Dow

nloa

ded

by [

Ein

dhov

en T

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ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

J N Patel M V Patel and R M Patel80

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Thermal Analysis

Thermogravimetric Analysis The results of TGA analysis of homo- and copolymers are

presented in Table 3 The data clearly indicate that all polymers undergo single step

decomposition in the temperature range of 190ndash5508C Activation energy (EA) and

integral procedural decomposition temperature (IPDT) were determined by Broidorsquos

method[25] and Doylersquos method[26] respectively

Differential Thermal Analysis The DTA data of homo- and copolymers are presented in

Table 4 The activation energy for thermal degradation and reaction order were obtained

by Reichrsquos method[27] The activation energy for thermal degradation of polymers ranges

from 139 to 171 kJmol21

Table 2Average molecular weights by GPC data for the copolymers of 24-DMA and styrene

Sample

code no Mn Mw

Polydispersity

(MwMn)

Intrinsic viscosity

[h] (dL g21)

S-1 5493 19800 360 0018

S-2 4781 13905 290 0015

S-3 5197 21613 415 0016

S-4 5082 22861 449 0012

S-5 5739 29126 507 0013

S-6 5021 25033 498 0015

S-7 4612 10046 217 0016

Table 3

TGA data for homo- and copolymers of 24-DMA and styrene

Sample

code

no

Weight loss at var-

ious temperature (8C) Decomposition

temperature

range (8C)Tmax

a

(8C)T50

b

(8C)IPDTc

(8C)

Activation

energyd

(EA)

(kJmol21)250 350 450 550

S-1 40 680 910 999 190ndash470 360 345 370 170

S-2 10 240 850 990 300ndash550 372 365 373 139

S-3 30 180 820 970 275ndash550 415 390 368 155

S-4 30 280 880 980 287ndash550 365 370 370 160

S-5 20 160 850 980 285ndash550 405 375 365 162

S-6 20 250 850 970 295ndash550 410 380 380 148

S-7 20 340 950 980 247ndash500 366 355 345 147

aTemperature for maximum rate of decompositionbTemperature for 50 wt losscIntegral procedural decomposition temperaturedBy Broidorsquos method

J N Patel M V Patel and R M Patel78

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

J N Patel M V Patel and R M Patel80

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Antimicrobial Activity

Antimicrobial activity of poly(24ndashDMA) poly(styrene) and poly(24-DMA-co-styrene)

on bacteria fungi and yeast are shown in Figs 5 6 and 7 respectively It has been

suggested that presence of chlorine is important for polymers to possess antimicrobial

property This has been found to be so in our recent work on copolymers of 24-DMA

with MMA[17] The activity was found to increase with increasing concentration of

chlorine in the polymer The growth of microorganisms in poly(24-DMA-co-styrene)

and poly(24-DMA-co-MMA) is compared in Table 5 Interestingly the poly(MMA)

registers higher growth of microorganism than that in poly(styrene) The copolymers of

styrene with 24-DMA consequently are better inhibitor than copolymers of MMA

Table 4DTA data for homo- and copolymers of 24-DMA and styrene

Sample

code no T1a(8C) T2

b(8C) TPc(8C)

Activation energyd

(EA) (kJmol21)

Reaction

order

S-1 338 494 414 171 1

S-2 352 526 380 158 1

S-3 353 528 420 139 1

S-4 356 529 479 167 1

S-5 341 510 463 155 1

S-6 326 491 455 145 1

S-7 318 482 404 150 1

aStarting temperature of DTAbEnding temperature of DTA tracecPeak maxima temperature of DTA tracedActivation energy by Reichrsquos method

Figure 5 Effect of homo- and copolymers on percentage growth of bacteria

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 79

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

J N Patel M V Patel and R M Patel80

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

All the copolymers systems showed almost similar antimicrobial properties against

bacteria fungi and yeast Poly(24-DMA) allowed almost 18ndash24 growth of bacteria

26ndash33 growth of fungi and 17ndash22 growth of yeast Replacement of 24-DMA by

styrene reduces the antimicrobial property of the polymer It is thus apparent that

lowering of chlorine content reduces the antimicrobial activity

The higher antimicrobial activity of the copolymer when MMA is replaced by styrene

may be traced to the presence of aromatic ring However these need further confirmation

Figure 6 Effect of homo- and copolymers on percentage growth of fungi

Figure 7 Effect of homo- and copolymers on percentage growth of yeast

J N Patel M V Patel and R M Patel80

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Table

5

Comparisonofantimicrobialactivityofcopolymer

ofpoly(24-D

MA-co-styrene)

andpoly(24-D

MA-co-M

MA)

Types

of

microorganisms

Growth

ofmicroorganismsin

copolymerswithstyrene

Growth

ofmicroorganismsin

copolymerswith

MMA

S-1

poly

(24-D

MA)

S-2

80

styrene

S-3

60

styrene

S-4

50

styrene

S-5

40

styrene

S-6

20

styrene

Poly

(styrene)

M-2

80

MMA

M-3

60

MMA

M-4

50

MMA

M-5

40

MMA

M-6

20

MMA

Poly

(MMA)

Bacteria

(i)Bsubtilis

24

38

35

33

32

29

82

46

43

40

38

32

95

(ii)Ecoli

19

29

27

25

22

20

76

41

37

33

31

27

90

(iii)Scitreus

21

31

29

27

24

22

79

43

40

37

32

30

91

Fungi

(i)Aniger

29

43

42

40

38

36

84

46

43

41

39

37

97

(ii)Spulverulentum

26

39

37

36

34

30

81

42

38

37

35

32

97

(iii)Tlignorum

32

45

43

42

40

39

88

51

44

44

42

41

99

Yeast (i)Cutilis

23

62

57

56

55

52

84

68

64

61

60

59

89

(ii)Scerevisiae

17

55

52

49

48

45

73

61

57

54

53

51

83

(iii)Pstipitis

20

57

54

53

50

49

77

63

60

55

54

54

84

81

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

Conclusion

The antimicrobial activity of the homo- and copolymers of 24-DMA with styrene was

studied The poly(24-DMA) was found to be excellent in inhibiting the growth of micro-

organisms This may be traced to the high chlorine content of the homopolymer As the

percentage of styrene in the copolymers increases the effectiveness of the copolymers

to inhibit the growth of the microorganisms decreases As expected poly(styrene) is

least effective in inhibiting the growth of microorganisms Although the chlorine

content of the polymers appears to be the most important component to impart antimicro-

bial properties other factors also need to be investigated

References

1 Tirrell DA Tirrell MH Bikales NM Overberger CG Menges G Encyclopedia of

Polymers Sciences and Engineering John Wiley amp Sons New York 1985 Vol 4 192

2 Zutty NL Faucher JA The stiffness of ethylene copolymers J Polym Sci 1962 60 (169)

s36ndashs37

3 Ibrahim E Cengiz S Synthesis characterization and polymerization of new methacrylate

esters having pendant amine moieties J Macromol Sci Pure Appl Chem 2002 39 (5)

405ndash417

4 Ibrahim E Zulfiye I Mehmet C Misir A Synthesis and characterization of two new aryl

cyclobutyl ketoethyl methacrylate monomers and their polymer J Polym Sci Part A

Polym Chem 2001 39 (23) 4167ndash4173

5 Cengiz S Ibrahim E Synthesis spectral and thermal properties of homo- and copolymers of

2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacry-

late and determination of monomer reactivity ratios Eur Polym J 2003 39 2261ndash2270

6 Williams DF Fundamental Aspects of Biocompatibility CRC Press Boca Raton FL 1981

7 Odian G Principles of Polymerization 3rd Ed Wiley-Interscience New York 1991

198ndash334

8 Chang TC Shen WS Chiu YS Ho SY Thermo-oxidative degradation of phosphorus

containing polyurethane Polym Degrad Stab 1995 49 (3) 353ndash360

9 Chang TC Wu KH Chen HB Ho SY Chiu YS Thermal degradation of aged polyte-

trahydrofuran and its copolymers with 3-azidomethyl-30-methyloxetane and 3-nitratomethyl-30-

methyloxetane by thermogravimetry J Polym Sci Polym Chem 1996 34 (16) 3337ndash3343

10 Chang TC Chen HB Ho SY Chiu YS Degradation of polydimethylsiloxane-block-

polystyrene copolymer Polym Degrad Stab 1997 57 (1) 7ndash14

11 Schroeder JD Scales JC Anti-microbial Packaging Polymer and its Method of Use US

Patent 5174 2002cf (Chem Abst 2002 136 (22) 345880k)

12 Edeole Y Barbin JY Antimicrobial Methacrylic Polymer Material and Shaped Articles

Obtained from Same PCT Int Appl WO 0232989 2002cf (Chem Abst 2002 136 (22)

341547j)

13 Lein EJ Hansch C Anderson SM Structurendashactivity correlation for antibacterial agents on

gram-positive and gram-negative cells J Med Chem 1968 11 (3) 430ndash441

14 Kulkarni VM Bothara KG Drug Design 1st Ed Nirali Prakashan Pune 1995 212

15 Oh ST Yoo H Chang S Byung K Ha CS Cho WJ Synthesis and biocidal activity of

polymeric bactericides Pollimo 1994 18 (2) 276ndash281

16 Oh ST Yoo H Chang S Cho WJ Synthesis and biocidal activity of polymer III Bacteri-

cidal activity of homopolymer of AcDP and copolymer of AcDP with styrene J Appl Polym

Sci 1994 54 859ndash866

17 Patel MV Patel SA Ray A Patel RM Antimicrobial activity on the copolymers of 24-

dichlorophenyl methacrylate with methyl methacrylate synthesis and characterization

J Polym Sci Part-A Polym Chem in press

J N Patel M V Patel and R M Patel82

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14

18 Stemped GH Cross RP Morewell RP The preparation of acryloyl chloride J Am Chem

Soc 1950 72 (5) 2299ndash2300

19 Miller GL Use of dinitro salicylic acid reagent for determination of reducing sugar Anal

Chem 1959 31 426ndash428

20 Patel MB Patel DA Ray A Patel RM Microbial screening of copolymers of 24-dichloro-

phenyl methacrylate with N-vinylpyrrolidone synthesis and characterization Polym Int 2003

52 367ndash372

21 Colthup NB Daly LH Wiberley SE Introduction to Infrared Spectroscopy Academics

Press New York 1990

22 Bellamy LJ Infrared Spectra of Complex Molecules Chapman-Hall London 1975

23 Fineman M Ross SD Linear method for determining monomer reactivity ratios in copoly-

merization J Polym Sci 1950 5 (2) 259ndash265

24 Gowariker VR Viswanathan NV Sreedhar J Polymer Science 1st Ed New Age Inter-

national (p) Limited New Delhi 1986 204

25 Broido A A simple sensitive graphical method of treating thermogravimetric analysis data

J Polym Sci A-2 1969 7 1761ndash1774

26 Doyle CD Estimating thermal stability of experimental polymers by empirical thermogravi-

metric analysis Anal Chem 1961 33 (1) 77ndash79

27 Reich L Estimation of kinetic parameters from a DTA thermograms Die Makromol Chem

1969 123 42ndash45

Copolymers of 24-Dichlorophenyl Methacrylate with Styrene 83

Dow

nloa

ded

by [

Ein

dhov

en T

echn

ical

Uni

vers

ity]

at 0

503

22

Nov

embe

r 20

14