copolymers of 2,4‐dichlorophenyl methacrylate with styrene: synthesis, thermal properties, and...
TRANSCRIPT
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
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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
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
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
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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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
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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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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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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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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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ded
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ical
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at 0
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22
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embe
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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
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
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
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ical
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ity]
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503
22
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embe
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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ded
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embe
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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
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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
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
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ity]
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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
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Ein
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ity]
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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
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ity]
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22
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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
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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
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ded
by [
Ein
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Uni
vers
ity]
at 0
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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
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ity]
at 0
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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
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ical
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ity]
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embe
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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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ded
by [
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ical
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ity]
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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
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