functionalmodificationeffectofepoxyoligomersonthe ... · 2019. 7. 30. · intermolecular...

Research ArticleFunctional Modification Effect of Epoxy Oligomers on theStructure and Properties of Epoxy Hydroxyurethane Polymers

Victor Stroganov1 Oleg Stoyanov2 Ilya Stroganov2 and Eduard Kraus 3

1Kazan State University of Architecture and Engineering Zelenaya 1 420043 Kazan Russia2Kazan National Research Technology University Karl Marx 68 420015 Kazan Russia3SKZ-German Plastic Center Friedrich-Bergius-Ring 22 97076 Wuerzburg Germany

Correspondence should be addressed to Eduard Kraus ekrausskzde

Received 15 March 2018 Revised 9 May 2018 Accepted 5 June 2018 Published 9 August 2018

Academic Editor Ana Marıa Dıez-Pascual

Copyright copy 2018 Victor Stroganov et al is is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited

We introduce different ways to solve the actual fragility problem of the epoxy-amine polymers by curing epoxidian oligomers withaliphatic amines without additional heat input e pathways are the oligomer-oligomeric modification of epoxy resins-epoxyoligomers (EO) with their conversion to oligoethercyclocarbonates (OECC) by carbonization with carbon dioxide e cocuringof these oligomers as a result of aminolysis competing reactions is ldquoepoxide-aminerdquo (forming a network polymer) andldquocyclocarbonate-aminerdquo (forming the linear hydroxyurethane extending the internodal chains) Formation of internal andintermolecular hydrogen bonds was established on hydroxycarbonates (HA) and linear polyhydroxyurethanes (PHU) modelcompounds by IR and NMR spectroscopye results of the hydrogen bond system formation processes explain the change in therelaxation and physicomechanical properties of hard polymers modified by the epoxy-amine compositions (OECC) containingaromatic and aliphatic links is paper presents a possible OECC modificator the optimal EOOECC ratio and its influence onthe cross-link frequency the polarity the fragment and chain flexibilities and as a consequence the possible stiffness regulationfor selected epoxy polymers us the causes of the increase in deformation-strength and adhesion characteristics wereestablished by a factor of 15 to 30 due to an increase in cohesive strength (as a result of the combined network operation withcovalent and physical bonds) as well as reduction of residual stresses (by adding the aliphatic fragments as additional relaxants)and reducing the defectiveness of the boundary layers (polymer-substrate)

1 Introduction

Materials based on epoxy oligomers such as epoxy polymersand composites with epoxy polymeric matrix possessa unique complex of valuable technological and operationalproperties Characteristics like high adhesion to most ma-terials low shrinkage during curing high strength low creepunder load good chemical biological stability and electricalinsulation ensure their successful and effective use in variousapplications and industries e production developmentand the use of epoxy-based compositions and materialsexpand very fast e new types of resin-oligomers hard-eners active diluents and compositions are emerging esetrends are undoubtedly associated with increasing interest inthe physicochemistry of epoxy polymers their structural

organization and connection with properties which is re-flected in monographic literature and reviews published incollections and journals Accordingly the need for devel-opment of new composite materials is also very high Rel-evant in this context are the novel possibilities of modifyingepoxy polymers [1ndash9]

2 Theory

A feature of highmolecular substances is their diverse natureand complex structure which can not be described in oneway Conventionally four interrelated structural levels canbe distinguished molecular topological supramolecularand dispersive colloidal [10ndash18] e main reason for thisinterrelation is the influence of the chemical structure of grid

HindawiAdvances in Materials Science and EngineeringVolume 2018 Article ID 6743037 16 pageshttpsdoiorg10115520186743037

fragments (atoms and atomic groups) on the realizingpossibility for each known type of the intermolecular in-teractions (physical bonds grid) In the chemical structure ofpolymers the elemental composition of structural units thetype and position of functional groups and the congura-tion and conformation of polymer chains characterize theirmolecular level

e topological structure characterizes the cohesion andbranching in a reticular polymer which can be representedas a macroscopic molecule combining a system of cyclicstructures with a system of dierent internode chains dis-tributed throughout the volume Such a molecule can berepresented as an innite graph [16] Within the frameworkof this representations the concept of nodes (cs) chains (nc)or the average static mass of the chain interstitial segment(Mc) is the main characteristics of the topological struc-ture under the assumption of ideal networks (tetrahedralcubic etc) e presence of topological defects (grid ir-regularity chain ineshyciency closed loops and unbound solfraction) is a characteristic dierence of real structures inreticular polymers from ideal ones It has been shown thatfor epoxy-amine polymers the main types of chemicaldefects are ldquofree endsrdquo and topological ones are chemicalassemblies that have dierent connectivity with the wiremesh [19] e abovementioned topological elements of thestructure (IndashV) can be conditionally classied 3- and 4-related nodes (I II) forming a grid 2-connected nodes (III)of linear fragments 1-bound (IV) nodes of free ends andsol-fraction connections (V) ese defects cause a decreaseof degree of conversion for the reactive groups to the valuesof αtoplim 92ndash93 (topological limit) at theoretical limitvalues αtheorlim 97-98 for three-dimensional grid models Itis generally accepted that these characteristics determine thebasic properties of network polymers [3 20 21]

e supramolecular structure is determined by the na-ture of intermolecular interactions of chemical structuralelements lateral active chains and the degree of ordering intheir mutual arrangement e nature of the intermolecularinteraction in epoxy polymers is determined by the presenceof polar atoms groupings and their interaction in the to-pological grid fragments (IndashIV) e following types ofintermolecular interactions are distinguished in polymers[22] dispersion inductive dipole and hydrogen bondsese named interactions form a labile spatial grid (witha stable network of covalent bonds) In particular in denselycross-linked epoxy polymers the physical grid of hydrogenbonds exceeds the concentration of chemical assemblies by2ndash4 times reaching densities up to 4times1021 1cm3 [23 24]e role of the hydrogen bond between the oxygen atoms ofthe oxirane ring and the hydrogen for hydrogen bonding ofthe hydroxyl group during the aminolysis of epoxy com-pounds has been considered in a number of works eresults of calculating the distribution of hydrogen-bondedgroups and the types of H-bonds are considered in detail in[25] Based on the literature data the authors believe that thedening inuence on the topological structure formation ofthe network polymers has the formation of an intra-molecular hydrogen bond between the epoxy and hydroxylgroups of the following type [26]

CH2 CH2 CH2

CHCHO

CHOH

O

O

RR N (1)

Formation of an intracellular bond system with hy-drogen bonds leads to the strengthening and ordering thespatial network of cured epoxy oligomers [27] Pochan et al[28] associate relatively high values of crystallizationtemperature Tc and destructive loading of polymers withintermolecular hydrogen bonds formed by hydroxylgroups

C

CC

O

OHH

(2)

Despite the contradictory nature of these researchers theprevailing view is that the inuence of intermolecular in-teractions is multifacetedis approach explains and causeswide possibilities for modifying the properties of epoxy-amine network polymers also due to covalent and physicalbonds

e presented data make possible the representation ofthe epoxy polymer structure as a superposition of two gridsa covalent bonds network characterized by inhomogeneity atthe molecular and topological levels and a thermouctuationphysical bonds grid caused by the realization of all possibletypes of intermolecular interactions groups and grid fragmentatoms e presented model assumes the possibility of reg-ulating the molecular mobility of network polymers due toa change in the chemical structure (the nature of the nodeinternodal fragments and their kinetic exibility polarity ofgroups etc) Numerous studies on the eect of the chemicalstructure and properties of epoxy polymers show thatchanging the initial oligomers nature hardeners and theirratio can aect the structure and physicomechanical prop-erties of epoxy polymers and materials based on them

By analyzing the properties of epoxy polymeric materialcomplexes the ldquobrittlenessrdquo of epoxide-amine polymersobtained with amine curing without additional heat input(such compositions are often used in practice in varioustechnologies) should be noted as a considerable disadvan-tage is drawback is due to an inhibition of the aminolysisreaction a decrease in the degree of reactive group con-version αtoplim and as a result a signicant reduction in thelevel of cohesive (σc εc) and adhesive strength (σa τa) It isknown that aliphatic chains increase the exibility of denselycross-linked epoxy-amine polymers eir conformationalset and kinetic exibility are practically independent fromlocation of these chains (eg in the oligomer molecule inthe linear polymer chain or in the mesh polymer) isprovision is very important since it indicates the funda-mental inuence of the initial molecule structure of oligo-mers and hardeners on the cured polymer propertiesAmong the main factors regulating the molecular level of thestructure the reactivity of the initial components (thepresence of functional groups in the oligomer the hardener

2 Advances in Materials Science and Engineering

and their potential activity in various types of reactions) thetemperature-time regimes for process realization themechanisms of polyreactions themselves (polymerizationpolycondensation and polyaddition) and so on were pre-sented [29]

Proceeding from the theoretical propositions above tosolve the epoxy-amine polymersrsquo ldquostinessrdquo problems fol-lowing purposes of this article have been formulated

(i) e analysis of theoretical bases for the formation ofepoxy-amine polymer networks

(ii) e process study of epoxy oligomers functionalmodication with dierent chemical structures andtheir carbonization into cyclic carbonates

(iii) e properties of epoxy hydroxyurethane polymersformed as a result of the competition of aminolysisoligomers reactions (EO and OECC) at their si-multaneously curing

It can be assumed that a partial change in the networkstructure of epoxy-amine polymers (due to the introductionof linear hydroxyurethane fragments obtained on the basis ofOETC with dierent structures containing highly polarhydroxyurethane groups) will provide the opportunity toregulate intermolecular interactions (a physical bonds net-work) and the molecular mobility of modied polymers invitreous and elastomeric states Such a functional modica-tion will make it possible to purposefully apply the relaxationand physicomechanical properties of epoxy-amine polymersand understand the reasons for their ldquorigidityrdquo

3 Materials and Methods

31 Materials e epoxy oligomer ED-20 was used in thecompositions studied ED-20 contains 215 epoxy withmolecular weight 400 to 450 gmol and oligomerizationdegree n 02 Following OECC modiers containingfragments diering in structural rigidity have been usedaromatic (based on ED-20) aliphatic with methyl chlor-omethyl and cyclic fragments in the side chain and anamine hardener the diethylenetriamine (DETA) OECCwere obtained by the interaction of various epoxy oligomerswith CO2 e structure can be represented by the followinggeneral formula

O-CH-CH2-O (R-O-CH2-CH-CH2-O)nR-O-CH2-CH-O

CH2-OOHO-CH2

O=C C=O

(3)

where R the is residues of alcohol phenol or carboxylic acidand n is the degree of oligomerization e characteristics ofthe OECC are shown in Table 1

It has been established that relatively close reactivityvalues are observed in the reactions of CO2 with glycidylethers of phenols alcohols and acids Consequently theconditions for the synthesis of cyclic carbonates based onglycidyl ethers [30] have been determined the ratio of re-agents temperature type and amount of catalyst massexchange conditions and others

32 Synthesis of theOECC e epoxy oligomers (1 mol) wereplaced in a reactor equipped with a stirring device a heatingelement and a coil to cool the reaction massemixture washeated to the prescribed temperature of 120 to 140degC therequired amount of catalyst was introducedCcasymp 0025molkgand after 2min a sample was taken to determine the epoxygroups initial concentration Subsequently the reactor wassealed and carbon dioxide was added (VCO2

45 lh withstirring n 300 rpm and P 03MPa) e reaction wasmonitored by changing the concentration of the epoxy groupsby the sampling method (1ml of the reaction mixture wastaken quenched and analyzed)

Various catalysts for the reaction of epoxide compoundswith carbon dioxide can be found in the literature today [31]Catalytic systems containing halide salts found actually thegreatest application among them e catalytic activity ofhaloanions increases in the series as follows IgtBrgtCl Foralkali metal halides the catalytic activity increases withincreasing cation radius e localization of the alkali metalaccelerates the reaction to a greater extentus the catalyticsystem ldquoKCl and crown ether of dibenzo-18-crown-6rdquoexhibit greater activity (reaction rate constant K 128times10minus2 kgmiddotmolminus1middotsminus1) as KCl (K 956times10minus3 kgmiddotmolminus1middotsminus1) Ithas been established that an increase in the reactor volumedoes not adversely aect the quality of the cyclocarbonatesobtained

33 Saponication Number Determination of CyclocarbonateGroups e analyzed product between 01 and 02 g wasweighed (plusmn00002) in a 100ml ask and dissolved in 10ml ofacetone Subsequently 5ml of 07M sodium hydroxide so-lution was poured in e resulting mixture was heated for 30minutes in a boiling water bath with a reux condenser Afterthat the ask was lifted slightly cooled and disconnectedfrom the refrigerator 20ml of distilled water and 10ml ofa 10 solution of barium chloride (previously neutralized byphenolphthalein) were added to the mixture e ask wasclosed with stopper mixed and cooled Excess sodiumhydroxide was titrated with 01M hydrochloric acid inthe presence of phenolphthalein until the pink colordisappeared

In parallel a blank test was carried out under the sameconditions but without analyzing the product e sapon-ication number (X) in of KOHg product was calculated bythe formula X (V0 minusV) middotK middot 56m where V0 and V arethe volumes of the hydrochloric acid solution consumed fortitration in the blank test and the sample of the productrespectively K is the correction factor to 01M HCl solution56 is the amount of potassium hydroxide corresponding toexactly 1ml of 01MHCl solution andM is the weight of thesample of the product For the result analysis the average ofthree parallel denitions was taken which discrepancy wasno more than 20mg KOHg with a condence level of 095

34 Mass Fraction Determination of Epoxy Groups (EpoxyNumber) To determine the residual epoxy number 1 g ofCC sample was used e reaction products (OECC) weredissolved in chloroform and DCCED-20 was solved in

Advances in Materials Science and Engineering 3

Tabl

e1

Characteristicsof

OEC

Cbasedon

epoxyoligom

ers

echem

ical

nature

ofepoxyoligom

ers(epoxy

number(

))

Radicals

reectingthenature

ofthe

OEC

CR

Con

ditio

nal

abbreviatio

nof

OEC

C

Con

tent

ofepoxy

grou

ps(

)(residual)

Sapo

nicationnu

mber

(mgKOHg)

Visc

osity

at25

deg C(Pamiddots

)

T m (deg C)

Density

20deg C

(gcm3)

App

earance

Determined

Calculated

Epoxidated

oligom

erED

-20(216

)based

onbispheno

l-A

СН3

СН3

CDCCED-20

010

452

459

mdash55

mdash

Ahard

brittle

massof

yello

wcolor(brown-

white

powderafter

grinding

)

Diglycidylo

ligom

erbasedon

diethylene

glycol

DEG

-1(268

)

ndashСН

2ndashСН

2ndashОndashС

Н2ndashСН

2ndashDCCD

EG-1

017

552

560

112

mdash14762

Low-visc

osity

liquidof

yello

wish

color

Diglycidylo

ligom

erbasedon

diprop

ylene

glycol

(255

)СН

3СН

3

-СН

2-СН

-О-С

Н-С

Н2-

DCCD

PG016

530

535

185

mdash14722

Liqu

idof

yello

wish

color

Diglycidylo

ligom

erbasedon

11-di

(oxymethyl)-3-

cycloh

exene(250

)

-СН

2СН

2-

DCCD

OC

006

555

560

2610

mdash14960

Visc

ousliquidof

cherry

color

Epoxyoligom

erbased

onepichloroh

ydrin

(polyepicholorhydrin)

-E-181

(259

)

СН2-

СН-С

Н2-

О (С

Н2-

CH-O

) СН

2-CH

-СН

2

OO

C=O

СН2C

lO

OC=

ODCCE-181

010

524

522

1704

mdash14906

Visc

ousliquidof

cherry

color


dioxane e epoxy number determining was carried outaccording to GOST 12497-78

35 Calculation of Amine Hardener Amount for CC-Compositions e hardener was always taken in a stoi-chiometric amount under consideration of its interactionwith epoxy and cyclocarbonate groups e amount ofhardener (X) per 100 g of the mixture of oligomers wasdetermined according to the following formula

X α times kEO times MEG + β times kcc times CC (4)

where α and β are the mass fractions of oligomers in themixture KEO and KCC are the stoichiometric coefficients ofthe hardener with respect to epoxy and cyclocarbonateoligomers CC is the mass fraction of cyclocarbonate groupsand MEG is the mass fraction of epoxy groups

36 Strength and Adhesion Properties For evaluating themechanical properties the following values were de-termined the tensile strength (σp) and the elongation (εp) atbreak according to DIN EN ISO 527 and the tensile shearstrength of adhesive joints (τ) in accordance with DIN EN1465 with uniform separation (σpo) in accordance with ISO4587 e data of physical and mechanical tests were pro-cessed using the software Statgrafica

37 Aermomechanical Analysis (TMA) TMA was carriedout under uniaxial compression at stress of 15MPa anda temperature rise rate of 25degCmin Samples of cylindricalshape with diameter 10mm and height 10mm were usede glass transition temperature (Tg) and the transitiontemperature to the high-elastic state (Tm) were determinedby conventional methods (by the tangents intersection)

38 Topological Grid Parameters e most important to-pological grid parameter is the interstitial chain fragmentmolecular mass (Mc) It was determined fromWallrsquos formula[12] that Mc 3 middot ρ middotR middotT middot εeσ where ρ is the density of thepolymer T is the absolute temperature R is the gas constantεe is the relative deformation in the highly elastic state andσ NS is the stress applied to the sample e effectivedensity of the polymer network nodes (cs) was determinedfrom the following relation cs 2 middot ρ middotN0(3 middotMs) where N0is the Avogadro number

39 IR Spectroscopy IR spectra of oligomeric and polymericsystems were recorded on a two-beam Carl Zeiss UR-20spectrophotometer with the detection range from 400 to4000 cmminus1 e following operating parameters were usedtarget program nr 4 scanning speed was 160 cmminus1 for normalspectrum and 32 cmminus1 for frequency refinement spectrume registration scale was 20min100 cmminus1e spectra of thepolymer samples were taken in the condensed state in the filmwith the thickness δ 10 to 20 μm between the KBr plates Atelevated temperatures a special thermocuvette was used esolutions spectra were recorded in KBr and KRS-5 cuvetteswith a thickness of 007 to 300mm

For investigating the curing processes of polymer sys-tems the cuvette windows were covered with a fluoroplasticfilm with thickness δ 10 μm e spectra were recorded inthe regions 800 to 1000 cmminus1 and 1600 to 1900 cmminus1 In theseranges an uncompensated absorption of the fluoroplasticfilm could be considered e fraction of unreacted func-tional groups (epoxy and cyclocarbonate) was determinedby normalizing the optical density of the correspondingband at time of the first measurement tc (1min after theoligomers were mixed with the curing system)

310 Dielectric Loss Method Measurement of the dielectricparameters was carried out in the frequency range from 103to 106Hz and the temperature range from minus180 to +250degCon samples in the disk form with a diameter of 50mm anda height of 2 and 3mme samples were previously coveredwith aluminum foil

311 Nuclear Magnetic Resonance Method Two methods aremost effective for research in solids and viscous liquids (olig-omers and polymers) pulsedNMRandNMRofwide linesefirst is based on the study of magnetic relaxation at varioustemperatures estimated by spin-lattice (T1) and spin-spin (T2)relaxation e second is based on the shape study of the lineand its temperature dependence e study was performed ona laboratory coherent NMR relaxometer at a frequency of17MHz e decay curves of the transverse magnetization(DCTM) were recorded by the CarrndashParcellndashMeibumndashGilmethod from the free induction decay [32] e measure-ment was carried out under isothermal conditions as well aswith a stepwise temperature rise in the range from 20 to 220degCwith an isothermal holding time of 15 minutes e molecularmobility was estimated from the times of transverse spin-spinrelaxation T2 In the general case the free induction decay isdescribed by a function as a superposition of several terms

f(t) Pa middot exp minust

T2a

1113888 1113889 + Pb middot minust

T2b1113888 1113889 + Pc middot exp minus

t

T2c1113888 1113889

(5)

where Pa Pb and Pc are the relative proton nuclei fractionsthat relax with transverse relaxation times T2a T2b and T2c

ldquoPhases ardquo is formed by nuclei with longer relaxationtimes and ldquophase b and crdquo with shorter ones respectively etimesT2b andT2c were determined by successively subtractingthe values of the longer relaxation component from the valuesof the experimental curves e population of the ldquophasesrdquo(the number of protons entering this ldquophaserdquo) Pa Pb and Pcwas calculated from the contribution to the initial amplitudeof the signal by extrapolating the lines to the zero line (the linepassing through the point of excitation of the oscillograph)Measurements by the wide-line method [33] were carried outon a laboratory NMR spectrometer at a frequency of 16MHz

4 Results and Discussion

By the development of new polymeric materials the modi-fication of epoxy polymers with urethanes is successfully used


[34 35] e most promising direction here is the oligomermodication containing urethane groups in the chain andepoxy groups at the ends One of the obstacles for its wide useis the dishyculty to obtain the urethane-containing materialsusing conventional isocyanate technology which also has itsdrawbacks such as toxicity of isocyanates the complexity oftheir production storage processing and the possibility ofside reactions in the presence of even small amounts of water[31 35] Some improvement in processing conditions forepoxy compositions provides the use of blocked isocyanates[36] Among the known nonisocyanate methods [37 38] forthe preparation of urethane-containing compounds theurethane-forming reaction ldquocyclocarbonate-aminerdquo deservesattention Cyclic carbonates (CC) are a relatively new andpoorly studied class of compounds that causes the urgency ofthe work analysis by methods of their production reactivityand methods for modifying polymers [31]

41 Oligomer-Analogous Transformations of Epoxy OligomersHighlighting the main stages of CC synthesis it should benoted that the carbonatization of glycidyl ethers can berepresented as a chemisorption process described by thefollowing equation

α 1minus eminuskT (6)

where α is the degree of reactive groups conversion T is thetime and K is the adsorption coeshycient which is a functionof the gas content (φ) the rotational speed of the stirrer (n)the uid viscosity (]L) and the apparatus diameter (D) equantitative interrelation of these parameters is establishedfor the process under study [30] by the following equation

K 166]LD2( )

0088middot φ034 middot n0912 (7)

By these studies the possibility of obtaining oligomericCC at both excess and atmospheric pressure was establishedMoreover the process of carbonization at atmosphericpressure can take place not only in solution but also in themass with a sushyciently high rate to high degrees of trans-formation (α) in the range from 120 to 140degC and concen-tration of catalyst (C2H5)4 NJ tetraethylammonium iodide inan amount of no more than 1times 10minus2molkg e reaction isdescribed by second-order kinetic equation [39]

dx

dτ K middotXY (8)

where X is the concentration of epoxide groups and Y is thecatalyst concentration (Cc) In the synthesis of the CC themass of the reaction mixture (m) increases with increasingconversion (α) and the catalyst concentration (Y) decreasesaccordingly Dependence of the change in the mass of thereaction mixture (m) and α is related by the following rela-tion m nEOtimes (MER + 44 middot f middot α) where MER is the molecularweight of epoxy resins (ER) f is the functionality of the ERand nEO is the number of the epoxy oligomer moles in initialtime e obtained experimental data on the interactionof α-oxides with CO2 allowed determining the conditionsfor the oligoethercyclocarbonate preparation based on epoxy

oligomers with dierent structures (Table 1) e stablequality of the OECC is probably similar due to the oligo-meramino conversion of epoxide groups to cyclocarbonateones e presence of such a transformation is conrmed byIR spectroscopy data (the peak presence at 1800 cmminus1 cor-responding to stretching vibrations gtCO groups in the CC)and chemical analysis (coincidence of the calculated anddetermined saponication number) After carbonatizationthe molecular-weight distribution of epoxy oligomers ispractically unchanged inherited by cyclocarbonate oligomersis was clearly conrmed for the epoxidian oligomer and thecorresponding cyclic carbonate DCCED-20 It was satis-factorily conrmed also for other epoxy oligomers

42 Structuring of Epoxyurethane Mesh Polymers epolymer formation process based on epoxy-cyclocarbonateamine curing compositions was determined by the condi-tions of two basic competing reactions epoxide-amine withthe formation of a network structure and cyclocarbonate-amine with the formation of linear hydroxyurethanefragments e variety in the resulting epoxyurethanepolymer properties cannot be excluded under the conditionsdetermining the formation of a single polymeric networka common curing agent (an aliphatic amine) and a closereactivity of epoxy and cyclocarbonate oligomers By varyingthe ratio of components and the structure of EC oligomers itis possible to regulate the cross-link density polarity andexibility of the grid chains formed by chemical bonds Inaddition the modication of OECC epoxy-amine compo-sitions leads to the formation of intermolecular hydrogenbonds involving urethane groups at can aect the mo-lecular mobility and the level of physical and mechanicalproperties of polymers (the contribution of a physical bondsnetwork) e totality of the modication processes can berepresented step by step as follows

43 Aminolysis of Cyclic Carbonates and eir Curingwith Epoxy Oligomers Kinetic studies of the CC aminolysiswere performed on the example of the interaction of1-tetrahydrophenylcarboxy-23-propylene carbonate (ob-tained on the basis of phenyl glycidyl ether (PGE) the contentof epoxy groups was 0 the determined saponicationnumber was 582 and the calculated saponication numberwas 577 Tm 93degC white powder) with benzylamine inchlorobenzene [40] It is established that the investigatedprocess proceeds by two parallel ows noncatalytic andcatalyzed by two amine molecules e mechanism of theprocess can be represented in the following form

CH2-O

R-CH-OC=O + NH2-Rprime H-NH-Rprime

CH2-O

R-CH-OC=O

(9)

Rprime-NHδndash-H NH2-Rprime2Rprime-NH2 (10)

In the rst stage of the process a formation of associatesis possible a hydrogen-bonded complex of benzylamine


with a CC and two amine molecules as a result of self-association Further the catalytic reaction develops with theopening of the cyclocarbonate ring obviously through anintermediate cyclic transition state formed by the interactionof the activated amine in the associate and cyclocarbonate inthe associate

CH2-O

CH-O

R

OH-NH-Rprime

H

H

R-CH-CH2-O-C-NH-Rprime + 2Rprime-NH2

OOH

Rprime

NH-Rprime

NH

C

(11)

Analogous assumptions about the formation possibilityof a cyclic transition compound were also expressed in [41]but with the participation of two amine molecules In thecase of noncatalytic aminolysis the cyclocarbonate isattacked by the carbonyl carbon atom by one amine mol-ecule e probability of a cyclic transition state is conrmedby the low activation energy in the catalytic reaction [42]calculated approximately at two temperatures With a de-crease in temperature and an increase in the amine con-centration the catalytic ow contribution increases to theoverall process of the CC aminolysis (Table 2)

By real curing conditions of oligomers EO and OECC(when the process is carried out in ldquomassrdquo) higher reactionrates should be expected since the amine concentrationunder these conditions is 4-5 gl which conrms the validityand possibility of using the CC as reactive epoxy modiers ofamine curing compositions

e curing process of the epoxy and cyclocarbonateoligomer was studied by IR spectroscopy Comparativestudies were performed on aromatic (DCCED-20) and ali-phatic oligoethercyclocarbonates (DCCDEG-1 and DCCE-181) (Table 3) When curing the (ED-20+DCCDEG-1+DETA) and (ED-20+DCCED-20+DETA) compositionsa redistribution of the intensities of the absorption bands of920 cmminus1 (epoxy groups) 1802 cmminus1 (cyclocarbonate Group)1700 and 1715 cmminus1 (carbonyl groups of urethane fragments)could be considered in IR spectra is indicates the occur-rence of simultaneous reactions over epoxide and cyclo-carbonate groups

In the aminolysis study on model compounds it wasshown that the reaction rate for cyclocarbonate is higherthan for epoxy is conclusion can be conrmed for OECC(with a content of 20 to 30) after 5 minutes the reactionrate is high (this is indicated by the intense peak of urethanecarbonyl) and after 60 minutes the conversion (α) is about60 With an OECC content of more than 30 theconsumption rate of the cyclocarbonate groups decreasesand that of the epoxide groups increases (slopes of the curvesin Figure 1)is may be a catalytic eect consequence of thehydroxyurethane groups formed

Further as a result of the predominant epoxy groupinteraction the composite system is depleted by the primaryamine e limiting degree of the CC group transformation

decreases since the interaction with the secondary CC aminesat 20 to 22degC is very slowis conclusion is conrmed by thefact that with an excess of amine (12 to 13 from stoichi-ometry) the degree of reactive group conversion increasessharply and after 5 to 8 h (for cyclocarbonate) and 16 to 20 h(for epoxy) changes in the intensity of the characteristicbands almost do not occur After 24 h α is 90 to 95 (forcyclocarbonate) and 80 to 90 (for epoxy) groups e notedsigns of inhibition due to the network polymer solidifying[43] are also retained when the OECC is modied reachingαasymp 70 to 75 e properties of unmodied epoxy-aminepolymers stabilize after 5 to 7 days but they do not reach thelevel of polymers characteristic for highly cured polymers(22degC with 24 h and 100degC with 10 h) (Table 3)

For systems containing DCC-DEG-1 this dierence isinsignicant which is quite convincing evidence of the eectof modication

It should be noted that with polymer characteristicsimprovement (σr εr and Ts) the adhesive properties alsoincrease (TB and σrp) is result is worthy of note sinceLipatov et al noted [44 45] that epoxy-amine systems havea low adhesive strength as a result of the weak boundarylayer formation due to the selective sorption of epoxypolymers on high-energy hard surfaces is as a conse-quence leads to a violation of the stoichiometry of thecomponents and the lack of solidication of the compositionin the boundary layer

To compare the adhesive strength in the boundarylayers of the systems (Table 4) the IR absorption spec-troscopy in absorption (1 2) and ATR arrangement (1prime 2prime)was used (Figure 2) It can be considered that for theunmodied system the degree of reactive epoxy groupsconversion (α) was 72 and in the boundary layer 36(high free surface energy-element KRS-5) For systemsmodied with 20 DCCDEG-1 the values α for epoxygroups are relatively close to 72 and 62 respectivelyese results make it possible to understand not only thereasons for the increase in adhesion strength as a result ofthe OECC modication but also the previously describedaminolysis features of the CC and EO As noted above inthe rst minutes of mixing oligomers with an aminehardener a signicant amount of urethane groups areformed in the system which are capable to blocking theactive centers of the substrate solid surface It prevents theselective sorption of EO and weak boundary layers for-mation after the composition is applied

44 e Contribution of Hydroxyurethane Fragments to theEpoxyPolymerProperties e topological structure studiesformed by epoxy-amine mesh modication with cycliccarbonate containing hydroxyurethane fragments were

TABLE 2

Value 60degC 80degC E (kJmol)Co (lmiddotmolminus1middotmin) 558times10minus1 995times10minus4 283Cv (lmiddotmolminus1middotmin) 992times10minus3 114times10minus2 68Note Co is the noncatalytic constant of the CC bimolecular interaction onthe PGE basis and Cv is the catalytic rate constant


performed by IR spectroscopy and a number of relaxationmethods As noted above the disadvantage of unmodiedepoxy-amine compositions is their high stiness (brittle-ness) which results in low cohesive strength especially forcured compositions without heat input (Table 3) ecohesive strength depends on both the density of thechemical bonds network and the intermolecular in-teraction forces (a grid of physical bonds) in the glassystate e increase in rigidity and heat resistance (toa greater extent for polymers cured at T lt 22degC) mainlydepends on intermolecular interactions (IMI) in chains andpacking of aromatic nuclei Based on these provisions itwas of interest to determine the manifestation and relativelevel of these factors in the initial epoxy-amine system and

to follow the changes that occur during the modiedcompositions curing

Controlling the optical density and the integrated in-tensity of the complex deformation vibration in benzene

100

80

60

40

201 2

34

0 6 12 18 24t (h)

(Dt 92

0D

0 920)

middot100

()

(a)

100

80

60

40

202

34

5

(Dt 16

02D

0 1602

)middot10

0 (

)

0 6 12 18 24t (h)

(b)

Figure 1 Changes in the content of epoxide (a) and cyclocarbonate groups (b) during the curing of ED-20 +DCCDEG-1 +DETAcompositions as a function of the DCCDEG-1 content with 0 (1) 20 (2) 40 (3) 50 (4) and 60 (5)

Table 3 Physicomechanical properties of polymers obtained under dierent conditions of curing epoxy-amine compositions

Composition Curing modePhysical and mechanical properties

σr (MPa) εr () τc (MPa) σrp (MPa) Ts (degC)

ED-20 +DETA 7 d at (22plusmn 2degC) 207 06 46 88 461 d at (22plusmn 2degC) and 10 h at 100degC 725 25 125 280 108

ED-20 +DCCDEG-1 +DETA 7 d at (22plusmn 2degC) 752 52 158 305 421 d at (22plusmn 2degC) and 10 h at 100degC 883 44 228 500 68

Table 4 Inuence of modiers (20 OECC) and ED-20 +DETAcomposition curing at the second moment of NMR absorption

Composition

Second moment of NMRabsorption

Curing 7 dat 22degC

Postcuring 10 hat 100degC

ED-20 +DETA 450 250ED-20 +DCCED-20 +DETA 450 520ED-20 +DCCDEG-1 +DETA 168 270

100

80

60

40

20

2prime

1 2

1prime

0 4 8 12 16 20 24t (h)

(Dt 92

0D

0 920)

middot100

()

Figure 2 e change in the content of unreacted epoxy groupsduring the curing of ED-20-DETA (1 1prime) and ED-20 +DCCDEG-1 +DETA (2 2prime) compositions determined by IR transmissionspectroscopy (1 2) and ATR-IR (1prime 2prime)


ring bands (wavenumbers of 1612 cmminus1 and 1584 cmminus1)which are sensitive to changes in the universal in-termolecular interaction of aromatic nuclei the changesoccurring during glass transition of the systems were fol-lowed During the ED-20 +DETA compositions curingprocess an increase in the integrated intensity of the spectralcontour in the frequency range of 1570 to 1650 cmminus1 wasobserved is is proportional to the change in the opticaldensity of 1612 cmminus1 band (D1612) which indicates theenhancement of the aromatic nuclei IMI

eD1612 values by curing for 3 d at 22degC increase from0681 to 0724 and after curing for 8 h at 100degC theydecrease to 0685 ese results indirectly indicatea change in the stiffness and molecular mobility of thepolymer structure elements which is also confirmed bydata determined from the second magnetic momentsvalues of NMR absorption (M2) It is known [32] that thelarger the value of M2 indicates the lower molecularmobility A polymer based on an unmodified epoxy-aminecomposition cured at 22degC is characterized by a high levelof M2 values with 45 E2 which decreases after postcuringat 100degC (Table 4) According to these results the addi-tional curing should help increase the chemical bondsnumber and further increase the rigidity of the polymerCan this fact be explained

For more rigid epoxy-amine systems containing slow-moving polyhedra fragments it was shown that by aminecuring without additional heat input linear polymerchains are predominantly formed in the composition asa result of the predominant interaction of more activeprimary amino groups with epoxy groups EO (with theexample of bisphenol A diglycidyl ether) e resultinglinear chains are capable of denser packaging in partic-ular aromatic nuclei (in the case of adamantanes bulkcycloaliphatic fragments) which determines the highrigidity of the polymer e postcure at T gt Tc not onlyleads to an increase in the cross-linking frequency (overthe secondary amino groups) but also to the destructionof the formed ordered structures [46] and consequentlyto a polymer rigidity reduction

For example when the ED-20 +DETA composition ismodified with an aromatic OECC the structure of the newlyformed polymer is characterized by the presence of urethanegroups and a lower cross-linking frequency (ηc) Howeverdespite a slight decrease in ηc the rigidity of the limit-curedpolymer is much higher (M2 52E2) than for an un-modified polymer is unambiguously demonstrates thecontribution of urethane groups to an increase in stiffnessand a decrease in molecular mobility Comparing with thestiffness of modified aliphatic OECC it can be seen that thelevel for polymers cured at 22degC with M2 168 E2 is muchlower and after the hardening the M2 value is close to thelevel of the highly cured unmodified polymer is is ob-viously a consequence of the combined effect of high-polarurethane groups (decreased mobility) and flexible dieth-ylenic fragments (increased mobility) According to thevalues ofM2 the optical density of the band is 1612 cmminus1 andthe values of D1612 increase during the curing process from1145 to 1205 and 1252 (after the postcuring) which

corresponds to the increase in rigidity of the system usthe cumulative effect is that the introduction of an aliphaticmodifier into the composition increases the system de-formation reserves and reduces the overall level of its rigidity(from M2 450 E2 to M2 168 E2) which provides a highlevel of cohesive strength of the polymers also curingwithout additional heat (Table 3)

e evidence for the urethane group role for increasingthe system rigidity can be confirmed by an experiment withthe blocking of these groups by lithium chloride (4 so-lution in dimethylformamide taken in the stoichiometricratio to the calculated number of urethane groups) ecomposition as well as the cured polymer remained trans-parent when combined with LiCl and after the addition ofthe hardenere Li+ and Clminus ions block the gtCO and NH-groups formed during the curing excluding (in part or inwhole) the intra- and intermolecular interactions e dataobtained clearly illustrate the effect of polymer hardeningdue to physical interactions of urethane groups (Table 5)e performed experiment indicates that the hydrogenbonds in the studied epoxy polyurethane combinations havea significant influence not only on the processes of polymerformation but also on their macroscopic properties Forunmodified epoxy-amine polymers the greater contributionof hydrogen bonds to the macroscopic properties of poly-mers should be expected in the temperature range below theβ transition [28] e linear homo- and copolymers ofstyrene and methacrylates showed [47] that the β-transitionldquoloosens uprdquo the hydrogen bonds and leads to their partialdestruction e hydrogen bonds shift Tc to higher tem-peratures preventing large-scale molecular motion

e molecular mobility in the range from minus100 to+200degC has been studied by the dielectric relaxation methodIt was established that for the investigated polymers twodifferent transitions are the low-temperature transition inthe range from minus70 to + 100degC corresponding to the pro-cesses of dipole-group β-relaxation and high-temperaturetransition by Tgt+100degC corresponding to dipole-segmentalα-relaxation (Figure 3) It can be seen from the relaxationcurves that the β-relaxation peak intensity decreases with anincrease in the OECC concentration (partial degeneration ofthe β-transition was observed) It can be assumed that theintra- and intermolecular hydrogen bonds of the hydroxylgroups on the urethane group carbonyl (minusOH middot middot middotOClt)prevent the internal rotation e defrosting of thesemovements obviously occurs with the onset of the polymermelting An increase in theM2 NMR absorption values thedegeneration of the β-transition and a sharp decrease inthe deformation-strength characteristics for the ED-20+DCCED-20 +DETA system indicate a decrease in themolecular mobility in the glassy state In the highly elasticstate its increase is obviously associated with the rotationof hydrogen-bonded hydroxyurethane fragments duringldquodefrostingrdquo of the aromatic nuclei movements (with theα-relaxation process) is is manifested by an increase inthe intensity of the α-transition peak on the dielectricrelaxation curves and the appearance of a second (longer)NMR relaxation time at T gtTc Modification of aliphaticDCCDEG-1 (graph 3 in Figure 3) differs from the


considered variant in the presence of mobile diethyleneglycol units in the polymer structure increasing its mo-lecular mobility in both glassy and highly elastic states

A characteristic feature of most epoxy-amine compo-sitions is the two-component decrease in magnetizationduring their curing with the appearance of the transverserelaxation times T2a and T2b (Figure 4) in the initial stage ofthe induction period e isolated relaxation times T2a andT2b decrease monotonically and are combined in one shorttime T2 at a level of 10 to 20 μs during the reaction pro-ceeding is is characteristic for rigid polymers withfrozen segmental mobility However the yield of T2 values atthis level does not mean the completion of the structure

formation processes as evidenced by the high values of Pa inthe range of 04 to 05 which are retained by the glasstransition of the polymers (Figures 4 and 5)

High values of Pa indicate the intermolecular in-teractions enhancement as well as the molecular mobilitylimitation Analyzing the data of NMR spectroscopy somepeculiarities for polymer system behavior (before gelation)should be noted First the induction period decreases and at20 to 30 of the OECC it is already absent which can beexplained by the reaction acceleration due to the realizationof the OECC catalytic aminoalkylation reaction Secondlythe time for achieving the glassy state is shortened and therate of in the dynamic rigidity increase for the system israised is is apparently not only the catalytic processconsequence but also a consequence of polarity increasein the polymer chains due to the formation of urethanegroups A similar picture was observed in other epoxyur-ethane systems irdly the values of Pa signicantly de-crease up to 030 (Figure 4)

A comparison on the transverse relaxation times ofultimately cured polymers and temperature dependencedata shows that unmodied epoxide-amine polymers haveonly one time T2 in a wide temperature range form +22 to+200degC e appearance of the time T2a is obviously asso-ciated with the formation of hydroxyurethane fragmentsemolecular mobility changes with increasing temperature(transition to a highly elastic state) in accordance with thepolymer structure for example the beginning and com-pletion of the increase in T2 level for unmodied (Figure 6graph 1) and modied with aromatic OECC (Figure 6graph 2) polymers dier from polymers modied with al-iphatic OECC (Figure 6 graph 3) Moreover in the case ofmodication with aliphatic OECC the time T2a was detectedmuch earlier (at 120degC) and the changes in the levels of T2aand T2b occur simultaneously is is typical for a non-uniform structure but a uniform polymer network Obvi-ously the time T2a corresponds to elongated internodechains containing hydroxyurethane fragments e molec-ular motion in them is initiated by the β-relaxation processby ldquolooseningrdquo the hydrogen bonds formed by urethane andhydroxyl groups

5 Discussion

e formation processes study of the developed system forthe hydrogen bonds (network of physical bonds) a decreasein molecular mobility in the glassy state and an increase inthe highly elastic state allows to understand the causes of thechange in the relaxation and physicomechanical propertiesof polymers due to the ldquodischargerdquo of the chemical bondsnetwork by the modication of hard epoxy-amine com-positions by oligoethercarbonates containing aromatic andaliphatic links e choice of the modifying by OECC andthe change in the ratio of components allow inuencingthe frequency of cross-linking the polarity the exibilityof fragments and chains and as a consequence the rigidityof epoxy polymers and adhesives For example the level ofpolymer hardness modied by aliphatic OECC (Table 4) ismuch lower (M2162E2) than unmodied or modied by

2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime

ndash80 ndash40 0 40 80 120 160 200T (degC)

Figure 3 e temperature dependence of the dielectric loss angletangents at a frequency of 106Hz (1ndash3) and 105Hz (1prime 2prime) forpolymers obtained on the basis of the modied ED-20 +DETA (11prime) modied 20DCCED-20 (2 2prime) and 20 of DCCDEG-1 (3)

Table 5 Eect of blocking of urethane groups by LiCl on the epoxypolymer properties

CompositionProperties of polymers

σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts

(degC)ED-20 +DETA with 20DCCDEG-1 883 44 228 500 68

ED-20 +DETA with 20DCCDEG-1 and 4 LiCl 624 51 205 322 38


aromatic OECC When the polymer is postcured thecombined eect of urethane groups is realized the man-ifestation and contribution of physical bond network(reduced mobility) and exible diethylenic fragments(increased mobility)

e observed changes are evidently due to the rotation ofhydrogen-bonded hydroxyurethane fragments during defreez-ing of the aromatic nuclei movements (in the α-relaxationprocess) is is manifested in an intensity increase of theα-relaxation transition peak (Figure 3 graph 2 2prime) and the

Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)

Figure 4 Change in the transverse relaxation times (andashd) and the protons population of the mobile ldquophaserdquo (andashd) during the curing of ED-20 +DCCDEG-1 +DETA with the content of DCCDEG-1 0 (a aprime) 10 (b bprime) 20 (c cprime) and 50 (d dprime)


appearance of the second (longer) NMR relaxation time atTgtTc (Figure 6) e introduction of aromatic DCCED-20(solid and as evidenced by the presence on the wide-angleX-ray diractogram of only amorphous halos amorphousproduct) leads to a sharp reduction in the deformationreserves of the polymer (despite the reduction in the cross-linking frequency) which is accompanied by a drop inthe physicomechanical characteristics of the polymerσr 200MPa and εp 03 (Table 6) that is signicantlylower than for the unmodied ED-20 +DETA (Table 6Figure 7(a)) with σr 752MPa and εp 25 A similarmanifestation of macroscopic properties is observed whenaliphatic OECC are used in the concentration range from 15to 30 (Figures 7ndash9)

e widely used in practice epoxy compositionmodication with aliphatic epoxy oligomers (eg DEG-1)is less eective Comparison of the absolute indicatorslevel in Figures 7(b) and 10 clearly demonstrates a moresignicant contribution of the urethane component in theapplication of aliphatic OECC e use of dierent OECCstructures (DCCDPG DCCCOC and DCCE-181) givessimilar dependences in physicomechanical properties

which dier in the positions of the maxima (Figures 8 9and 11)

A number of examples on the practical applicationconvincingly conrm the OECCmodication eectiveness ofepoxy-amine compositions and the perspectives of theirapplication in solving a number of problems in polymermaterials science For example for technologies of adhesivebonding parts with large tolerances in honeycomb structureslightweight products and so on operated in the temperaturerange from minus150 to +200degC fast-setting foam-adhesives havebeen developed ese adhesives have a relative low density(045 gcm3) and higher strength (15 times) and adhesion (2times) compared to the known foam-adhesives VK-9V andCW2513 HM and DY050 (manufacturer Ciba Geigy)

A low viscosity composition based on a mixture of ali-phatic and aromatic EO aliphatic OECC and a mixture ofamine- curing agent for the reinforced concrete structuresrepair was developed Due to the elimination of the selectivesorption eect for the composition components it waspossible to ensure the reliability of products (water pipes witha diameter of 2000mm and a length of 6000mm) which isevaluated under hydraulic tests at a pressure of 10MPa iscomposition combines low viscosity (06MPamiddots) with highadhesion and deformation characteristics for steel andglass-ceramic up to 270MPa (concrete breaks at lower loads)σp up to 50MPa εp 5 which is comparable or superior tothe analog Araldite K-79 Kit (manufacturer Ciba Geigy)A number of the ldquoVicor-UPrdquo-type compositions have beendeveloped for corrosion protection of chemical equipmentoperating under conditions of 5 to 30 mineral acids solu-tions (hydrochloric sulfuric and phosphoric acids) at

1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime

Figure 5 Change in the transverse relaxation times (andashc) and the population of the mobile ldquophaserdquo protons (aprimendashcprime) during the curing of ED-20 +DCCED-20 +DETA composition with a content of DCCED-20 10 (a aprime) 20 (b bprime) and 30 (c cprime)

1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321

Figure 6 Temperature dependences of transverse relaxation timesfor polymers based on ED-20 +DETA (1) ED-20 +DCCED-20+DETA (2 2prime) ED-20 +DCCDEG-1 +DETA (3 3prime) 20 OECC

Table 6 Mechanical properties of polymers based on epoxycompositions modied by OECC and cured DETA

OECCtype

σr (MPa)εr () of polymers by ratio OE OECC100 0 90 10 80 20 70 30 60 40

Aromatic 72525 42008 20003 80mdash mdashAliphatic 72525 82523 88344 77028 55050


+120degC as well as for cold-drying technology e compo-sition and technology of polymer-sand mandrels obtainingwith an increased (by 15 times) strength by reducingthickness and mass in the technology of manufacturing

products have also been developed ese applications testifythe wide possibilities for OECC as modiers in epoxy-aminecompositions in various technologies and prospects for theresearch and development in this direction

6 Conclusions

One of the promising directions of epoxy-amine networkpolymers in order to eliminate their ldquohardnessrdquo is the

0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)

Figure 7 Dependence of the epoxyurethane polymer properties on the basis of ED-20 +DCCED-20 +DETA (a) and ED-20 +DCCDEG-1 +DETA (b) on the OECC modifying concentration σp (1) τc (2) σro (3) Er (4) and Ts (5)

20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400

Figure 8 Dependence of the tensile strength of polymers obtainedon the basis of ED-20 +OECC+DETA compositions on theconcentration and modier type DCCUP-675 (1) DCCUP-650D(2) and DCC-181 (3)

10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132

Figure 9 Dependence of the adhesive properties of the ED-20+OECC+DETA compositions on the concentration and modiertype DCCUP-675 (1 1prime) DCCUP-650D (2 2prime) and DCE-181(3prime) τc (1ndash3) and σpo (1primendash3prime)


preparation of oligoethercyclocarbonates (OECC) and theiruse in joint curing with epoxy oligomers e resultingpolymers contain in the network structure additional linearhydroxyurethane fragments ese ldquorelaxatorsrdquo are capableof manifesting intermolecular interactions that aect therelaxation properties and molecular mobilitye last causesan increase in adhesion and elastic-deformation charac-teristics and opens additional opportunities in the devel-opment of new materials and technologies in the polymermaterial science

Data Availability

e data used to support the ndings of this study areavailable from the corresponding author upon request

Conflicts of Interest

e authors declare that they have no conicts of interest

Acknowledgments

e work was carried out within the framework of StateAssignment number 104763201789 e authors wouldlike to thank the companies and employees of KSUAEKNRTU and SKZ for the supporting work which havemade a signicant contribution to the implementation ofthese results

References

[1] B Erman and J E Mark Structure and Properties of Rub-berlike Networks Oxford University Press New York NYUSA 1997

[2] R F Stepro Polymer Networks Principles of eir FormstionStructure and Properties Springer Luxemburg Belgium1998

[3] Y Osada and A R Khokhlov Polymer Gels and NetworksMarcel Dekker New York NY USA 2002

[4] A S Lipatov T T Alekseeva L A Sorochinskaya andG V Dudarenko ldquoConnement eects on the kinetics offormation of sequential semi-interpenetrating polymernetworksrdquo Polymer Bulletin vol 59 no 6 pp 739ndash7472008

[5] S Goswami and D Chakrabarty ldquoSequential interpenetratingpolymer networks of novolac resin and poly(n-butyl meth-acrylate)rdquo Journal of Applied Polymer Science vol 102 no 4pp 4030ndash4039 2006

[6] M Patri C V Reddy C Narasimhan and A B SamuildquoSequential interpenetrating polymer network based on sty-rene butadiene rubber and polyalkyl methacrylatesrdquo Journalof Applied Polymer Science vol 103 no 2 pp 1120ndash11262007

[7] L V Karabanova L M Sergeeva and A V SvyatynaldquoHeterogeneity of glass transition dynamics in polyurethane-poly(2-hydroxyethyl methacrylate) semi-interpenetratingpolymer networksrdquo Journal of Polymer Science Part BPolymer Physics vol 45 no 8 pp 963ndash975 2007

[8] J F Fu L Y Shi S Yuan Q D Zhong D S Zhang andY Chen ldquoMorphology toughness mechanism and thermalpropertiesof hyperbranched epoxy modied diglycidyl ether

0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)

Figure 10 e eect of the DEG-1 content in the composition ofED-20 +DEG-1 +DETA on the properties of polymers σr (1)τc (2) σro (3) εr (4) and Ts (5)

0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()

Figure 11 Dependence of the mechanical and adhesion proper-ties of polymers obtained on the basis of the E-181 +DCCED-20 +DETA compositions on the modier concentration σr (1) τc(2) σro (3) and εr (4)


of bisphenol A (DGEBA) interpenetrating polymer net-worksrdquo Polymers for Advanced Technologies vol 19pp 1597ndash1607 2008

[9] AMartinelli L Tighzert L DrsquoIlario I Francolini andA PiozzildquoPoly(vinyl acetate)polyacrylate semi-interpenetrating polymernetworks II ermal mechanical and morphological char-acterizationrdquo Journal of Applied Polymer Science vol 111 no 6pp 2675ndash2683 2009

[10] V I Irzhak and S M Mezhikovski ldquoKinetics of oligomercuringrdquo Russian Chemical Reviews vol 77 no 1 pp 77ndash1042008 in Russian

[11] A A Askadski and V I Kondrashenko Computer MaterialScience of Polymers Scientific World Moscow Russia 1999in Russian

[12] D W Van Krevelen and K T Nijenhuis Properties ofPolymers Elsevier Amsterdam Netherlands 2009

[13] D R Wentzel andW Oppermann ldquoOrientation relaxation oflinear chains enclosed in a network studied by birefringencemeasurementsrdquo Colloid and Polymer Science vol 275 no 3pp 205ndash213 1997

[14] I T Smith ldquoe mechanism of the crosslinking of epoxideresins by aminesrdquo Polymer vol 2 pp 95ndash108 1961

[15] B A Rozenberg ldquoEpoxy resins and composites IIrdquo Advancesin Polymer Science vol 75 pp 113ndash165 1986

[16] A M Elyashevich ldquoComputer simulation of network for-mation processes structure and mechanical properties ofpolymer networksrdquo Polymer vol 20 no 11 pp 1382ndash13881979

[17] P J Flory Principles of Polymer Chemistry Cornell UniversityPress New York NY USA 1953

[18] V M Lanzov V F Stroganov and L A AbdrahmanovaldquoInterrelation of kinetic and structural-topological hetero-geneity of molecules in polycondensation epoxy-amine net-workrdquo High-Molecular Compounds vol 31 pp 409ndash4131989 in Russian

[19] V I Irzhak Architecture of Polymers in Russian ScienceMoscow Russia 2012

[20] K Dusek and M Duskova-Smrckova ldquoNetwork structureformation during crosslinking of organic coating systemsrdquoProgress in Polymer Science vol 25 no 9 pp 1215ndash12602000

[21] V I Irzhak ldquoMethods of description of the polycondensationkinetics and the structures of the polymers formedrdquo RussianChemical Reviews vol 66 no 6 pp 541ndash552 1997

[22] V Bellenger J Verdu and J Francillette ldquoInfra-red study ofhydrogen bonding in amine-crosslinked epoxiesrdquo Polymervol 28 no 7 pp 1079ndash1086 1987

[23] E Morel V Bellenger and J Verdu ldquoStructure-water ab-sorption relationships for amine-cured epoxy resinsrdquo Poly-mer vol 26 no 11 pp 1719ndash1724 1985

[24] P J Bell ldquoMechanical properties of a glassy epoxide poly-mer effect of molecular weight between crosslinksrdquo Journalof Applied Polymer Science vol 14 no 7 pp 1901ndash19061970

[25] R E Cuthrell ldquoMacrostructure and environment-influencedsurface layer in epoxy polymersrdquo Journal of Applied PolymerScience vol 11 no 6 pp 949ndash952 1967

[26] T Hirai and D E Kline ldquoDynamic mechanical properties ofnonstoichiometric amine-cured epoxy resinrdquo Journal ofApplied Polymer Science vol 16 no 12 pp 3145ndash31571972

[27] D M Brewis J Comyn and J R Fowler ldquoAn aliphatic aminecured rubber modified epoxide adhesive 2 further evalua-tionrdquo Polymer vol 18 no 9 pp 951ndash954 1977

[28] J M Pochan R J Gruber and D F Pochan ldquoDielectricrelaxation phenomena in a series of polyhydroxyether co-polymers of bisphenol-a engcopped polyethelene glycol withepichlorhydrinrdquo Journal of Polymer Science Polymer PhysicsEdition vol 19 no 1 pp 143ndash149 1981

[29] H Batzer and S A Zahir ldquoStudies in the molecular weightdistribution of epoxide resins IV Molecular weight distri-butions of epoxide resins made from bisphenol A and epi-chlorohydrinrdquo Journal of Applied Polymer Science vol 21no 7 pp 1843ndash1857 1977

[30] V Besse F Camara C Voirin R Auvergne S Caillol andB Boutevin ldquoSynthesis and applications of unsaturatedcyclocarbonatesrdquo Polym Chem vol 4 no 17 pp 4545ndash45612013

[31] V F Stroganov V N Savchenko and S I OmelchenkoCyclocarbonates and Aeir Use for the Synthesis of PolymersInstitute of Technical and Economic Research MoscowRussia 1984 in Russian

[32] A C Lind ldquoAn NMR study of inhomogeneities in epoxyresinsrdquo American Chemical Society Division of PolymerChemistry vol 21 pp 241-242 1980

[33] D W Larsen and J H Strange ldquoDiglycidyl ether ofbisphenol-A with 44prime-methylenedianiline a pulsed NMRstudy of the curing processrdquo Journal of Polymer SciencePart A-2 Polymer Physics vol 11 no 7 pp 1453ndash14591973

[34] T I Kadurina V A Prokopenko and S I OmelchenkoldquoCuring of epoxy oligomers by isocyanatesrdquo Polymer vol 33no 18 pp 3858ndash3864 1992

[35] Z S Petrovic Z Zavargo J H Flyn and W J Macknightldquoermal degradation of segmented polyurethanesrdquo Journalof Applied Polymer Science vol 51 no 6 pp 1087ndash10951994

[36] A DWicks and ZWWicks ldquoBlocked isocyanates III part Buses and applications of blocked isocyanatesrdquo Progress inOrganic Coatings vol 41 no 1ndash3 pp 1ndash83 2001

[37] J Guan Y Song Y Lin et al ldquoProgress in study of non-isocyanate polyurethanerdquo Industrial and Engineering Chem-istry Research vol 50 no 11 pp 6517ndash6527 2011

[38] W Zhijun C Wang C Ronghua and Q Jinqing ldquoSynthesisand properties of ambient-curable non-isocyanate poly-urethanesrdquo Progress in Organic Coatings vol 119 pp 116ndash122 2018

[39] M A Levina V G Krasheninnikov and M V ZabalovldquoNonisocyanate polyurethanes from amines and cyclic car-bonates kinetics and mechanism of a model reactionrdquoPolymer Science Series B vol 56 no 2 pp 139ndash147 2014

[40] V F Stroganov and I V Stroganov ldquoPeculiarities of struc-turization and properties of nonisocyanate epoxyurethanepolymersrdquo Polymer Science Series C vol 49 no 3 pp 258ndash263 2007

[41] J Tabushi and R Oda ldquoKinetic study of the reaction ofethylene carbonate and aminesrdquo Nippon Kagaki Zasshivol 84 no 2 pp 162ndash167 1963

[42] V F Stroganov V N Savchenko and G D Tizkij ldquoAmi-nolysis of 1-phenoxy-23-propylene carbonate benzylamine inchlorobenzenerdquo Journal of Organic Chemistry vol 24pp 501ndash504 1988 in Russian

[43] Y Smirnov B Komarov P Kushch T Ponomareva andV Lantsov ldquoStructural and kinetic features of formation ofhigh-strength epoxy-amine cross-linked polymers by com-bined polycondensation-polymerization processrdquo RussianJournal of Applied Chemistry vol 75 no 2 pp 265ndash2752002


[44] Y S Lipatov ldquoInterfacial regions in the phase-separatedinterpenetrating networksrdquo Polymer Bulletin vol 58 no 1pp 105ndash118 2007

[45] Y S Lipatov R A Veselovsky and Y K Znachkov ldquoSomeproperties of glues based on interpenetrationg polymerisnetworksrdquo Journal of Adhesion vol 10 no 2 pp 157ndash1611979

[46] V F Stroganov V M Mihalchuk and V M Lanzov ldquoStudy ofmolecularmobility during the curing of diphenylolpropane-13-bis(aminomethyl) adamant digymondyl ether systemrdquo RussianAcademy of Sciences vol 291 pp 908ndash912 1986 in Russian

[47] V A Bershtein N N Peschanskaya J L Halary andL Monnerie ldquoe sub-Tg relaxations in pure and anti-plasticized model epoxy networks as studied by high reso-lution creep rate spectroscopyrdquo Polymer vol 40 no 24pp 6687ndash6698 1999


CorrosionInternational Journal of

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Analytical ChemistryInternational Journal of


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TribologyAdvances in



ChemistryAdvances in


Advances inPhysical Chemistry


BioMed Research InternationalMaterials

Journal of


Na

nom

ate

ria

ls


Journal ofNanomaterials

Submit your manuscripts atwwwhindawicom

fragments (atoms and atomic groups) on the realizingpossibility for each known type of the intermolecular in-teractions (physical bonds grid) In the chemical structure ofpolymers the elemental composition of structural units thetype and position of functional groups and the congura-tion and conformation of polymer chains characterize theirmolecular level

e topological structure characterizes the cohesion andbranching in a reticular polymer which can be representedas a macroscopic molecule combining a system of cyclicstructures with a system of dierent internode chains dis-tributed throughout the volume Such a molecule can berepresented as an innite graph [16] Within the frameworkof this representations the concept of nodes (cs) chains (nc)or the average static mass of the chain interstitial segment(Mc) is the main characteristics of the topological struc-ture under the assumption of ideal networks (tetrahedralcubic etc) e presence of topological defects (grid ir-regularity chain ineshyciency closed loops and unbound solfraction) is a characteristic dierence of real structures inreticular polymers from ideal ones It has been shown thatfor epoxy-amine polymers the main types of chemicaldefects are ldquofree endsrdquo and topological ones are chemicalassemblies that have dierent connectivity with the wiremesh [19] e abovementioned topological elements of thestructure (IndashV) can be conditionally classied 3- and 4-related nodes (I II) forming a grid 2-connected nodes (III)of linear fragments 1-bound (IV) nodes of free ends andsol-fraction connections (V) ese defects cause a decreaseof degree of conversion for the reactive groups to the valuesof αtoplim 92ndash93 (topological limit) at theoretical limitvalues αtheorlim 97-98 for three-dimensional grid models Itis generally accepted that these characteristics determine thebasic properties of network polymers [3 20 21]

e supramolecular structure is determined by the na-ture of intermolecular interactions of chemical structuralelements lateral active chains and the degree of ordering intheir mutual arrangement e nature of the intermolecularinteraction in epoxy polymers is determined by the presenceof polar atoms groupings and their interaction in the to-pological grid fragments (IndashIV) e following types ofintermolecular interactions are distinguished in polymers[22] dispersion inductive dipole and hydrogen bondsese named interactions form a labile spatial grid (witha stable network of covalent bonds) In particular in denselycross-linked epoxy polymers the physical grid of hydrogenbonds exceeds the concentration of chemical assemblies by2ndash4 times reaching densities up to 4times1021 1cm3 [23 24]e role of the hydrogen bond between the oxygen atoms ofthe oxirane ring and the hydrogen for hydrogen bonding ofthe hydroxyl group during the aminolysis of epoxy com-pounds has been considered in a number of works eresults of calculating the distribution of hydrogen-bondedgroups and the types of H-bonds are considered in detail in[25] Based on the literature data the authors believe that thedening inuence on the topological structure formation ofthe network polymers has the formation of an intra-molecular hydrogen bond between the epoxy and hydroxylgroups of the following type [26]

CH2 CH2 CH2

CHCHO

CHOH

O

O

RR N (1)

Formation of an intracellular bond system with hy-drogen bonds leads to the strengthening and ordering thespatial network of cured epoxy oligomers [27] Pochan et al[28] associate relatively high values of crystallizationtemperature Tc and destructive loading of polymers withintermolecular hydrogen bonds formed by hydroxylgroups

C

CC

O

OHH

(2)

Despite the contradictory nature of these researchers theprevailing view is that the inuence of intermolecular in-teractions is multifacetedis approach explains and causeswide possibilities for modifying the properties of epoxy-amine network polymers also due to covalent and physicalbonds

e presented data make possible the representation ofthe epoxy polymer structure as a superposition of two gridsa covalent bonds network characterized by inhomogeneity atthe molecular and topological levels and a thermouctuationphysical bonds grid caused by the realization of all possibletypes of intermolecular interactions groups and grid fragmentatoms e presented model assumes the possibility of reg-ulating the molecular mobility of network polymers due toa change in the chemical structure (the nature of the nodeinternodal fragments and their kinetic exibility polarity ofgroups etc) Numerous studies on the eect of the chemicalstructure and properties of epoxy polymers show thatchanging the initial oligomers nature hardeners and theirratio can aect the structure and physicomechanical prop-erties of epoxy polymers and materials based on them

By analyzing the properties of epoxy polymeric materialcomplexes the ldquobrittlenessrdquo of epoxide-amine polymersobtained with amine curing without additional heat input(such compositions are often used in practice in varioustechnologies) should be noted as a considerable disadvan-tage is drawback is due to an inhibition of the aminolysisreaction a decrease in the degree of reactive group con-version αtoplim and as a result a signicant reduction in thelevel of cohesive (σc εc) and adhesive strength (σa τa) It isknown that aliphatic chains increase the exibility of denselycross-linked epoxy-amine polymers eir conformationalset and kinetic exibility are practically independent fromlocation of these chains (eg in the oligomer molecule inthe linear polymer chain or in the mesh polymer) isprovision is very important since it indicates the funda-mental inuence of the initial molecule structure of oligo-mers and hardeners on the cured polymer propertiesAmong the main factors regulating the molecular level of thestructure the reactivity of the initial components (thepresence of functional groups in the oligomer the hardener











CH2-OOHO-CH2

O=C C=O

(3)










Tabl

e1

Characteristicsof

OEC

Cbasedon

epoxyoligom

ers

echem

ical

nature

ofepoxyoligom

ers(epoxy

number(

))

Radicals

reectingthenature

ofthe

OEC

CR

Con

ditio

nal

abbreviatio

nof

OEC

C

Con

tent

ofepoxy

grou

ps(

)(residual)

Sapo

nicationnu

mber

(mgKOHg)

Visc

osity

at25

deg C(Pamiddots

)

T m (deg C)

Density

20deg C

(gcm3)

App

earance

Determined

Calculated

Epoxidated

oligom

erED

-20(216

)based

onbispheno

l-A

СН3

СН3

CDCCED-20

010

452

459

mdash55

mdash

Ahard

brittle

massof

yello

wcolor(brown-

white

powderafter

grinding

)

Diglycidylo

ligom

erbasedon

diethylene

glycol

DEG

-1(268

)

ndashСН

2ndashСН

2ndashОndashС

Н2ndashСН

2ndashDCCD

EG-1

017

552

560

112

mdash14762

Low-visc

osity

liquidof

yello

wish

color

Diglycidylo

ligom

erbasedon

diprop

ylene

glycol

(255

)СН

3СН

3

-СН

2-СН

-О-С

Н-С

Н2-

DCCD

PG016

530

535

185

mdash14722

Liqu

idof

yello

wish

color

Diglycidylo

ligom

erbasedon

11-di

(oxymethyl)-3-

cycloh

exene(250

)

-СН

2СН

2-

DCCD

OC

006

555

560

2610

mdash14960

Visc

ousliquidof

cherry

color

Epoxyoligom

erbased

onepichloroh

ydrin


-E-181

(259

)

СН2-

СН-С

Н2-

О (С

Н2-

CH-O

) СН

2-CH

-СН

2

OO

C=O

СН2C

lO

OC=

ODCCE-181

010

524

522

1704

mdash14906

Visc

ousliquidof

cherry

color














T2a



t

T2c1113888 1113889

(5)










K 166]LD2( )



dx

dτ K middotXY (8)





CH2-O


CH2-O

R-CH-OC=O

(9)





CH2-O

CH-O

R

OH-NH-Rprime

H

H


OOH

Rprime

NH-Rprime

NH

C

(11)











TABLE 2






100

80

60

40

201 2

34

0 6 12 18 24t (h)

(Dt 92

0D

0 920)

middot100

()

(a)

100

80

60

40

202

34

5

(Dt 16

02D

0 1602

)middot10

0 (

)

0 6 12 18 24t (h)

(b)








Composition


Curing 7 dat 22degC



100

80

60

40

20

2prime

1 2

1prime

0 4 8 12 16 20 24t (h)

(Dt 92

0D

0 920)

middot100

()
















5 Discussion


2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime





σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls













CH2-OOHO-CH2

O=C C=O

(3)










Tabl

e1

Characteristicsof

OEC

Cbasedon

epoxyoligom

ers

echem

ical

nature

ofepoxyoligom

ers(epoxy

number(

))

Radicals

reectingthenature

ofthe

OEC

CR

Con

ditio

nal

abbreviatio

nof

OEC

C

Con

tent

ofepoxy

grou

ps(

)(residual)

Sapo

nicationnu

mber

(mgKOHg)

Visc

osity

at25

deg C(Pamiddots

)

T m (deg C)

Density

20deg C

(gcm3)

App

earance

Determined

Calculated

Epoxidated

oligom

erED

-20(216

)based

onbispheno

l-A

СН3

СН3

CDCCED-20

010

452

459

mdash55

mdash

Ahard

brittle

massof

yello

wcolor(brown-

white

powderafter

grinding

)

Diglycidylo

ligom

erbasedon

diethylene

glycol

DEG

-1(268

)

ndashСН

2ndashСН

2ndashОndashС

Н2ndashСН

2ndashDCCD

EG-1

017

552

560

112

mdash14762

Low-visc

osity

liquidof

yello

wish

color

Diglycidylo

ligom

erbasedon

diprop

ylene

glycol

(255

)СН

3СН

3

-СН

2-СН

-О-С

Н-С

Н2-

DCCD

PG016

530

535

185

mdash14722

Liqu

idof

yello

wish

color

Diglycidylo

ligom

erbasedon

11-di

(oxymethyl)-3-

cycloh

exene(250

)

-СН

2СН

2-

DCCD

OC

006

555

560

2610

mdash14960

Visc

ousliquidof

cherry

color

Epoxyoligom

erbased

onepichloroh

ydrin


-E-181

(259

)

СН2-

СН-С

Н2-

О (С

Н2-

CH-O

) СН

2-CH

-СН

2

OO

C=O

СН2C

lO

OC=

ODCCE-181

010

524

522

1704

mdash14906

Visc

ousliquidof

cherry

color














T2a



t

T2c1113888 1113889

(5)










K 166]LD2( )



dx

dτ K middotXY (8)





CH2-O


CH2-O

R-CH-OC=O

(9)





CH2-O

CH-O

R

OH-NH-Rprime

H

H


OOH

Rprime

NH-Rprime

NH

C

(11)











TABLE 2






100

80

60

40

201 2

34

0 6 12 18 24t (h)

(Dt 92

0D

0 920)

middot100

()

(a)

100

80

60

40

202

34

5

(Dt 16

02D

0 1602

)middot10

0 (

)

0 6 12 18 24t (h)

(b)








Composition


Curing 7 dat 22degC



100

80

60

40

20

2prime

1 2

1prime

0 4 8 12 16 20 24t (h)

(Dt 92

0D

0 920)

middot100

()
















5 Discussion


2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime





σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls




Tabl

e1

Characteristicsof

OEC

Cbasedon

epoxyoligom

ers

echem

ical

nature

ofepoxyoligom

ers(epoxy

number(

))

Radicals

reectingthenature

ofthe

OEC

CR

Con

ditio

nal

abbreviatio

nof

OEC

C

Con

tent

ofepoxy

grou

ps(

)(residual)

Sapo

nicationnu

mber

(mgKOHg)

Visc

osity

at25

deg C(Pamiddots

)

T m (deg C)

Density

20deg C

(gcm3)

App

earance

Determined

Calculated

Epoxidated

oligom

erED

-20(216

)based

onbispheno

l-A

СН3

СН3

CDCCED-20

010

452

459

mdash55

mdash

Ahard

brittle

massof

yello

wcolor(brown-

white

powderafter

grinding

)

Diglycidylo

ligom

erbasedon

diethylene

glycol

DEG

-1(268

)

ndashСН

2ndashСН

2ndashОndashС

Н2ndashСН

2ndashDCCD

EG-1

017

552

560

112

mdash14762

Low-visc

osity

liquidof

yello

wish

color

Diglycidylo

ligom

erbasedon

diprop

ylene

glycol

(255

)СН

3СН

3

-СН

2-СН

-О-С

Н-С

Н2-

DCCD

PG016

530

535

185

mdash14722

Liqu

idof

yello

wish

color

Diglycidylo

ligom

erbasedon

11-di

(oxymethyl)-3-

cycloh

exene(250

)

-СН

2СН

2-

DCCD

OC

006

555

560

2610

mdash14960

Visc

ousliquidof

cherry

color

Epoxyoligom

erbased

onepichloroh

ydrin


-E-181

(259

)

СН2-

СН-С

Н2-

О (С

Н2-

CH-O

) СН

2-CH

-СН

2

OO

C=O

СН2C

lO

OC=

ODCCE-181

010

524

522

1704

mdash14906

Visc

ousliquidof

cherry

color














T2a



t

T2c1113888 1113889

(5)










K 166]LD2( )



dx

dτ K middotXY (8)





CH2-O


CH2-O

R-CH-OC=O

(9)





CH2-O

CH-O

R

OH-NH-Rprime

H

H


OOH

Rprime

NH-Rprime

NH

C

(11)











TABLE 2






100

80

60

40

201 2

34

0 6 12 18 24t (h)

(Dt 92

0D

0 920)

middot100

()

(a)

100

80

60

40

202

34

5

(Dt 16

02D

0 1602

)middot10

0 (

)

0 6 12 18 24t (h)

(b)








Composition


Curing 7 dat 22degC



100

80

60

40

20

2prime

1 2

1prime

0 4 8 12 16 20 24t (h)

(Dt 92

0D

0 920)

middot100

()
















5 Discussion


2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime





σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls
















T2a



t

T2c1113888 1113889

(5)










K 166]LD2( )



dx

dτ K middotXY (8)





CH2-O


CH2-O

R-CH-OC=O

(9)





CH2-O

CH-O

R

OH-NH-Rprime

H

H


OOH

Rprime

NH-Rprime

NH

C

(11)











TABLE 2






100

80

60

40

201 2

34

0 6 12 18 24t (h)

(Dt 92

0D

0 920)

middot100

()

(a)

100

80

60

40

202

34

5

(Dt 16

02D

0 1602

)middot10

0 (

)

0 6 12 18 24t (h)

(b)








Composition


Curing 7 dat 22degC



100

80

60

40

20

2prime

1 2

1prime

0 4 8 12 16 20 24t (h)

(Dt 92

0D

0 920)

middot100

()
















5 Discussion


2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime





σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls








K 166]LD2( )



dx

dτ K middotXY (8)





CH2-O


CH2-O

R-CH-OC=O

(9)





CH2-O

CH-O

R

OH-NH-Rprime

H

H


OOH

Rprime

NH-Rprime

NH

C

(11)











TABLE 2






100

80

60

40

201 2

34

0 6 12 18 24t (h)

(Dt 92

0D

0 920)

middot100

()

(a)

100

80

60

40

202

34

5

(Dt 16

02D

0 1602

)middot10

0 (

)

0 6 12 18 24t (h)

(b)








Composition


Curing 7 dat 22degC



100

80

60

40

20

2prime

1 2

1prime

0 4 8 12 16 20 24t (h)

(Dt 92

0D

0 920)

middot100

()
















5 Discussion


2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime





σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls





CH2-O

CH-O

R

OH-NH-Rprime

H

H


OOH

Rprime

NH-Rprime

NH

C

(11)











TABLE 2






100

80

60

40

201 2

34

0 6 12 18 24t (h)

(Dt 92

0D

0 920)

middot100

()

(a)

100

80

60

40

202

34

5

(Dt 16

02D

0 1602

)middot10

0 (

)

0 6 12 18 24t (h)

(b)








Composition


Curing 7 dat 22degC



100

80

60

40

20

2prime

1 2

1prime

0 4 8 12 16 20 24t (h)

(Dt 92

0D

0 920)

middot100

()
















5 Discussion


2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime





σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls







100

80

60

40

201 2

34

0 6 12 18 24t (h)

(Dt 92

0D

0 920)

middot100

()

(a)

100

80

60

40

202

34

5

(Dt 16

02D

0 1602

)middot10

0 (

)

0 6 12 18 24t (h)

(b)








Composition


Curing 7 dat 22degC



100

80

60

40

20

2prime

1 2

1prime

0 4 8 12 16 20 24t (h)

(Dt 92

0D

0 920)

middot100

()
















5 Discussion


2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime





σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls

















5 Discussion


2

6

8

10

12

1430

32

42

44

tan

δ middot 1

02

1

1prime

2

2prime3

3

3

2prime





σr(MPa)

εr()

τc(MPa)

σrp(MPa)

Ts






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls






Р а

0

02

04

06

0 20 40 60 80 100t (h)

bprime

0

02

04

06

0 20 40 60 80 100

Р а

Р аР а

аprime

t (h)

0

02

04

06

0 20 40 60 80 100

cprime

t (h)

0

02

04

06

0 20 40 60 80 100t (h)

dprime

0 20 40 60 80 100 120

c

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

а

t (h)

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120t (h)

b

1

2

3

4

5

Lg (T

2)

0 20 40 60 80 100 120

t (h)

d

1

2

3

4

5

Lg (T

2)








1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls









1

2

3

4

5

0 20 40 60 80 100Lg

(T2)

t (h)

a

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5b

Lg (T

2)

t (h)0 20 40 60 80 100

1

2

3

4

5c

0 20 40 600

02040608 bprime

Р а

t (h)

002040608

0 20 40 60

Р а

t (h)

aprime

Р а

t (h)0 20 40 60

02040608 cprime


1

2

3

4

5

0 40 80 120 160 200

Lg (T

2)

T (degC)

2prime

3prime

321



OECCtype






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls






6 Conclusions


0

20

40

60

80

100

0 10 20 30OECC ()

2 3

14

5σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC

)

(a)σ р

о σ

р τ в

(MPa

) ε p

() T c

(degC)

0

20

40

60

80

100

120

0 20 40 60OECC ()

2

3

1

45

(b)


20

40

60

80

100

60

σ р (M

Pa)

OECC ()

2

3

1

20 400


10

20

30

40

50

0 20 40 60

σ ро

τв (

MPa

)

OECC ()

3prime

2prime

1prime132




Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls





Data Availability




Acknowledgments


References









0

20

40

60

80

100

0 20 40 60 80DEG-1 ()

23

5

4

1

σ ро

σр τ в

(MPa

) ε p

() T c

(degC)


0

20

40

60

80

0 20 40 60DCCED-20 ()

2

3

1

4

σ ро

σр τ в

(MPa

) ε p

()















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls
















































Advances in



Journal of

Chemistry















Journal of





Volume 2018









Journal of


Na

nom

ate

ria

ls




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