Research Article Copolymerization of 4-Acetylphenyl...

Research ArticleCopolymerization of 4-Acetylphenyl Methacrylate with EthylMethacrylate Synthesis Characterization Monomer ReactivityRatios and Thermal Properties

Gamze Barim1 and Mustafa Gokhun Yayla2

1 Department of Chemistry Faculty of Science and Arts University of Adiyaman 02040 Adiyaman Turkey2 Physics Engineering Department Faculty of Science and Letters Istanbul Technical University Maslak 34469 Istanbul Turkey

Correspondence should be addressed to Gamze Barim gbarimgmailcom

Received 27 August 2013 Revised 2 November 2013 Accepted 3 November 2013 Published 4 February 2014

Academic Editor Giridhar Madras

Copyright copy 2014 G Barim and M G Yayla This 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 is properlycited

Methacrylates have high glass transition temperature (119879119892) values and high thermal stability A newmethacrylate copolymer poly(4-

acetylphenyl methacrylate-co-ethyl methacrylate) (APMA-co-EMA) was synthesized The thermal behaviors of copolymers wereinvestigated by differential scanning calorimetry and thermogravimetric analysisThey behaved as new single polymers with single119879119892rsquos and the thermal stability of the copolymers increased with increasing 4-acetylphenyl methacrylate (APMA) fraction leading

to the manufacture of copolymers with desired 119879119892values Structure and composition of copolymers for a wide range of monomer

feed ratios were determined by Fourier transform infrared (FT-IR) and 1H-nuclear magnetic resonance (1H-NMR) spectroscopictechniques Copolymerization reactions were continued up to 40 conversions The monomer reactivity ratios for copolymersystem were determined by the Kelen-Tudos (119903

119886(APMA) = 081 119903119887(EMA) = 061) and extended Kelen-Tudos (119903

119886= 077 119903

119887= 054)

methods and a nonlinear least squares (119903119886= 074 119903

119887= 049) method

1 Introduction

In recent years many studies have been carried on aromaticacrylate and methacrylate monomers and polymers [1ndash4]They are highly reactivemonomers because of the presence ofthe aromatic ring and thus form an interesting class ofpolymers [5ndash7] Poly(phenyl methacrylates) have higherthermal stability and gainmuch interest due to their potentialindustrial uses [8ndash10] Copolymers of phenyl methacrylatewith various acrylates are reported as adhesives for leather tocloth bonding [11ndash15] Poly(phenyl methacrylate)s are harderpolymers of higher tensile strength and find applicationsin pressure-sensitive photo imaging materials [16] and inelectrophotographic photoreceptors for offset printing plates[17] Other uses include photo luminescent [18] photo resis-tive [19] photosensitive materials [20] biomaterials [21 22]optical telecommunication materials [23] and a polymersupported catalyst [24]

The chemical composition of the copolymers and distri-bution of the monomer units on the chain depend on theirincorporation rates which in turn depend on their reactivityratios Monomer reactivity ratios are essential quantitativevalues to predict the copolymer composition for any startingfeed ratio and to understand the kinetic and mechanisticaspects of copolymerization [25ndash27]

To the best of the authorrsquos knowledge there are no reportsin the literature on APMA with ethyl methacrylate (EMA)copolymerization Reddy et al have investigated the copoly-merization of another phenylmonomer (n-phenylmethacry-lamide) with EMA [28] Roy et al have investigated the RAFTcopolymerization of NN-(dimethylamino)ethyl methacry-late and methyl methacrylate [29] There are also studiesrelated to the synthesis and reactivity ratios of copolymersof APMA with glycidyl methacrylate [30] All these studieswere low conversion investigations On the other hand theindustry always works at moderate or high conversionThere

Hindawi Publishing CorporationInternational Journal of Polymer ScienceVolume 2014 Article ID 643789 10 pageshttpdxdoiorg1011552014643789

2 International Journal of Polymer Science

C

C O

O

C O

C

C O

O

C

C O

O

C O

C

C O

O

C

C O

O C

O

C

O

HO C

C O

Cl

CH3 CH3

CH3 CH3

CH3

CH3

CH3

CH2

CH3 CH3

CH3

H2C

H2C H2C

H2C H2C

+

+

C2H5

AIBN 14-dioxane

70∘C

CH2CH3

n

NR3

0ndash5∘C

Scheme 1 Synthesis of APMA and poly(APMA-co-EMA)

are no moderate or high conversion investigations related todetermining reactivity ratios of APMA-co-EMA system

For this reason in this study the synthesis and character-ization of copolymers of APMA with EMA are investigatedat moderate conversion The monomer reactivity ratios arecalculated using three different methods Kelen-Tudos (KT)[31] extended Kelen-Tudos (EKT) [32] and a nonlinear leastsquares (NLLS) [33] The EKT and the NLLS methods takethe composition drift into account and are suitable for highconversion experiments

119879119892rsquos of new copolymers and the effect of APMA contenton the thermal properties of resulting copolymers are alsoinvestigated

2 Experimental

21 Materials 4-Hydroxy acetophenone (Aldrich) andmethacryloyl chloride (Merck) were used as received EMAwas freed from inhibitor by being washed with 5 sodiumhydroxide solution several times followed by being washedwith distilled water and then was dried over anhydroussodium sulphate subsequently it was distilled under reducedpressure 2-21015840-Azobisisobutyronitrile (AIBN) was recrystal-lized from chloroform and methanol mixture 14-Dioxanetriethylamine tetrahydrofuran (THF) sodium hydroxidesodium sulphate (Merck) and ethanol (Merck) were ofanalytical grade and were used as received

22 Synthesis of 4-Acetylphenyl Methacrylate APMA mon-omerwas prepared from reaction of 4-hydroxy acetophenonewith methacryloyl chloride in the presence of triethylamineand THF at 0 to 5∘C range [26] (Scheme 1 the first row)

The monomer was characterized by FT-IR and 1H-NMRspectra as follows

IR (cmminus1) 3100 and 3070 (=CH) 2988 and 2848 (CndashHstretching) 1731 (C=O in ester) 1673 (C=O in ketone)1635 (CH2=C) 1596 (C=C on aromatic ring) 1200and 1165 respectively (OndashC=O and OndashCndashC)1H-NMR (120575 ppm CDCl3) 800 and 722 (protons onaromatic ring) 638 and 581 (CH2=C) and 191 (CH3protons)

23 Homopolymerization andCopolymerization Homopoly-merization and copolymerization reactions were carried outin 14-dioxane solution at 70∘C using AIBN (1 based onthe total weight of the monomers) as the initiator (Scheme 1the second row) Required amounts of APMA and EMAwith 14-dioxane and AIBN were mixed in a polymerizationtube purged with N2 atmosphere for 15min Polymerizationwas performed at 70∘C in a thermostatic oil bath After 3hours the copolymerswere precipitated in excess ethanol andfiltered The precipitated polymers were purified by repeatedreprecipitation from chloroform solution using ethanol andfinally dried in a vacuum oven at 40∘C for 24 hours Theconversion was determined by gravimetric measurementsThe reaction scheme of the copolymer is shown in Scheme 1Initial monomer compositions and copolymer conversionsare given in the second third and fourth columns andfinal monomer compositions are given in the fifth and sixthcolumns of Table 1

24 Polymer Characterization Infrared spectra were obtain-ed with a Perkin Elmer Spectrum One FT-IR system andrecorded using universal ATR sampling accessory within

International Journal of Polymer Science 3

Table1Mon

omer

andcopo

lymer

compo

sitiondatam

olecular

weights

andPI

indiceso

fcop

olym

ers

Expno

Initialmon

com

positions

conversio

nFinalm

oncom

positions

119862

Cop

olym

ercompo

sition

from

1 HNMR

Cop

olym

ercompo

sitions

from

FTIR

Molecular

weights

[119860]

[119861]

[119860]fin

[119861]fin

APM

A119875119860

EMA

119875119861

APM

A119875119860

EMA

119875119861

119872119899

PI

1010

090

33007

060

0179

015

085

018

082

8900

013

72

020

080

33013

054

0340

025

075

027

073

mdashmdash

3035

065

31024

045

0615

038

062

038

062

107800

144

050

050

36032

032

1298

056

044

050

050

mdashmdash

5070

030

37044

019

2500

071

029

066

034

112000

128

6090

010

38056

006

7690

088

012

081

019

11900

012

5


the wavelengths of 4000ndash650 cmminus1 1H-NMR spectra ofcopolymers were recorded in deuterated chloroform (CDCl3)solution on a 400MHz Bruker AVIII 400 using tetramethyl-silane as an internal reference

The molecular weights and polydispersity index (PI)of all polymers were determined by using gel permeationchromatography (GPC)The GPC consisted of an Agilent IsoPump a refractive index detector and both Mixed ldquoDrdquo andMixed ldquoErdquo columns (ex Polymer Labs) THF was used asthe eluent and poly(methyl metacrylate)s were employed asstandards for calibration

The glass transition temperatures were measured by aShimadzu DSC 50 thermal analyzer under nitrogen atmo-sphere at a heating rate of 10∘CminThermal stabilities of thepolymers were investigated with a Perkin Elmer TGADTA7300

3 Results and Discussion1H-NMR spectra of homo- and copolymers are given inFigure 1 The chemical shifts assignments for the copolymerswere based on the chemical shifts observed for the respectivehomopolymers In the copolymers the resonance signals ofaromatic protons were shown between 800 and 728 ppmAnd the peak at 406 ppm is due to the OCH2 protons ofEMA unit Copolymer compositions were calculated frompeak integrations of 1H-NMR signalsThus themole fractionof APMA in copolymer was determined by measuring theintegrated peak areas of the aromatic protons of APMAat 800 ppm which is adjacent to the carbonyl and OCH2protons of EMA at 406 ppm The following equation wasused to determine the composition of copolymers

Let 119875119860 be the mole fraction of APMA unit and 119875119861 = (1 minus119875119860) that of the EMA unit

2119875119860

2 (1 minus 119875119860)

=Integral intensities of aromatic protons adjacent to the carbonyl

Integral intensities of OCH2 protons

= 119862

(1)

On simplification

119875119860 =119862

119862 + 1 (2)

The value of119862 corresponding mole fractions of APMA in thecopolymer is given in the seventh column of Table 1

FT-IR spectra of homo- and copolymers are given inFigure 2 In the copolymers the peaks at 1751 and 1724 cmminus1were attributed to the ester carbonyl stretching of APMAand EMA units respectively Besides the ketone carbonylstretching shows absorption band at 1685 cmminus1 APMA unitsIn the IR spectrum the ester carbonyl stretching vibra-tion in APMA shifted from 1731 cmminus1 to 1751 cmminus1 dueto removal of conjugation with polymerization Copolymercompositions were also determined from IR technique Theabsorption ratios between characteristic analytical bands of

1685 cmminus1 (for APMA unit) and 1724 cmminus1 (for EMA unit)(119860 = log(119868119900119868)) and the least changing absorption band of1357 cmminus1 as a standard band were used to determine thecopolymer compositions Copolymer compositions were cal-culated from FT-IR using

119875119860 =Δ1198601685

119872APMAΔ1198601685119872APMA + Δ119860

1724119872EMA100

119875119861 =Δ1198601724

119872EMAΔ1198601685119872APMA + Δ119860

1724119872EMA100

(3)

where Δ119860 = 1198601198941198601357 (least changing standard band) and

119872APMA and119872EMA aremolecular weights of APMA and EMAmonomer units respectively

Copolymer compositions determined byNMR technique[27] are given in the eighth and ninth columns of Table 1 andIR technique [34] is given in the tenth and eleventh columnsof Table 1The slight discrepancies between the solutionNMRand solid state FTIR measurements can be attributed toinhomogeneity of the solid sample and other measurementerrors

The number average molecular weights (Mn) and poly-dispersity index (PI) of the polymer samples are given inthe last two columns of Table 1 The molecular weightsincreased with increasing percentage of APMA in the feedcomposition The molecular weights of the monomers are204 gmol (APMA) and 114 gmol (EMA) APMA is about80 heavier The higher molecular weights of the polymerswith higher APMA content are due to this difference Thepolydispersity index of the copolymers ranged from 125to 14 The value of polydispersity index means that thechain termination of polymers takes place predominantly bycoupling rather than by disproportionation [35]

31 Monomer Reactivity Ratios The ratio of the rates of entryof the comonomers is given by the Mayo-Lewis copolymer-ization equation [36]

119889 [119860]

119889 [119861]=[119860]

[119861](119903119886 [119860] + [119861])

([119860] + 119903119887 [119861]) (4)

Here [119860] that represents APMAand [119861] that represents EMAare the molar concentrations of the two comonomers in thefeed and 119889[119860]119889[119861] is the molar ratio of the two monomersentering the copolymer The parameters 119903119886 that representsthe reactivity ratio of APMA and 119903119887 that represents EMA areknown as the monomer reactivity ratios The composition ofthe copolymer depends not only on the feed composition butalso on these two parameters For this reason the knowledgeof these ratios is essential for the manufacture of copolymersof desired properties

Designating the initial monomer ratio by 119883 = [119860][119861]

and resulting copolymer ratio by 119884 = 119889[119860]119889[119861] furtherarranging 119883 and 119884 in the form of 119866 = 119883(119884 minus 1)119884 119865 =

1198832119884 and 120572 = radic119865min sdot 119865max and using 120578 = 119866(120572 + 119865) and

120585 = 119865(120572 + 119865) Mayo-Lewis equation is transformed into thelinearized Kelen-Tudos version

120578 = (119903119886 +119903119887

120572) 120585 minus

119903119887

120572 (5)


CC

C O

a

c

c

O

CH2

CH2

CH2

CH3

CH3

CH3

11234(ppm)

(ppm)

(ppm)

567891011

CH3 CH3

H2C C CCH2

C COO

OO

a

a

b

b

ab

C O

CH3

038 062

P(APMA-co-EMA)

P(EMA)

056 044

12345678910

12345678910

(ppm)12345678910

(ppm)12345678910

(ppm)12345678910

071 029

088 012

CCO

Oa

CH3

CH2

C OCH3

ab

ab

P(APMA)

ab

Figure 1 1H-NMR spectra of homopolymer and copolymers


P(APMA)

P(APMA-co-EMA)088 012

071 029

056 044

038 062

4000 2800 1800 1200 650

T(

)

Wavenumber (cmminus1)

Figure 2 IR spectra of homopolymer and copolymers

Table 2 KT parameters for APMA-co-EMA copolymer system

Polymer 119883 119884 119866 119865 120578 120585

1 011 017 minus0518 0069 minus0586 00732 025 033 minus0500 0187 minus0432 01753 053 058 minus0382 0495 minus0152 03604 100 127 0214 0785 0015 04725 233 244 1380 2223 0385 07166 900 733 7772 11050 0702 0926120572 = 087905

Table 3 Extended KT parameters for APMA-co-EMA copolymersystem

Polymer 1205851

1205852

119885 119865 119866 120578 120585

1 0493 0310 1828 005 minus045 minus0572 00602 0411 0308 1436 016 minus046 minus0423 01653 0334 0308 1105 047 minus037 minus0132 03694 0403 0317 1354 069 020 minus0004 04595 0375 0357 1062 216 136 0376 07266 0371 0456 0763 1250 830 0680 0939120572 = 081562

The parameters of KT and EKT equations are presented inTables 2 and 3 The KT plot is given as Figure 3 The KTcoefficient 120572 = 087 indicates that the experimental planningwas good The data lie on the straight line with very littlescatter The monomer reactivity ratios are found as 119903119886 = 081and 119903119887 = 061 The KT method has the advantages thatthe data are uniformly distributed and the results do notdepend on which monomer is labeled monomer (119860) andwhich is labeled monomer (119861) Its disadvantage is that ituses the initial ratio of the two monomers rather than thereaction weighted cumulative average When one monomerenters the reaction faster and is depleted more rapidly thanthe other the feed composition continuously drifts during thereaction The KT method fails to take into account this driftKelen and Tudos later proposed an extended version of theirmethod which takes the composition drift into account [32]Since the experiments are stopped at 30ndash40 conversion thecomposition drift can affect the results For this reason the

ξ

08

06

04

02

0

minus02

minus04

minus06

minus0801 02 03 04 05 06 07 08 09

KTEKT

120578

120585

Figure 3 KT and EKT plot for APMA-EMA copolymerization

data were reanalyzed using the extended Kelen-Tudos (EKT)method

EKT equation is the same as KT equation shown in(5) The difference between KT and EKT methods is thecalculation of 119865 and 119866 In EKT method they are calculatedthrough 119865 = 119884119885

2 119866 = (119884 minus 1)119885 where 119885 = log (1 minus1205851) log (1 minus 1205852) and 1205851 = [119860]0119889[119860] 1205852 = [119861]0119889[119861] Here[119860]0 and [119861]0 are the initial molar monomer fractions

The EKT plot is given in Figure 3The reactivity ratios arefound as 119903119886 = 077 and 119903119887 = 054

In the NLLSmethod used the data is fitted to a numericalsolution of theMayo-Lewis copolymerization equationThuserrors emanating from linearization are eliminated For each119903119886 119903119887 pair the copolymerization equation (4) is integratednumerically from initial monomer concentrations to finalconcentration ofmonomer (119861)The squares of the differencesof the final calculated value of the monomer (119860) from itsexperimental value

Δ [119860] = [119860]final experimental minus [119860]final calculated (6)

are added for each experiment and the chi-square for that setof monomer reactivity ratios are calculated

1205942=

119899

sum

119894=1

Δ[119860]2

119894

1205751198602 (7)

Here 120575119860 is the error bar for the relevant pointThe procedureis than repeated for each pair of 119903119886 and 119903119887 in the scanningrange The map thus produced is used for the best parameterestimate and the confidence intervals As the data is fitted tothe nonlinear Mayo equation itself and not to a linearizedform of it distortion of the error structure is avoided Theresulting contour map is given as Figure 4 and monomerreactivity ratios are found as 119903119886 = 074 and 119903119887 = 049

Using three separate methods to evaluate the reactivityratios ensures that no algorithmic errors are present In addi-tion the differences of monomer reactivity ratios calculated


09

085

08

075

07

065

0603 035 04 045 05 055 06 065 07

rb

r a

KTEKTNLLS

Figure 4 Probability contours and the best fit point (+) obtained byNLLS Results of EKT (Δ) and KT(lowast) are also shown on the graph

DataKT

EKTNLLS

90

80

70

60

50

40

30

20

10

09080706050403020100

[A]

[B]

Figure 5 Evolution of the concentrations of the comonomers for allexperiments The molar concentrations are given as percentages ofthe initial total molar concentration

by the three methods give an estimate on the dependence ofthe results on the method of evaluation and the weightingof data points by the three methods The EKT and NLLSresults are close to each other while the KT method givesslightly larger values (closer to one) Since the original KTmethod does not take composition drift into account and asthe conversions ranged up to 40 this is expected

Figure 5 shows the numerical integration of the copoly-merization equation beginning from the initial conditions foreach experiment using themonomer reactivity ratios given by

Table 4 The reactivity ratios calculated by the three methods

Monomer reactivity ratio KT EKT NLLS119903119886

081 077 074119903119887

061 054 049119886 APMA 119887 EMA

Hea

t flow

(mW

)0 50 100 150 200

5

minus5

(a)(b)(c)(d)

(e)(f)(g)

Figure 6 DSC thermograms of investigated copolymers (a)poly(APMA) APMA unit in copolymer (b) 088 (c) 056 (d) 038(e) 025 (f) 015 (g) poly(EMA)

the three calculation techniquesThe three lines starting fromeach initial point are the numerical integration results usingthe reactivity ratios calculated by the three methods and thesquares are the experimental data As themonomer reactivityratios found by the three methods are close the curvesare similar and although results differ from experiment toexperiment overall NLLS results give the best fit

The results are summarized in Table 4 As can be seenfrom the table EKT and NLLS results are nearly equal withKT results slightly higher (closer to one) This is because thecomposition drift is not taken into account by theKTmethod

The reactivity ratios found by the NLLS method are 119903119886 =074 119903119887 = 049 and their product is 119903119886sdot119903119887 = 036The reactivityratios published by Roy et al [29] are much closer to onethan our reactivity ratios presented in this paper (Table 4) sothat the copolymer in the referred work is in almost perfectlyrandom structure while here the product of the reactivityratios is 036 and there is a tendency to alternate

32 Glass Transition Temperature Differential scanningcalorimetry (DSC) curves of all the copolymers are shownin Figure 6 All of copolymers are observed to have a single119879119892 indicating the absence of a mixture of homopolymers orthe formation of a block copolymer The 119879119892 of poly(APMA)is at 146∘C and that of poly(EMA) is at 84∘C 119879119892 of copolymeris increased as the APMA fraction in the copolymer isincreased

33 Thermogravimetric Analysis (TGA) TGA thermogramsof the polymers were shown in Figure 7 The thermograms


Table 5 Thermal behaviour and decomposition temperatures of the copolymers and homopolymers

Polymer 119879119892(∘C) 119879max

a (∘C) IDTb (∘C) Temperatures (∘C) at selected weight loss10 30 50 70 90

P(APMA) 146 398 250 296 353 383 400 421P(APMA088) 138 275 256 271 309 370 396 422P(APMA071) 132 408 253 270 327 383 405 428P(APMA056) 125 404 253 272 350 387 407 436P(APMA038) 120 404 243 270 359 390 409 443P(EMA) 84 392 175 286 345 376 397 429aTemperature for maximum rate of decomposition bInitial decomposition temperature

50045040035030025020015010050

100908070605040302010

0

Wei

ght l

oss (

)

Temperature (∘C)

P(APMA)P(EMA)P(APMA 088)

P(APMA 071)P(APMA 056)P(APMA 038)

Figure 7 Thermal degradation curves of homo- and copolymers

clearly indicate that all the polymers undergo two stagesdecompositionThe thermal behavior of any polymer shouldbe affected appreciably by the introduction of a comonomerin the polymer chain Thus it was important to investigatethe thermal behavior of the prepared copolymers 119879119892rsquostemperatures for maximum rate of decomposition initialdecomposition temperatures and temperatures at selected weight loss are given in Table 5

For the study of the kinetics of the thermal degradation ofpolymers there can be selected isothermal thermogravimetry(ITG) or thermogravimetry (TG) at different heating rates[37] Although ITG is superior in obtaining an accurateactivation energy for thermal degradation in cases wheredepolymerization is competing with cyclization or crosslink-ing due to the side groups TG at different heating rates ismuch more convenient than ITG for the investigation ofthermal degradation kinetics Therefore in this study TGcurves at various heating rates have been obtained and theactivation energies (Δ119864119889) for the thermal degradation of thepolymers were calculated with Ozawa plots Degradationshave been performed in the scanningmode from35 to 500∘Cunder a nitrogen flow (20mLminminus1) at various heating rates(50 100 150 and 250∘Cminminus1) The TGA thermograms ofpoly(APMA) are given in Figure 8

50004000 4500300020001000 1500 2500 3500500

Wei

ght l

oss (

)

1000

500

600

700

800

900

100

200

300

400

00

Temperature (∘C)

5∘Cmin10∘Cmin

15∘Cmin25∘Cmin

(d)

(a)(b)

(c)

Figure 8 The thermal degradation curves of poly(APMA) atdifferent heating rates

According to the method of Ozawa [38] the apparentthermal decomposition activation energy 119864119889 can be deter-mined from the TGA thermograms under various heatingrates as in the following equation

119864119889 = minus119877

119887[119889 log120573119889 (1119879)

] (8)

Here 119877 has been the gas constant (8314 Jmol) 119887 is a constant(04567) and120573has been the heating rate (∘Cmin) Accordingto (8) the activation energy of degradation can be determinedfrom the slope of the linear relationship between log120573 andthe 1119879 As shown in Figure 9 the activation energy has beenfound as 186 kJmol

4 Conclusions

Copolymers of APMA with EMA were synthesized by freeradical polymerization The monomer reactivity ratios ofthe copolymers were calculated using KT EKT and linearand a nonlinear NLLS method The results show that bothmonomer reactivity ratios are less than one with APMA


0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T

Figure 9 Ozawa plots of the logarithm of the heating rate (120573)versus the reciprocal temperature (1000119879) at different conversionsfor poly(APMA)

the more active monomer All three methods gave consistentresults This leads to copolymers with a tendency for alterna-tion and a slight composition drift

Both molecular weights increased with increasing per-centage of APMA in the feed composition GPC data implythat the polydispersity index of the copolymers is between125 and 14 and this implies a strong tendency for chaintermination by coupling

The DSC analysis indicated that the 119879119892 of copolymersincreased with increase in APMA content The thermal sta-bility of the copolymers increased with the increase of APMAunits in the copolymer Initial decomposition temperature ofall copolymers is higher than that of poly(EMA) (Table 5)Decomposition energy (119864119889) of poly(APMA) was found as186 kJmol

Poly-EMA is a soft methacrylate polymer and poly-APMA is a hard and strong one Using the copolymer com-position and thermal analysis results together it is possible toobtain copolymers with desired thermal properties

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

Dr Gamze Barim acknowledges the financial support pro-vided by theAdiyamanUniversity Research Fund (Project noFEFBAP 2009-16)

References

[1] I Erol and S Kolu ldquoCopolymers of a new methacrylate mon-omer bearing oxime ester and ether with methyl methacrylatesynthesis characterization monomer reactivity ratios andbiological activityrdquo Journal of Applied Polymer Science vol 120no 1 pp 279ndash290 2011

[2] C Soykan A Delibas and R Coskun ldquoNovel copolymers of 4-chloronaphthyl methacrylate with acrylonitrile determinationofmonomer reactivity ratios and antimicrobial activityrdquo Journalof Macromolecular Science Part A vol 46 no 3 pp 250ndash2672009

[3] P S Vijayanand C S Unnithan A Penlidis and S NanjundanldquoCopolymerization of benzoylphenyl methacrylate with methylmethacrylate synthesis characterization and determination ofmonomer reactivity ratiosrdquo Journal of Macromolecular SciencePart A vol 42 no 5 pp 555ndash569 2005

[4] T Narasimhaswamy S C Sumathi and B S R Reddy ldquo4-acetylphenyl acrylate-glycidyl methacrylate copolymers syn-thesis characterization and reactivity ratiosrdquo European PolymerJournal vol 27 no 3 pp 255ndash261 1991

[5] K Demirelli E Kaya and M Coskun ldquoPolymers based onphenyl methacrylate synthesis via atom transfer radical poly-merization characterization monomer reactivity ratios andthermal stabilitiesrdquo Journal of Applied Polymer Science vol 99no 6 pp 3344ndash3354 2006

[6] O B Abdyev ldquoRadical copolymerization of glycidyl methacry-late and carbonyl-containing phenyl methacrylatesrdquo PolymerScience Series B vol 53 no 5-6 pp 278ndash282 2011

[7] G Kumar N Nisha S Mageswari and K SubramanianldquoSynthesis characterization of poly (4-benzyloxyphenylmeth-acrylate) and its copolymer with butyl methacrylate and deter-mination of monomer reactivity ratiosrdquo Journal of PolymerResearch vol 18 no 2 pp 241ndash250 2011

[8] S K Das and S Lenka ldquoPolymers from renewable resourcesXXIX Synthesis and characterization of interpenetrating net-works derived from castor-oil-based polyurethane-4-acetylphenyl methacrylaterdquo Polymer-Plastics Technology and Engi-neering vol 38 no 1 pp 149ndash157 1999

[9] U Senthilkumar R Balaji and S Nanjundan ldquoCopolymer-ization of 2-(n-phthalimido)ethyl methacrylate with glycidylmethacrylate synthesis characterization and monomer reac-tivity ratiosrdquo Journal of Applied Polymer Science vol 81 no 1pp 96ndash103 2001

[10] L J FMary andA V R Reddy ldquoSynthesis characterization andthermal properties of copolymers of 3-hydroxy-4-acetylphenylmethacrylate with methyl acrylaterdquo European Polymer Journalvol 27 no 7 pp 627ndash631 1991

[11] S Mageswari and K Subramanian ldquoSynthesis characteriza-tion and study of antibacterial activity of homopolymersand copolymers of 4-benzyloxyphenylacrylates for pressure-sensitive adhesive applicationrdquo Journal of Applied PolymerScience vol 125 no 4 pp 3115ndash3124 2012

[12] S Nanjundan C S Unnithan C S J Selvamalar and APenlidis ldquoHomopolymer of 4-benzoylphenyl methacrylate andits copolymers with glycidyl methacrylate synthesis character-izationmonomer reactivity ratios and application as adhesivesrdquoReactive and Functional Polymers vol 62 no 1 pp 11ndash24 2005

[13] P Samatha T Thimma Reddy P V S S Srinivas and NKrishnamurti ldquoEffect of addition of various acrylates on theperformance of ethyl cyanoacrylate adhesiverdquo Polymer-PlasticsTechnology and Engineering vol 39 no 2 pp 381ndash392 2000


[14] C S Jone Selvamalar P S Vijayanand A Penlidis and SNanjundan ldquoHomopolymer and copolymers of 4-benzyloxy-carbonylphenyl acrylate with glycidyl methacrylate synthesischaracterization reactivity ratios and application as adhesivefor leatherrdquo Journal of Applied Polymer Science vol 91 no 6pp 3604ndash3612 2004

[15] N Soto M Sanmiguel and F Vazquez ldquoSynthesis and char-acterization of water-borne adhesives based on 2-ethylhexyl-acrylate-butylacrylate copolyrners functionalized with acrylicacidrdquo International Journal of Polymeric Materials vol 54 no9 pp 871ndash881 2005

[16] P S Vijayanand C S J Selvamalar A Penlidis and S Nanjun-dan ldquoCopolymers of 35-dimethylphenyl acrylate and methylmethacrylate synthesis characterization and determination ofmonomer reactivity ratiosrdquo Polymer International vol 52 no12 pp 1856ndash1862 2003

[17] P G Vijayaraghavan and B S R Reddy ldquo4-Chlorophenyl acry-late and glycidyl methacrylate copolymers synthesis charac-terization reactivity ratios and applicationrdquo Journal of Macro-molecular Science Part A vol 36 no 9 pp 1181ndash1195 1999

[18] J L Hua J W Y Lam H Dong L Wu K S Wong and BZ Tang ldquoSynthesis light emission and photo-cross-linking ofluminescent polyacetylenes containing acrylic pendant groupsrdquoPolymer vol 47 no 1 pp 18ndash22 2006

[19] K Ichimura and Y Nishio ldquoPhotocrosslinkable polymers hav-ing p-phenylenediacrylate group in the side chain argon laserphotoresistrdquo Journal of Polymer Science Part A vol 25 no 6pp 1579ndash1590 1987

[20] R Balaji D Grande and S Nanjundan ldquoPhotoresponsivepolymers having pendant chlorocinnamoyl moieties synthesisreactivity ratios and photochemical propertiesrdquo Polymer vol45 no 4 pp 1089ndash1099 2004

[21] A Arun and B S R Reddy ldquoIn vitro drug release studies fromthe polymeric hydrogels based on HEA and HPMA using 4-(E)-[(3Z)-3-(4-(acryloyloxy)benzylidene)-2-hexylidene]met-hyl phenyl acrylate as a crosslinkerrdquo Biomaterials vol 26 no10 pp 1185ndash1193 2005

[22] S C Pandeya N Rathor and A Singh ldquoSynthesis and char-acterisation of biologically active barium containing polymerfilmsrdquo Journal of Polymer Materials vol 16 no 3 pp 253ndash2581999

[23] M Johnck L Muller A Neyer and J W Hofstraat ldquoCopoly-mers of halogenated acrylates and methacrylates for the appli-cation in optical telecommunication optical properties ther-mal analysis and determination of unsaturation by quantitativeFT-Raman and FT-IR spectroscopyrdquo European Polymer Journalvol 36 no 6 pp 1251ndash1264 2000

[24] R V Yarapathi S Kurva and S Tammishetti ldquoSynthesisof 34-dihydropyrimidin-2(1H)ones using reusable poly(4-vinylpyridine-co-divinylbenzene)-Cu(II)complexrdquo CatalysisCommunications vol 5 no 9 pp 511ndash513 2004

[25] N Ayaz F Bezgin and K Demırellı ldquoPolymers based onmethacrylate bearing coumarin group synthesis via free radicalpolymerization monomer reactivity ratios dielectric behaviorand thermal stabilitiesrdquo ISRN Polymer Science vol 2012 ArticleID 352759 13 pages 2012

[26] P S Vijayanand S Kato S Satokawa M Kishimoto and TKojima ldquoSynthesis characterization and thermal properties ofhomo and copolymers of 35-dimethoxyphenyl methacrylatewith glycidyl methacrylate determination of monomer reactiv-ity ratiosrdquo Reactive and Functional Polymers vol 69 no 6 pp333ndash340 2009

[27] G Barim K Demirelli and M Coskun ldquoConventional andatom transfer radical copolymerization of phenoxycarbonyl-methyl methacrylate-styrene and thermal behavior of theircopolymersrdquo Express Polymer Letters vol 1 no 8 pp 535ndash5442007

[28] G J Reddy S V Naidu and A V Rami Reddy ldquoSynthesis andCharacterization of Poly(N-phenyl methacrylamide-co-methylmethacrylate) and Reactivity Ratios Determinationrdquo Journal ofApplied Polymer Science vol 90 no 8 pp 2179ndash2186 2003

[29] S G Roy K Bauri S Pal A Goswami G Madras andP De ldquoSynthesis characterization and thermal degradationstudies of dual temperature- and pH-sensitive RAFT-madecopolymers of NN-(dimethylamino)ethyl methacrylate andmethyl methacrylaterdquo Polymer International vol 62 no 3 pp463ndash473 2013

[30] S Thamizharasi P Gnanasundaram and B S R Reddy ldquo4-acetylphenyl methacrylate-co-glycidyl methacrylate polymerssynthesis characterization and reactivity ratiosrdquo Journal ofPolymer Materials vol 15 no 3 pp 229ndash236 1998

[31] T Kelen and F Tudos ldquoAnalysis of linearmethods for determin-ing copolymerization reactivity ratios I New improved lineargraphic methodrdquo Journal of Macromolecular Science ChemistryA vol 9 no 1 pp 1ndash27 1975

[32] T Kelen F Tudos B Turcsanyi and J P Kennedy ldquoAnalysis ofthe linear methods for determining copolymerization reactivityratios IV A comprehensive and critical reexamination of car-bocationic copolymerization datardquo Journal of Polymer SciencePolymer Chemistry Edition vol 15 no 12 pp 3047ndash3074 1977

[33] D Sunbul H Catalgil-Giz W Reed and A Giz ldquoAn error-in-variables method for determining reactivity ratios by on-linemonitoring of copolymerization reactionsrdquo MacromolecularTheory and Simulations vol 13 no 2 pp 162ndash168 2004

[34] Z M O Rzaev A Guner G Kibare H Kaplan Can andA Asc ldquoTerpolymerization of maleic anhydride trans-stilbeneand acrylic monomersrdquo European Polymer Journal vol 38 no6 pp 1245ndash1254 2002

[35] S Teramachi A Hasegawa M Akatsuka A Yamashita andN Takemoto ldquoMolecular Weight Distribution and correlationbetween chemical composition and Molecular Weight in ahigh-conversion copolymer of styrene-methyl acrylaterdquoMacro-molecules vol 11 no 6 pp 1206ndash1210 1978

[36] F R Mayo and F M Lewis ldquoCopolymerization I A basis forcomparing the behavior of monomers in copolymerization thecopolymerization of styrene and methyl methacrylaterdquo Journalof the American Chemical Society vol 66 no 9 pp 1594ndash16011944

[37] W I Kim S D Kim S B Lee and I K Hong ldquoKineticcharacterization of thermal degradation process for commercialrubbersrdquo Journal of Industrial and Engineering Chemistry vol 6no 5 pp 348ndash355 2000

[38] J H Flynn and L A Wall ldquoA quick direct method for thedetermination of activation energy from thermogravimetricdatardquo Journal of Polymer Science Polymer Letters vol 4 no 5pp 323ndash328 1966

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


C

C O

O

C O

C

C O

O

C

C O

O

C O

C

C O

O

C

C O

O C

O

C

O

HO C

C O

Cl

CH3 CH3

CH3 CH3

CH3

CH3

CH3

CH2

CH3 CH3

CH3

H2C

H2C H2C

H2C H2C

+

+

C2H5

AIBN 14-dioxane

70∘C

CH2CH3

n

NR3

0ndash5∘C

Scheme 1 Synthesis of APMA and poly(APMA-co-EMA)

are no moderate or high conversion investigations related todetermining reactivity ratios of APMA-co-EMA system

For this reason in this study the synthesis and character-ization of copolymers of APMA with EMA are investigatedat moderate conversion The monomer reactivity ratios arecalculated using three different methods Kelen-Tudos (KT)[31] extended Kelen-Tudos (EKT) [32] and a nonlinear leastsquares (NLLS) [33] The EKT and the NLLS methods takethe composition drift into account and are suitable for highconversion experiments

119879119892rsquos of new copolymers and the effect of APMA contenton the thermal properties of resulting copolymers are alsoinvestigated

2 Experimental

21 Materials 4-Hydroxy acetophenone (Aldrich) andmethacryloyl chloride (Merck) were used as received EMAwas freed from inhibitor by being washed with 5 sodiumhydroxide solution several times followed by being washedwith distilled water and then was dried over anhydroussodium sulphate subsequently it was distilled under reducedpressure 2-21015840-Azobisisobutyronitrile (AIBN) was recrystal-lized from chloroform and methanol mixture 14-Dioxanetriethylamine tetrahydrofuran (THF) sodium hydroxidesodium sulphate (Merck) and ethanol (Merck) were ofanalytical grade and were used as received

22 Synthesis of 4-Acetylphenyl Methacrylate APMA mon-omerwas prepared from reaction of 4-hydroxy acetophenonewith methacryloyl chloride in the presence of triethylamineand THF at 0 to 5∘C range [26] (Scheme 1 the first row)

The monomer was characterized by FT-IR and 1H-NMRspectra as follows

IR (cmminus1) 3100 and 3070 (=CH) 2988 and 2848 (CndashHstretching) 1731 (C=O in ester) 1673 (C=O in ketone)1635 (CH2=C) 1596 (C=C on aromatic ring) 1200and 1165 respectively (OndashC=O and OndashCndashC)1H-NMR (120575 ppm CDCl3) 800 and 722 (protons onaromatic ring) 638 and 581 (CH2=C) and 191 (CH3protons)

23 Homopolymerization andCopolymerization Homopoly-merization and copolymerization reactions were carried outin 14-dioxane solution at 70∘C using AIBN (1 based onthe total weight of the monomers) as the initiator (Scheme 1the second row) Required amounts of APMA and EMAwith 14-dioxane and AIBN were mixed in a polymerizationtube purged with N2 atmosphere for 15min Polymerizationwas performed at 70∘C in a thermostatic oil bath After 3hours the copolymerswere precipitated in excess ethanol andfiltered The precipitated polymers were purified by repeatedreprecipitation from chloroform solution using ethanol andfinally dried in a vacuum oven at 40∘C for 24 hours Theconversion was determined by gravimetric measurementsThe reaction scheme of the copolymer is shown in Scheme 1Initial monomer compositions and copolymer conversionsare given in the second third and fourth columns andfinal monomer compositions are given in the fifth and sixthcolumns of Table 1

24 Polymer Characterization Infrared spectra were obtain-ed with a Perkin Elmer Spectrum One FT-IR system andrecorded using universal ATR sampling accessory within


Table1Mon

omer

andcopo

lymer

compo

sitiondatam

olecular

weights

andPI

indiceso

fcop

olym

ers

Expno

Initialmon

com

positions

conversio

nFinalm

oncom

positions

119862

Cop

olym

ercompo

sition

from

1 HNMR

Cop

olym

ercompo

sitions

from

FTIR

Molecular

weights

[119860]

[119861]

[119860]fin

[119861]fin

APM

A119875119860

EMA

119875119861

APM

A119875119860

EMA

119875119861

119872119899

PI

1010

090

33007

060

0179

015

085

018

082

8900

013

72

020

080

33013

054

0340

025

075

027

073

mdashmdash

3035

065

31024

045

0615

038

062

038

062

107800

144

050

050

36032

032

1298

056

044

050

050

mdashmdash

5070

030

37044

019

2500

071

029

066

034

112000

128

6090

010

38056

006

7690

088

012

081

019

11900

012

5







2119875119860

2 (1 minus 119875119860)



= 119862

(1)

On simplification

119875119860 =119862

119862 + 1 (2)




119875119860 =Δ1198601685

119872APMAΔ1198601685119872APMA + Δ119860

1724119872EMA100

119875119861 =Δ1198601724

119872EMAΔ1198601685119872APMA + Δ119860

1724119872EMA100

(3)






119889 [119860]

119889 [119861]=[119860]

[119861](119903119886 [119860] + [119861])

([119860] + 119903119887 [119861]) (4)






120578 = (119903119886 +119903119887

120572) 120585 minus

119903119887

120572 (5)


CC

C O

a

c

c

O

CH2

CH2

CH2

CH3

CH3

CH3

11234(ppm)

(ppm)

(ppm)

567891011

CH3 CH3

H2C C CCH2

C COO

OO

a

a

b

b

ab

C O

CH3

038 062

P(APMA-co-EMA)

P(EMA)

056 044

12345678910

12345678910

(ppm)12345678910

(ppm)12345678910

(ppm)12345678910

071 029

088 012

CCO

Oa

CH3

CH2

C OCH3

ab

ab

P(APMA)

ab



P(APMA)


071 029

056 044

038 062

4000 2800 1800 1200 650

T(

)




Polymer 119883 119884 119866 119865 120578 120585



Polymer 1205851

1205852

119885 119865 119866 120578 120585



ξ

08

06

04

02

0

minus02

minus04

minus06

minus0801 02 03 04 05 06 07 08 09

KTEKT

120578

120585









1205942=

119899

sum

119894=1

Δ[119860]2

119894

1205751198602 (7)




09

085

08

075

07

065

0603 035 04 045 05 055 06 065 07

rb

r a

KTEKTNLLS


DataKT

EKTNLLS

90

80

70

60

50

40

30

20

10

09080706050403020100

[A]

[B]






081 077 074119903119887

061 054 049119886 APMA 119887 EMA

Hea

t flow

(mW

)0 50 100 150 200

5

minus5

(a)(b)(c)(d)

(e)(f)(g)









Polymer 119879119892(∘C) 119879max



50045040035030025020015010050

100908070605040302010

0

Wei

ght l

oss (

)

Temperature (∘C)






50004000 4500300020001000 1500 2500 3500500

Wei

ght l

oss (

)

1000

500

600

700

800

900

100

200

300

400

00

Temperature (∘C)

5∘Cmin10∘Cmin

15∘Cmin25∘Cmin

(d)

(a)(b)

(c)



119864119889 = minus119877

119887[119889 log120573119889 (1119879)

] (8)


4 Conclusions



0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T








Acknowledgment


References















































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




Table1Mon

omer

andcopo

lymer

compo

sitiondatam

olecular

weights

andPI

indiceso

fcop

olym

ers

Expno

Initialmon

com

positions

conversio

nFinalm

oncom

positions

119862

Cop

olym

ercompo

sition

from

1 HNMR

Cop

olym

ercompo

sitions

from

FTIR

Molecular

weights

[119860]

[119861]

[119860]fin

[119861]fin

APM

A119875119860

EMA

119875119861

APM

A119875119860

EMA

119875119861

119872119899

PI

1010

090

33007

060

0179

015

085

018

082

8900

013

72

020

080

33013

054

0340

025

075

027

073

mdashmdash

3035

065

31024

045

0615

038

062

038

062

107800

144

050

050

36032

032

1298

056

044

050

050

mdashmdash

5070

030

37044

019

2500

071

029

066

034

112000

128

6090

010

38056

006

7690

088

012

081

019

11900

012

5







2119875119860

2 (1 minus 119875119860)



= 119862

(1)

On simplification

119875119860 =119862

119862 + 1 (2)




119875119860 =Δ1198601685

119872APMAΔ1198601685119872APMA + Δ119860

1724119872EMA100

119875119861 =Δ1198601724

119872EMAΔ1198601685119872APMA + Δ119860

1724119872EMA100

(3)






119889 [119860]

119889 [119861]=[119860]

[119861](119903119886 [119860] + [119861])

([119860] + 119903119887 [119861]) (4)






120578 = (119903119886 +119903119887

120572) 120585 minus

119903119887

120572 (5)


CC

C O

a

c

c

O

CH2

CH2

CH2

CH3

CH3

CH3

11234(ppm)

(ppm)

(ppm)

567891011

CH3 CH3

H2C C CCH2

C COO

OO

a

a

b

b

ab

C O

CH3

038 062

P(APMA-co-EMA)

P(EMA)

056 044

12345678910

12345678910

(ppm)12345678910

(ppm)12345678910

(ppm)12345678910

071 029

088 012

CCO

Oa

CH3

CH2

C OCH3

ab

ab

P(APMA)

ab



P(APMA)


071 029

056 044

038 062

4000 2800 1800 1200 650

T(

)




Polymer 119883 119884 119866 119865 120578 120585



Polymer 1205851

1205852

119885 119865 119866 120578 120585



ξ

08

06

04

02

0

minus02

minus04

minus06

minus0801 02 03 04 05 06 07 08 09

KTEKT

120578

120585









1205942=

119899

sum

119894=1

Δ[119860]2

119894

1205751198602 (7)




09

085

08

075

07

065

0603 035 04 045 05 055 06 065 07

rb

r a

KTEKTNLLS


DataKT

EKTNLLS

90

80

70

60

50

40

30

20

10

09080706050403020100

[A]

[B]






081 077 074119903119887

061 054 049119886 APMA 119887 EMA

Hea

t flow

(mW

)0 50 100 150 200

5

minus5

(a)(b)(c)(d)

(e)(f)(g)









Polymer 119879119892(∘C) 119879max



50045040035030025020015010050

100908070605040302010

0

Wei

ght l

oss (

)

Temperature (∘C)






50004000 4500300020001000 1500 2500 3500500

Wei

ght l

oss (

)

1000

500

600

700

800

900

100

200

300

400

00

Temperature (∘C)

5∘Cmin10∘Cmin

15∘Cmin25∘Cmin

(d)

(a)(b)

(c)



119864119889 = minus119877

119887[119889 log120573119889 (1119879)

] (8)


4 Conclusions



0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T








Acknowledgment


References















































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials









2119875119860

2 (1 minus 119875119860)



= 119862

(1)

On simplification

119875119860 =119862

119862 + 1 (2)




119875119860 =Δ1198601685

119872APMAΔ1198601685119872APMA + Δ119860

1724119872EMA100

119875119861 =Δ1198601724

119872EMAΔ1198601685119872APMA + Δ119860

1724119872EMA100

(3)






119889 [119860]

119889 [119861]=[119860]

[119861](119903119886 [119860] + [119861])

([119860] + 119903119887 [119861]) (4)






120578 = (119903119886 +119903119887

120572) 120585 minus

119903119887

120572 (5)


CC

C O

a

c

c

O

CH2

CH2

CH2

CH3

CH3

CH3

11234(ppm)

(ppm)

(ppm)

567891011

CH3 CH3

H2C C CCH2

C COO

OO

a

a

b

b

ab

C O

CH3

038 062

P(APMA-co-EMA)

P(EMA)

056 044

12345678910

12345678910

(ppm)12345678910

(ppm)12345678910

(ppm)12345678910

071 029

088 012

CCO

Oa

CH3

CH2

C OCH3

ab

ab

P(APMA)

ab



P(APMA)


071 029

056 044

038 062

4000 2800 1800 1200 650

T(

)




Polymer 119883 119884 119866 119865 120578 120585



Polymer 1205851

1205852

119885 119865 119866 120578 120585



ξ

08

06

04

02

0

minus02

minus04

minus06

minus0801 02 03 04 05 06 07 08 09

KTEKT

120578

120585









1205942=

119899

sum

119894=1

Δ[119860]2

119894

1205751198602 (7)




09

085

08

075

07

065

0603 035 04 045 05 055 06 065 07

rb

r a

KTEKTNLLS


DataKT

EKTNLLS

90

80

70

60

50

40

30

20

10

09080706050403020100

[A]

[B]






081 077 074119903119887

061 054 049119886 APMA 119887 EMA

Hea

t flow

(mW

)0 50 100 150 200

5

minus5

(a)(b)(c)(d)

(e)(f)(g)









Polymer 119879119892(∘C) 119879max



50045040035030025020015010050

100908070605040302010

0

Wei

ght l

oss (

)

Temperature (∘C)






50004000 4500300020001000 1500 2500 3500500

Wei

ght l

oss (

)

1000

500

600

700

800

900

100

200

300

400

00

Temperature (∘C)

5∘Cmin10∘Cmin

15∘Cmin25∘Cmin

(d)

(a)(b)

(c)



119864119889 = minus119877

119887[119889 log120573119889 (1119879)

] (8)


4 Conclusions



0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T








Acknowledgment


References















































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




CC

C O

a

c

c

O

CH2

CH2

CH2

CH3

CH3

CH3

11234(ppm)

(ppm)

(ppm)

567891011

CH3 CH3

H2C C CCH2

C COO

OO

a

a

b

b

ab

C O

CH3

038 062

P(APMA-co-EMA)

P(EMA)

056 044

12345678910

12345678910

(ppm)12345678910

(ppm)12345678910

(ppm)12345678910

071 029

088 012

CCO

Oa

CH3

CH2

C OCH3

ab

ab

P(APMA)

ab



P(APMA)


071 029

056 044

038 062

4000 2800 1800 1200 650

T(

)




Polymer 119883 119884 119866 119865 120578 120585



Polymer 1205851

1205852

119885 119865 119866 120578 120585



ξ

08

06

04

02

0

minus02

minus04

minus06

minus0801 02 03 04 05 06 07 08 09

KTEKT

120578

120585









1205942=

119899

sum

119894=1

Δ[119860]2

119894

1205751198602 (7)




09

085

08

075

07

065

0603 035 04 045 05 055 06 065 07

rb

r a

KTEKTNLLS


DataKT

EKTNLLS

90

80

70

60

50

40

30

20

10

09080706050403020100

[A]

[B]






081 077 074119903119887

061 054 049119886 APMA 119887 EMA

Hea

t flow

(mW

)0 50 100 150 200

5

minus5

(a)(b)(c)(d)

(e)(f)(g)









Polymer 119879119892(∘C) 119879max



50045040035030025020015010050

100908070605040302010

0

Wei

ght l

oss (

)

Temperature (∘C)






50004000 4500300020001000 1500 2500 3500500

Wei

ght l

oss (

)

1000

500

600

700

800

900

100

200

300

400

00

Temperature (∘C)

5∘Cmin10∘Cmin

15∘Cmin25∘Cmin

(d)

(a)(b)

(c)



119864119889 = minus119877

119887[119889 log120573119889 (1119879)

] (8)


4 Conclusions



0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T








Acknowledgment


References















































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




P(APMA)


071 029

056 044

038 062

4000 2800 1800 1200 650

T(

)




Polymer 119883 119884 119866 119865 120578 120585



Polymer 1205851

1205852

119885 119865 119866 120578 120585



ξ

08

06

04

02

0

minus02

minus04

minus06

minus0801 02 03 04 05 06 07 08 09

KTEKT

120578

120585









1205942=

119899

sum

119894=1

Δ[119860]2

119894

1205751198602 (7)




09

085

08

075

07

065

0603 035 04 045 05 055 06 065 07

rb

r a

KTEKTNLLS


DataKT

EKTNLLS

90

80

70

60

50

40

30

20

10

09080706050403020100

[A]

[B]






081 077 074119903119887

061 054 049119886 APMA 119887 EMA

Hea

t flow

(mW

)0 50 100 150 200

5

minus5

(a)(b)(c)(d)

(e)(f)(g)









Polymer 119879119892(∘C) 119879max



50045040035030025020015010050

100908070605040302010

0

Wei

ght l

oss (

)

Temperature (∘C)






50004000 4500300020001000 1500 2500 3500500

Wei

ght l

oss (

)

1000

500

600

700

800

900

100

200

300

400

00

Temperature (∘C)

5∘Cmin10∘Cmin

15∘Cmin25∘Cmin

(d)

(a)(b)

(c)



119864119889 = minus119877

119887[119889 log120573119889 (1119879)

] (8)


4 Conclusions



0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T








Acknowledgment


References















































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




09

085

08

075

07

065

0603 035 04 045 05 055 06 065 07

rb

r a

KTEKTNLLS


DataKT

EKTNLLS

90

80

70

60

50

40

30

20

10

09080706050403020100

[A]

[B]






081 077 074119903119887

061 054 049119886 APMA 119887 EMA

Hea

t flow

(mW

)0 50 100 150 200

5

minus5

(a)(b)(c)(d)

(e)(f)(g)









Polymer 119879119892(∘C) 119879max



50045040035030025020015010050

100908070605040302010

0

Wei

ght l

oss (

)

Temperature (∘C)






50004000 4500300020001000 1500 2500 3500500

Wei

ght l

oss (

)

1000

500

600

700

800

900

100

200

300

400

00

Temperature (∘C)

5∘Cmin10∘Cmin

15∘Cmin25∘Cmin

(d)

(a)(b)

(c)



119864119889 = minus119877

119887[119889 log120573119889 (1119879)

] (8)


4 Conclusions



0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T








Acknowledgment


References















































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





Polymer 119879119892(∘C) 119879max



50045040035030025020015010050

100908070605040302010

0

Wei

ght l

oss (

)

Temperature (∘C)






50004000 4500300020001000 1500 2500 3500500

Wei

ght l

oss (

)

1000

500

600

700

800

900

100

200

300

400

00

Temperature (∘C)

5∘Cmin10∘Cmin

15∘Cmin25∘Cmin

(d)

(a)(b)

(c)



119864119889 = minus119877

119887[119889 log120573119889 (1119879)

] (8)


4 Conclusions



0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T








Acknowledgment


References















































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




0

02

04

06

08

1

12

14

16

135 155 175 195

1020304050

60708090

log120573

1000T








Acknowledgment


References















































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



Research Article Copolymerization of 4-Acetylphenyl...

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