Macromolecular Research, Vol. 19, No. 2, pp 156-165 (2011) www.springer.

com/13233
DOI 10.1007/s13233-011-0213-5

Microstructure of Poly(vinyl acetate)-block-Poly(methyl acrylate-co-methyl

methacrylate) Block Terpolymers. 2D NMR and Thermal Study

Mahdi Moeud Ajjalallah and Mohammad Reza Rostami Daronkola*

Polymer Group, Chemical Engineering Department, Tarbiat Modares University,
Jalal Al Ahmad Highway, P.O. Box 14115-143, Tehran, I.R., Iran

Received June 12, 2010; Revised September 15, 2010; Accepted September 18, 2010

Abstract: Structural analysis of the poly(vinyl acetate)-block-poly(methyl acrylate-co-methyl methacrylate) with

different MA/MMA ratios was characterized by 1D and 2D NMR. The effect of the sequence distribution, compo-
sition and stereoregularity on the unknown signals of α-CH3, backbone methylene and methin carbons were ana-
lyzed by 1D (13C/DEPT-135) and 2D HSQC NMR. Furthermore, the theoretical values of triad, dyad and triad
fractions of these carbons confirmed the spectral assignments. The sensitivity of the vicinal and geminal couplings
of methin and methylene protons to the sequence distribution and composition were characterized using the 2D
TOCSY NMR method. The influence of the sequence distribution on the theoretical glass transition temperatures of
the MA/MMA copolymers was also examined using the Johnston (extended Fox) equation and experimental Tg.
Keywords: 2D NMR, block terpolymer, microstructure, sequence distribution, glass transition temperature.

Introduction of the copolymers were also reported.25

The correlation between the microstructures such as sequence
distribution, configuration, composition, and functionality
with macroscopic properties of macromolecules is the main
future in study of structural analysis.1-8 Among the several
block copolymers and terpolymers with controlled struc-
tures which were synthesized via ATRP,9-20 good agreement
between the molecular structures and morphological, ther-
mal, electrical, mechanical, and transport properties have
been observed.
The effect of composition, sequence distribution and ste-
reochemistry along the chemical bonds of copolymers was
described in various papers21-36 using two-dimensional HSQC,
TOCSY, and HMBC NMR spectroscopy.
Agarwal et al.23 characterized structure of 5,6-benzo-2-
methylene-1,3-dioxepane and MMA random copolymers
using 1H, 13C, 2D HMQC, and HMBC NMR. The effect of
composition and configuration on resonated peaks and also
analysis of sequence distributions of copolymers were char-
acterize.
In another work, Brar et al.25 analyzed effect of composi-
tion, stereoregularity and sequence distribution of the syn-
thesized 2-N-carbazolylethyl acrylate/methyl methacrylate
copolymers using 1D (1H, 13C, DEPT-45, 90, 135) and 2D
(HSQC, TOCSY, HMBC) NMR methods. The effect of MMA
composition on flexibility and glass transition temperatures
*Corresponding Author. E-mail: mr_rostami@modares.ac.ir
750 MHz 1D and 2D NMR techniques were used to char-
acterize poly(ethylene-co-vinyl acetate-co-carbon monox-
ide)28 at high temperature (120 oC). Assignment of major triads
was studied by 2D gradient HSQC, HMBC and assisted
HSQC-TOCSY NMR.
Hooda et al. synthesized various MA/VAc/N-vinyl carba-
zole terpolymers via CFRP in solution.32 Two-dimensional
HSQC, TOCSY, and HMBC NMR spectra were used to
assign the methylene, methin and 3-4 bond order coupling
of carbonyl carbon with neighboring protons.
Harwood et al.33 used 150 MHz 13C NMR spectrum to
analyze sequence distribution of various MA/MMA copoly-
mers which were synthesized via CFRP in bulk at 50 oC.
Dyad, triad, tetrad, and partial pentad distribution of MA/
MMA copolymers were characterized in the regin of α-
methyl, methin, and methylene carbon resonances. In another
work, the effect of configuration and composition on cou-
plings of carbonyl carbon and 13C-1H correlation of various
carbons (α-CH3, CH2, and CH) were analyzed using 13C and
2D HSQC NMR spectroscopy. The vicinal and geminal
couplings of the protons were also studied by 2D TOCSY
NMR.36
Recently, we synthesized novel block terpolymers via
atom transfer radical copolymerization of MA and MMA
with PVAc-CCl3 as macroinitiator.10,15 These block terpoly-
mers with excellent control over the topology, microstruc-
ture and composition have been used as surfactant, dispersant
and alloying compounds.1 The compositions of the MA/

The Polymer Society of Korea 156

 Microstructure of PVAc-b-Poly(MA-co-MMA) Block Terpolymers. 2D NMR and Thermal Study

MMA copolymers were determined by 1H NMR spectra.15

But sequence distribution determination, couplings, micro-
structure/thermal properties relationship, and phase behav-
ior of the block terpolymers were not studied in detail.
In this paper, we report the effect of structure, composi-
tion, sequence distribution, and stereoregularity on the spec-
tral assignment, 13C-1H correlation and couplings in PVAc-
b-poly(MA-co-MMA) block terpolymers using 1D (13C NMR
and DEPT-135) and 2D (HSQC and TOCSY) NMR tech-
niques. A first-order Markov statistical model was used to
confirm the spectral assignments of α-CH3, methin, and meth-
ylene carbons. Moreover, the microstructures/glass transi-
tion temperature (Tg) correlation and miscibility of the block
terpolymers were also studied.

Experimental

Materials. The block terpolymers of PVAc-b-poly(MA-

co-MMA) were synthesized via atom transfer radical copo-
lymerization of MA and MMA with PVAc-CCl3 macroiniti-
ator in bulk at 80 oC.10-15 During three reactions of 1-3, the
mole fractions of MA monomer in feed were 0.438, 0.56,
and 0.825.10-15
The synthesized block terpolymers were dissolved in THF
and passed through a neutral alumina column to remove
remaining copper catalyst.10-15 The sample was then dried at
55 oC under vacuum up to a constant weight and character-
ized by 1D and 2D NMR spectroscopy.
The mole fractions of MMA and MA units in copolymers
were also calculated by 1H NMR around 0.733/0.267, 0.619/
0.381, and 0.358/0.642.10-15 Furthermore, on the basis of
extended Kelen-Tudos (KT) method, the reactivity ratio of
MA and MMA monomers were also reported to be 0.3766
and 2.0524.37
Polymer Characterization. The 1D (13C and DEPT-135)
and 2D (HSQC and TOCSY) NMR spectra of purified
block terpolymers were recorded by Bruker DPX-500 spec-
trometer with 13C and 1H NMR measurements of 125 and
500 MHz in CDCl3 at 25 oC. In 13C NMR spectrum, decou-
pling of the attached protons such as 13C-1H (1JCH), 13C-C-1H
(2JCH), and 13C-C-C-1H (3JCH) carried out with proton broad-
band decoupling irradiation and detection of 13C signals.
The distortionless enhancement by polarization transfer, DEPT-
135 spectrum recorded with negative and positive phase of
methylene and both methin and methyl carbon signals.
Differential scanning calorimetery (DSC) analyses were
performed by using a Pyris 1 instrument at a heating rate of 10 oC/
min under nitrogen atmosphere in the range of 20 to 150 oC.13
Results and Discussion
Microstructure Analysis.
13
C NMR and DEPT-135 Studies of the Block Terpolymer:
Figure 1(A),(B) compares the 13C NMR/DEPT-135 spec-
Figure 1. DEPT-135 (A, above) and 13C NMR (B, bottom) spec-
trums of the PVAc-b-poly(MA-co-MMA) (FM=0.619) in CDCl3.
trums of the PVAc-b-poly(MA-co-MMA) block tercopoly-
mer (mole fraction of MMA (FM) equal to 0.619).
The α-methyl carbon resonance of MMA in repeating
unit (1) and chain end (2) appears around 15.7-21.8 and 30
ppm.25-27 The O-CH3 carbon of MMA (3) and MA (4) units
in copolymer and (C=0)-CH3 carbon of VAc (5) segment
resonate as singlet at 52.0, 52.3, and 21.2 ppm.
The peak at 169.3-170.6 ppm and complex peaks around
174.9-178.3 ppm corresponding to carbonyl carbons of VAc
unit and MA/MMA copolymer.38,39 The methin (CH) carbon
of the VAc unit resonates at δ 65.8-68.2 ppm.28-38
The complex and overlapped peaks around 32.4-54.3 ppm
can be assigned to the backbone methylene of the VAc, MA,
and MMA units and also methin and quaternary carbon res-
onance of MA and MMA units. Both DEPT-135 and 13C
NMR spectra (Figure 1(A),(B)) were used to resolve this
region. The signals around 38.9-39.7 and 46.3-54.3 ppm can
be assigned to backbone methylene carbons of the VAc and
MA/MMA copolymer. The methin and quaternary carbon
of MA and MMA units resonate at 37.17-41.1 and 43.65-
45.4 ppm.33-36
The carbons of C-Cl (6), CHCl (7), and C-Cl2 (8) groups
in the block terpolymer resonate at 69, 70, and 77 ppm.22
The peaks at 60 and 39 ppm corresponding to methylene
carbons in terpolymer chain end (9) and neighbor of the C-

Macromol. Res., Vol. 19, No. 2, 2011 157

 M. M. Ajjalallah and M. R. R. Daronkola

Cl2 group (10).

2D HSQC and TOCSY NMR Studies of the Block Ter-
polymers.
α-Methyl Carbon Resonances of Poly(MA-co-MMA)
Segment: The α-methyl carbon of the methyl methacrylate
unit resonates at 16.0-21.83 ppm in the 13C NMR spectrum
corresponding to the syndiotactic (rr, 16.0-16.7 ppm), atactic
(mr, 18.45-18.95 ppm) and isotactic (mm, 21.6-21.8 ppm)
of triad sequence. The variation in the resonance signals of
the α-methyl carbon in various copolymer compositions in
comparison with the PMA and PMMA homopolymers are
also shown in Figure 2. The intensities of the resonance pat-
terns differ with MMA content in the copolymers and can
be assigned to various triad sequence distributions of the
MMA (M) and MA (A) units. The resonance peaks show
splitting up which can be assigned to various M-centered
pentads by observing the change in intensity of signals with
increase of MMA unit in copolymers.
Figure 3 shows the 2D HSQC spectrum of α-methyl region
for three different compositions of MMA unit in copolymer
(FM = 0.733, 0.619, and 0.358). The cross peaks at 16.3/0.78,
16.5/0.9, and 16.9/0.88 ppm corresponding to MMrMrMM
(1), AMrMrMM (2), and AMrMrMA (3) pentads while the Figure 3. 13C-1H correlation (2D HSQC NMR) spectrums of
cross peaks centered at 17.7/0.74, 17.85/0.74, and 18.0/1.1 PVAc-b-poly(MA-co-MMA) block terpolymers showing α-methyl
ppm corresponding to MMrMrAM (4), AMrMrAM (5), and region in CDCl3 at 25 oC. (FM is mole fraction of MMA unit in
copolymers).

AMrMrAA (6). Thee cross peaks centered at 18.5/0.9, 18.9/

0.94, and 19.1/1.02 ppm corresponding to MMmMrMM (7),
AMmMrMM (8), and AMmMrMA (9) pentads. AMA triad

Table I. The Assignments of α-CH3 Carbon Resonance in Various

Copolymers by 13C and 2D HSQC NMR Spectra
13
Peak 2D HSQC C NMR
Assignments
Number (13C-1H) ppm (ppm)
1 MMrMrMM 16.3/0.78 15.95
2 AMrMrMM 16.5/0.9 16.3
3 AMrMrMA 16.9/0.88 16.8
4 MMrMrAM 17.7/0.74 17.27
5 AMrMrAM 17.85/0.74 17.52
6 AMrMrAA 18.0/1.1 17.95
7 MMmMrMM 18.5/0.9 18.3
8 AMmMrMM 18.9/0.94 18.42
9 AMmMrMA 19.1/1.02 18.52
10 MAMAM 19.4/0.9 18.9
11 AAMAM 20.01/1.05 19.65
Figure 2. The region of expanded α-methyl carbon-13 resonance 12 AAMAA 21.01/1.12 20.1
patterns of PMA, PMMA, and MA/MMA copolymers with dif- 13 MMmMmMM 21.6/1.24 21.3
ferent mole fraction of MMA in CDCl3 at 25 oC. (FM is mole
14 AMmMmMM 21.7/1.32 21.61
fraction of methyl methacrylate in copolymers).

158 Macromol. Res., Vol. 19, No. 2, 2011

 Microstructure of PVAc-b-Poly(MA-co-MMA) Block Terpolymers. 2D NMR and Thermal Study

Table II. The Observed and Calculated α-Methyl Triad Fractions

from 13C NMR Spectrum and First-Order Markov Statistical
Model
FM Fexp(MMM) Fcal(MMM) Fexp(MMA+AMM) Fcal(MMA+AMM) Fexp(AMA) Fcal(AMA)
0.733 0.56 0.52 0.32 0.40 0.12 0.08
0.619 0.46 0.38 0.37 0.47 0.17 0.15
0.358 0.17 0.09 0.35 0.42 0.48 0.49

shows three cross peaks centered at 19.4/0.9, 20.01/1.05, and

21.01/1.12 ppm corresponding to MAMAM (10), AAMAM
(11), and AAMAA (12) pentads. The cross peaks around
21.6/1.24 and 21.7/1.32 ppm corresponding to MMmMmMM
(13) and AmmMmMM (14) pentads.
Table I show the complete spectral assignments of various
M- centered pentads which were analyzed by 13C and 2D
HSQC NMR spectra.
Table II compares the experimental and theoretical values
of α-methyl triad fractions. The experimental values were
estimated by summation of the area under the resonance
peaks in 13C NMR spectrum. The first-order Markov statisti-
cal model was also used on the basis of reaction probability40 to
calculate the theoretical values. A reasonably agreement
between the theoretical and experimental triad fractions
confirms the assignments (standard deviation and standard
deviation as a percentage of average were calculated to be
0.0278 and 8.3). Figure 4. The region of methin carbon resonance patterns of
Methin Carbon Resonances of Poly(MA-co-MMA) PMA and MA/MMA copolymers with different mole fraction of
Segment. The DEPT-135 NMR spectra of methin carbon MA by DEPT-135 NMR in CDCl3 at 25 oC.
resonance of poly(MA/MMA) copolymers with various MA
fractions were compared with PMA in Figure 4. On consid-
ering the changes in the intensities of signals with MA con- the backbone methylene protons of AmA/MmA (H1 and H2)
tent, methin carbon can be divided into MAM, 37.0-37.8 ppm, and ArA.
MAA, 39.55-40.7 ppm, and AAA triad regions, 40.8-41.4 ppm. Table III shows the complete spectral assignments of
In addition, each of these regions split to pentad and 2D methin region which were analyzed by DEPT-135 (Figure
HSQC NMR spectrum was used to clear the methin carbon 4) and 2D HSQC NMR (Figure 5) spectra.
assignments of copolymers with three MMA (M) composi- Table IV compares the experimental and theoretical val-
tions (Figure 5). MAA triad shows three cross peaks in 2D ues of methin triad fractions. The experimental values were
HSQC NMR spectrum (Figure 5) at 37.0/2.04, 37.3/2.17 estimated by summation of the area under the resonance
and 37.75/2.14 ppm corresponding to the MMAMM (15), peaks in DEPT-135 spectra (Figure 4). The theoretical ones
MMAMA (16), and AMAMA (17) pentads. Three cross were also calculated using first-order Markov statistical
peaks at 38.8/2.04, 39.6/2.2, and 40.03/2.17 ppm also corre- model. Good agreement between the theoretical and experi-
sponding to MMAAM (18), MMAAA (19), and AMAAA mental methin triad fractions confirms the assignments. The
(20) pentads. AAA triad shows a cross peak in 2D HSQC standard deviation and standard deviation as percentage of
NMR spectrum at 41.0/2.19 ppm corresponding to AAAAA average were also calculated to be 0.008 and 2.5.
(21) pentad. Backbone Methylene Carbon Resonances of Poly(MA-
According to these results, 2D TOCSY NMR spectra (Figures co-MMA) Segment. Figure 9 compares the 13C NMR spec-
6-8) were used to study of vicinal couplings between methin tra of backbone methylene carbon region of MA/MMA co-
protons of MA unit in AA and AM centered dyads with the polymers for different composition with PMA and PMMA
methylene protons of MA and MMA units in copolymers. homopolymers. The signals can be assigned to AA (33.8-
Three cross 1H-1H correlation peaks at 1.54/2.02 (a), 1.68/ 36.5), AM (46.6-50.7), and MM (52.2-55.2) dyads.
2.02 (b), and 1.64/2.02 ppm (c) corresponding to the vicinal In addition, each of these regions split to tetrad and 2D
coupling between methin proton of AA and MA dyads with HSQC NMR spectrum was used to clear the methylene car-

Macromol. Res., Vol. 19, No. 2, 2011 159

 M. M. Ajjalallah and M. R. R. Daronkola

Table III. Complete Spectral Assignments of Methin Carbon

Resonance Based on the DEPT-135 and 2D HSQC NMR
Peak DEPT-135 2D HSQC
Assignment
Number (ppm) (13C-1H) ppm
15 MMAMM 37.1 37.0/2.04
16 MMAMA 37.28 37.3/2.17
17 AMAMA 37.70 37.75/2.14
18 MMAAM 39.6 38.8/2.04
19 MMAAA 40.10 39.6/ 2.2
20 AMAAA 40.3 40.03/2.17
21 AAAAA 40.95 41.0/2.19

Table IV. The Observed and Calculated Methin Triad Fractions

from 13C NMR Spectrum and First-Order Markov Statistical
Model
FM Fexp(MAM) Fcal(MAM) Fexp(AAM+MAA) Fcal(AAM+MAA) Fexp(AAA) Fcal(AAA)
0.733 0.61 0.60 0.32 0.35 0.07 0.05
0.619 0.48 0.46 0.43 0.44 0.08 0.10
0.358 0.14 0.13 0.46 0.46 0.40 0.41

Figure 6. 2D TOCSY NMR spectrum of the MA/MMA copoly-

mer with FM = 0.358 in CDCl3 at 25 oC.
Figure 5. 13C-1H correlation (2D HSQC NMR) spectrums of
PVAc-b-poly(MA-co-MMA) block terpolymers showing methin
and backbone methylene regions in CDCl3 at 25 oC. (FM is mole
fraction of MMA in copolymers).
bon assignments of MA and MMA units (Figure 5).
The cross peaks centered at 34.8/1.73, 34.8/1.82, and
34.8/1.78 ppm in 2D HSQC NMR spectrum (Figure 5) cor-
responding to the non-equivalent protons AAmAA (H1) (22),
AAmAA (H2) (23), and AArAA (24) tetrad. A single cross
1
H-1H correlation peak centered at 1.73/1.82 ppm (d) is
observed due to geminal coupling of H1 and H2 in 2D TOCSY
NMR spectra (Figure 6).
As shown in Figure 5, the AAmAM tetrad shows two
cross peaks at 37.6/1.51 and 37.6/1.73 ppm corresponding
to the non-equivalent meso protons of AAmAM (H1) (25)
and AAmAM (H2) (26) and also a single cross peak at 37.6/
1.69 ppm corresponding to AArAM (27) tetrad. In 2D TOCSY
NMR spectrum (Figures 6-8), a single cross peak at 1.51/1.73

160 Macromol. Res., Vol. 19, No. 2, 2011

 Microstructure of PVAc-b-Poly(MA-co-MMA) Block Terpolymers. 2D NMR and Thermal Study
Figure 7. 2D TOCSY NMR spectrum of the MA/MMA copoly-
mer with FM = 0.619 in CDCl3 at 25 oC.
Figure 8. 2D TOCSY NMR spectrum of the MA/MMA copoly-
mer with FM = 0.733 in CDCl3 at 25 oC.
ppm (e) corresponding to the geminal coupling between the
H1 and H2 protons.
Two cross peaks centered at 37.8/1.44 and 37.8/1.78 ppm
in 2D HSQC NMR can be assigned to the two non-equiva-
lent meso protons of MCmCM (H1) (28) and MAmAM (H2)
(29) tetrads. MArAM (30) tetrad also appears as a cross
peak at 37.8/1.51 ppm. As shown in Figures 6, these two
protons show a cross peak at 1.44/1.78 ppm (f).
The racemic protons of methylene carbon are different
chemical environments in case of the AM dyad. Therefore,
they appear as two individual peaks in 2D HSQC NMR
spectra and a cross peak in 2D TOCSY NMR spectra.
Macromol. Res., Vol. 19, No. 2, 2011
In Figure 5, the AAmMA tetrad shows two cross peaks at
40.07/1.57 and 40.07/1.78 ppm corresponding to AAmMA
(H1) (31) and AAmMA (H2) (32). These protons give a
cross peak at 1.57/1.78 ppm (g) in 2D TOCSY NMR spec-
tra (Figures 6-8) due to the geminal coupling. A single cross
peak at 40.07/1.68 ppm can be assigned to AArMA (33) tetrad.
Two cross peaks at 44.1/1.26 and 44.1/1.75 ppm in 2D
HSQC NMR (Figure 5) can be assigned to the AAmMM
(H1) (34) and AAmMM (H2) (35) tetrads. A cross peak cen-
tered at 1.26/1.75 ppm (h) is observed in 2D TOCSY NMR
spectra due to their geminal coupling (Figures 6-8).
As shown in Figure 5, the AArMM tetrad with non-equiv-
alent racemic protons presents two cross peaks in 2D HSQC
NMR spectra at 44.1/1.53 and 44.1/1.57 ppm corresponding
to AArMM (H3) (36) and AArMM (H4) (37). The geminal
coupling of these protons resonate as a cross peak in the 2D
TOCSY NMR spectra at 1.53/1.57 ppm (i) (Figures 6-8).
MAmMM tetrad shows two cross peaks at 47.3/1.2 and
47.3/1.97 ppm corresponding to MAmMM (H1) (38) and
MAmMM (H2) (39). Similarly, MArMM shows two cross
peaks at 47.3/1.45 and 47.3/1.61 ppm corresponding to
MArMM (H3) (40) and MArMM (H4) (41). These protons
appear as two cross peaks in 2D TOCSY NMR spectra at
1.2/1.97 ppm (j) and 1.45/1.61 (k) (Figures 6-8) due to the
H1/H2 and H3/H4 geminal couplings.
A single cross peak appears at 48.2/1.84 can be assigned
to AMMA tetrad (42).
AMmMM tetrad gives two cross peaks at 53.01/1.68 and
53.01/1.88 ppm corresponding to AMmMM (H1) (43) and
AMmMM (H2) (44) (Figure 5). A cross peak at 53.01/1.79
ppm can be assigned to AMrMM tetrad (45). As shown in
2D TOCSY NMR spectra (Figures 6-8), the geminal cou-
pling in AMmMM tetrad appears as a cross 1H-1H correla-
tion peak at 1.68/1.88 ppm (l).
Two cross peaks at 54.3/1.71 and 54.3/1.87 ppm can be
assigned to MMmMM (H1) (46) and MMmMM (H2) (47)
(Figure 5). 2D TOCSY NMR spectrum shows a cross peak
at 1.71/1.87 ppm (m) due to H1/H2 geminal coupling (Figures
6-8). As shown in Figure 5, MMrMM tetrad (48) appears as
a cross peak at 54.3/1.76 ppm.
Table V shows the complete spectral assignments of
backbone methylene carbon which were done by 2D HSQC
(Figure 5) and TOCSY NMR (Figures 6-8) methods.
Table VI compares the theoretical (Calculated with first-
order Markov statistical model) and experimental (Obtained
by summation of the area under the resonance peaks in Fig-
ure 9) dyad fractions of backbone methylene. The theoreti-
cal triad fractions were in good agreement with the experimental
ones confirms the assignments. The standard deviation and
standard deviation as percentage of average were also cal-
culated to be 0.018 and 5.57.
2D HSQC and TOCSY NMR of PVAc Segment. The
backbone methylene (CH2) and methin (CH) carbon of poly
(vinyl acetate) (V) segment resonates at 38.3-40.0 and 65.8-
161
 M. M. Ajjalallah and M. R. R. Daronkola

Table V. Complete Spectral Assignments of Backbone Methylene Carbon Resonance Based on the 2D HSQC and TOCSY NMR
Spectra
Peak Number Assignment 2D HSQC (13C-1H) ppm 2D TOCSY (1H-1H) ppm
22 AAmAA (H1) 34.8/1.73 1.73/1.82 (H1 and H2 coupled, a)
23 AAmAA (H2) 34.8/1.82 1.73/1.82 (H1 and H2 coupled, a)
24 AArAA 34.8/1.78 -
25 MAmAA (H1) 37.6/1.51 1.51/1.73 (H1 and H2 coupled, b)
26 MAmAA (H2) 37.6/1.73 1.51/1.73 (H1 and H2 coupled, b)
27 MArAA 37.6/1.69 -
28 MAmAM (H1) 37.8/1.44 1.44/1.78 (H1 and H2 coupled, c)
29 MAmAM (H2) 37.8/1.78 1.44/1.78 (H1 and H2 coupled, c)
30 MArAM 37.8/1.51 -
31 AMmAA (H1) 40.07/1.57 1.57/1.78 (H1 and H2 coupled, d)
32 AMmAA (H2) 40.07/1.78 1.57/1.78 (H1 and H2 coupled, d)
33 AMrAA 40.07/1.68 -
34 MMmAA (H1) 44.1/1.26 1.26/1.75 (H1 and H2 coupled, e)
35 MMmAA (H2) 44.1/1.75 1.26/1.75 (H1 and H2 coupled, e)
36 MMrAA (H3) 44.1/1.53 1.53/1.57 (H3 and H4 coupled, f)
37 MMrAA (H4) 44.1/1.57 1.53/1.57 (H3 and H4 coupled, f)
38 MMmAM (H1) 47.3/1.2 1.2/1.97 (H1 and H2 coupled, g)
39 MMmAM (H2) 47.3/1.97 1.2/1.97 (H1 and H2 coupled, g)
40 MMrAM (H3) 47.3/1.45 1.45/1.61 (H3 and H4 coupled, h)
41 MMrAM (H4) 47.3/1.61 1.45/1.61 (H3 and H4 coupled, h)
42 AMMA 48.2/1.84 -
43 MMmMA (H1) 53.01/1.68 1.68/1.88 (H1 and H2 coupled, i)
44 MMmMA (H2) 53.01/1.88 1.68/1.88 (H1 and H2 coupled, i)
45 MMrMA 53.01/1.79 -
46 MMmMM (H1) 54.3/1.71 1.71/1.87 (H1 and H2 coupled, j)
47 MMmMM (H2) 54.3/1.87 1.71/1.87 (H1 and H2 coupled, j)
48 MMrMM 54.3/1.76 -

Table VI. The Observed and Calculated Backbone Backbone (H1) (49), VVmVV (H2) (50), and VVrVV (51) tetrads. Fur-
Methylene Dyad Fractions from 13C NMR Spectrum and thermore, a single peak centered at 1.60/1.80 (n) is observed
First-Order Markov Statistical Model due to geminal coupling between the methylene protons of
FM Fob(AA) Fcal(AA) Fob(AM) Fcal(AM) Fob(MM) Fcal(MM) H1 and H2 in 2D TOCSY NMR spectrum (Figures 6-8).
Three cross 1H-1H correlation peaks at 1.62/4.81 (o), 1.78/
0.733 0.02 0.02 0.25 0.30 0.73 0.68
4.81 (p), and 1.85/4.81 ppm (q) can be assigned to vicinal
0.619 0.04 0.04 0.38 0.42 0.58 0.54 coupling between the methin proton of VV unit and back-
0.358 0.28 0.27 0.51 0.56 0.21 0.17 bone methylene proton of VmV (H1), VrV and VmV (H2)
(Figure 10).
The spectral assignments of methin and methylene car-
68.1 ppm.28,32,38 bons of VAc unit based on the 2D HSQC and TOCSY NMR
The cross peaks centered at 39.1/1.60, 39.1/1.80, and 39.1/ spectra were summarized in Table VII.
1.73 ppm in 2D HSQC NMR spectrum (Figure 5) are the Carbonyl Carbon Resonances of Poly(MA-co-MMA)
characteristic peak of the non-equivalent protons VVmVV Segment. The highly complex and overlapped signals of

162 Macromol. Res., Vol. 19, No. 2, 2011

 Microstructure of PVAc-b-Poly(MA-co-MMA) Block Terpolymers. 2D NMR and Thermal Study

Figure 10. 2D TOCSY NMR spectrum of VAc unit in the PVAc-

b-poly(MA-co-MMA) block terpolymer in CDCl3 at 25 oC.

Figure 9. The region of expanded backbone methylene carbon-

13 resonance patterns of PMA, PMMA, and MA/MMA copoly-
mers with different mole fraction of MMA in CDCl3 at 25 oC. (FM
is mole fraction of MMA in copolymers).

carbonyl carbon of MA and MMA units in 13C NMR spec-

tra are observed around 174-178 ppm. This may probably
attribute to different couplings of carbonyl carbon with α-
CH3 and CH2 protons which vary with composition and ste-
reoregularity.25,27,35
As shown in Figure 11, the coupling of carbonyl carbon
Figure 11. 13C NMR spectra of the carbonyl carbon resonance
pattern of PMA, PMMA, and MA/MMA copolymers with differ-
ent mole fraction of MMA in CDCl3 at 25 oC. (FM is mole frac-
tion of MMA in copolymers).

Table VII. 13C, 2D HSQC, and TOCSY NMR Spectra of the Backbone Methylene and Methin Carbon Resonances of Vinyl Acetate
(V) Unit in the PVAc-b-Poly(MA-co-MMA) Block Terpolymer
13
Number Assignment C NMR (ppm) 2D HSQC (13C-1H) (ppm) 2D TOCSY (1H-1H) (ppm)
49 VVmVV / CH2 39.3 39.1/1.60 -
50 VVmVV / CH2 39.3 39.1/1.80 -
51 VVrVV / CH2 39.3 39.1/1.73 -
n In CH2 (VmV), H1 and H2 coupled - - 1.60/ 1.80
o CH (VV) coupled with CH2 (VmV, H1) - - 1.62/4.81
p CH (VV) coupled with CH2 (VrV) - - 1.78/ 4.81
q CH (VV) coupled with CH2 (VmV, H2) - - 1.82 /4.81
r CH (VV), Vicinal Coupling - - 4.78/ 4.79

Macromol. Res., Vol. 19, No. 2, 2011 163

 M. M. Ajjalallah and M. R. R. Daronkola

Table VIII. Complete Spectral Assignments of Carbonyl Carbon and DSC. The Tg values of PVAc, and A/M copolymers with
Resonance Based on the 13C NMR of MA/MMA Copolymers different MMA mole fractions of 0.733, 0.619, and 0.358
13
C NMR were obtained as 3713, 91, 77, and 49 oC.41
Number Carbonyl Carbon Coupled with Proton On the basis of the Fox equation, the Tg of these copoly-
(ppm)
53 C=O coupled with α-CH3 of MMrMrMM 177.80 mers with MMA weight fractions of 0.762, 0.654, and 0.393
were calculated to be 78, 66, and 40 oC (Table IX).
50 C=O coupled with α-CH3 of MMrMmMM 176.75
The experimental Tg of MA/MMA copolymer decreased
51 C=O coupled with α-CH3 of AMrMmMM 176.70 with MA fraction and deviate positively from the linear the-
52 C=O coupled with α-CH3 of AMrMmMA 176.90 oretical ones. Two different ranges of glass transitions tem-
peratures for PVAc and poly(MA-co-MMA) segments
53 C=O coupled with α-CH3 of MMmMmMM 176.66
indicating these block terpolymers are not miscible and
54 C=O coupled with α-CH3 of MAMAM 176.36 there is no specific interaction between these segments.13
55 C=O coupled with α-CH3 of AAMAM 175.6 The positive deviation between the experimental Tg from
56 C=O coupled with α-CH3 of AAMAA 175.2 the theoretical ones can be attributed to sequence distribu-
tion effects which in this study considered with the Fox
57 C=O coupled with CH2 of MMmMM (H1) 177.23 expanding or Johnston equation:42
58 C=O coupled with CH2 of MMmMM (H2) 178.07
1 W1 ⋅ P11 W2 ⋅ P22 1
59 C=O coupled with CH2 of AMmMM (H1) 177.1 -------------------- - + ----------------- + --------- ( W1 ⋅ P12 + W2 ⋅ P21 )
= ----------------
Tg, Johnston Tg1 Tg2 Tg12
60 C=O coupled with CH2 of AMmMM (H2) 178.0
1 1 [ M1 ]
61 C=O coupled with CH2 of AMmAM 176.45 P12 =1 – P11 = ------------------- &P21 =1 – P22 = ------------ &X = ----------
-
1 + r1 ⋅ X r2 [ M2 ]
1 + ----
62 C=O coupled with CH2 of AMmAA 176.55 X (1)
In this equation, Tg, Wi , Pij, Tgi, Tg12, and X are glass transi-
with α-methyl protons of MMrMrMM (52), MMrMmMM tion temperature of copolymers, weight fractions of MMA
(53), AMrMmMM (54), AMrMmMA (55), and MMmMmMM (1) and MA (2) units, probability of the addition of mono-
(56) resonate at 177.80, 176.75, 176.70, 176.90, and 176.66 mer j to growing chain terminated with an active species of
ppm. The peaks at 176.36, 175.6, and 175.2 ppm correspond i, Tg of MMA (108 oC13) and MA (8 oC41) homopolymers, Tg
to coupling of carbonyl carbon of AMA with α-methyl pro- of the alternating copolymer and molar ratio of MMA to
tons of MAMAM (57), AAMAM (58), and AAMAA (59) MA in feed.42 The results of calculations are summarized in
pentads. Table IX. The theoretical Tg which were calculated with
The coupling of carbonyl carbon with backbone methyl- Johnston equation are similar to experimental one confirm
ene protons of MMmMM (H1) (60), MMmMM (H2) (61), the effect of sequence distribution on Tg of MA/MMA
AMmMM (H1) (62), AMmMM (H2) (63) tetrads appear at copolymers.
177.23, 178.07, 177.1, and 178.0 ppm. The coupling of car-
bonyl carbon of AMA triad with protons of AMmAM (64) Conclusions
and AMmAA (65) tetrads appear as peaks at 176.45 and
176.55 ppm. These results were summarized in Table VIII. The complete spectral assignment by 1D and 2D NMR
Glass Transition Temperature. The theoretical and experi- showed that α-CH3, backbone methylene and methin car-
mental glass transition temperatures (Tg) of these block ter- bons were sensitive to sequence distribution, composition
polymers were studied by extended Fox (Johnston) equation and sterioregularity. Triad, dyad, and triad fractions of these

Table IX. Experimental Values of Tg Obtained by DSC and Compared with Theoretical Ones from Fox and Extended Fox (Johnston)
Equations
Sample Tg,exp (oC)a Tg,Fox (oC)b X W1 P11 P22 Tg,Johnston (oC)c
1 91 78 1.28 0.762 0.7243 0.2273 86.3
2 77 66 0.7874 0.654 0.6177 0.3235 76.4
3 49 40 0.2122 0.393 0.3034 0.6396 47.3
a
Obtained by DSC. Calculated with the Fox equation. The reactivity ratio of M and A units were reported to be 2.0524 and 0.3766.37
41 b

The Tg of MMA and MA units were reported to be 108 and 8 oC.41 Wi (i=1-2), Pij and X are weight fractions of MMA (1) and MA (2) units (W1
=1–W2), probability of the addition of monomer j to growing chain terminated with an active species of i and molar ratio of MMA to MA
in feed. P11, P22, P12, and P21 were calculated with equation 1. The Tg1,2=345oK is calculated from the linear line of the plot of
1 W1 ⋅ P 11 W2 ⋅ P 22
- + ------------------ versus (W1 ⋅ P 12 + W2 ⋅ P21) with R2=0.99. cCalculated with the equation 1.
---------------------- – -----------------
Tg, Johnston T g1 Tg2

164 Macromol. Res., Vol. 19, No. 2, 2011

 Microstructure of PVAc-b-Poly(MA-co-MMA) Block Terpolymers. 2D NMR and Thermal Study
carbons which were calculated by first-order Markov statis-
tical model confirmed the total assignments. The vicinal
and geminal couplings of the methin and methylene proton
atoms varied with sequence distribution and composition.
The theoretical glass transition temperatures of copolymers
were in good agreement with experimental ones and sup-
ported the effect of sequence distribution.
References
(1) K. Matyjaszewski, Prog. Polym. Sci., 30, 858 (2005).
(2) N. Hadjichristidis, H. Iatroua, M. Pitsikalisa, and J. Mays,
Prog. Polym. Sci., 31, 1068 (2006).
(3) N. A. Lynda, A. J. Meulerb, and M. A. Hillmyer, Prog. Polym.
Sci., 33, 875 (2008).
(4) G. Kwak, H. Kim, M.-W. Kim, S.-H. Hyun, Ch.-H. Baek, and
W.-S. Kim, Macromol. Res., 18, 67 (2010).
(5) B. J. Busche, A. E. Tonelli, and C. M. Balik, Polymer, 51, 454
(2010).
(6) S. V. Dvinskikh, U. H. N. Dürr, K. Yamamoto, and A. Ramamoorthy,
J. Am. Chem. Soc., 129, 794 (2007).
(7) M. K. Nguyen and D. S. Lee, Macromol. Res., 18, 284 (2010).
(8) Y. Nishiyama, T. Tanaka, T. Yamazaki, and T. Iwata, Macro-
molecules, 39, 4086 (2006).
(9) A. Ramakrishnan and R. Dhamodharan, Macromolecules, 36,
1039 (2003).
(10) M. A. Semsarzadeh and M. R. Rostami Daronkola, Iran. Polym.
J., 15, 829 (2006).
(11) A. Debuigne, J.-R. Caille, N. Willet, and R. Jérôme, Macro-
molecules, 38, 9488 (2005).
(12) M. A. Semsarzadeh and M. Abdollahi, Polymer, 49, 3060
(2008).
(13) M. R. Rostami Daronkola and M. A. Semsarzadeh, J. Polym.
Res., 15, 403 (2008).
(14) P. Li, Z. Xia, A. Zerroukhi, J. Chen, Y. Chalamet, and T. Jean-
maire, J. Appl. Polym. Sci., 115, 1958 (2010).
(15) M. A. Semsarzadeh and M. R. Rostami Daronkola, Iran. Polym.
J., 16, 47 (2007).
(16) L. Wang, J. Lin, and L. Zhang, Macromolecules, 43, 1602
(2010).
(17) D. P. Christy, R. F. Barlow, and D. A. Shipp, J. Polym. Sci.
Part A: Polym. Chem., 46, 7200 (2008).
(18) S. Mendrek, A. Mendrek, H.-J. Adler, A. Dworak, and D. Kuck-
ling, J. Polym. Sci. Part A: Polym. Chem., 47, 1782 (2009).
(19) H.-C. Kim, S.-M. Park, and W. D. Hinsberg, Chem. Rev., 110,
Macromol. Res., Vol. 19, No. 2, 2011
146 (2010).
(20) W. Z. Wang, W. Song, R. Wang, and T. X. Liu, J. Polym. Sci.
Part A: Polym. Chem., 47, 1478 (2009).
(21) I. Noda, J. Molecul. Struct., 799, 2 (2006).
(22) A. Malinowskab, P. Vl čeka, J. Kří ž a, L. Tomana, P. Láta-
lováa, M. Janataa, and B. Masa řa, Polymer, 46, 5 (2005).
(23) H. Wickel, S. Agarwal, and A. Greiner, Macromolecules, 36,
2397 (2003).
(24) S.-C. Lim, S.-W. Kim, M.-H. Jung, M.-K. Cho, J.-H. Kim,
H.-S. Cho, and J.-H. Ok, J. Molecul. Struct., 886, 166 (2008).
(25) A. S. Brar and M. Markanday, Polymer, 46, 11527 (2005).
(26) A. S. Brar, A. K. Goyal, S. Hooda, and R. Shankar, J. Polym.
Sci. Part A: Polym. Chem., 47, 25 (2009).
(27) S. Hooda, A. K. Goyal, and A. S. Brar, J. Molecul. Struct.,
920, 424 (2009).
(28) D. M. Savant, D. V. Reddy, E. F. McCord, and P. L. Rinaldi,
Macromolecules, 40, 4199 (2007).
(29) F. Ziaee, H. Bouhendi, and F. Ziaie, Iran. Polym. J., 18, 947
(2009).
(30) X. H. Qiu, D. Redwine, and G. Gobbi, Macromolecules, 40,
6879 (2007).
(31) S. Hooda, A. K. Goyal, and A. S. Brar, J. Appl. Polym. Sci.,
111, 2381 (2009).
(32) S. Hooda, A. K. Goyal, and A. S. Brar, J. Molecul. Struct.,
963, 27 (2010).
(33) Y. Kim and H. J. Harwood, Polymer, 43, 3229 (2002).
(34) R. Aggarwal, J. Sumran, R. M. Claramunt, D. Sanz, and J.
Elguero, J. Molecul. Struct., 934, 96 (2009).
(35) R. Ramachandran, M. Rani, and S. Kabilan, J. Molecul. Struct.,
970, 42 (2010).
(36) A. S. Brar, G. Singh, and R. Shankar, J. Appl. Polym. Sci., 99,
1437 (2006).
(37) M. A. Semsarzadeh, M. R. Rostami Daronkola, and M.
Abdollahi, J. Mac. Sci. Part A: Pure Appl. Chem., 44, 953
(2007).
(38) K. Katsuraya, K. Hatanaka, K. Matsuzaki, and K. Yamaura,
Macromol. Rapid Commun., 21, 697 (2000).
(39) M. Matlengiewicz, M. Pasich, P. Bujak, and N. Henzel, Inter.
J. Polym. Analys. Charac., 14, 686 (2009).
(40) A. S. Brar, G. Singh, and R. Shankar, Eur. Polym. J., 40, 2679
(2004).
(41) M. A. Semsarzadeh and M. R. Rostami-Daronkola, Iran. J.
Polym. Sci. Technol., 22, 197 (2009).
(42) S.-W. Kuo, H.-C. Kao, and F.-C. Chang, Polymer, 44, 6873
(2003).
165