Synthesis of novel tetrahydrofuran-epichlorohydrin [Poly(THF-b-ECH)] macromonomeric peroxy initiators by cationic copolymerization and the quantum chemically investigation of initiation system effects

Article abstract of DOI:10.1002/pola.24069

Cationic polymerization of tetrahydrofuran (THF) and epichlorohydrin (ECH) was performed with peroxy initiators synthesized from bis (4,4′- bromomethyl benzoyl peroxide (BBP) or bromomethyl benzoyl t-butyl peroxy ester (t-BuBP) and AgSbF₆ or Zn

Full text of DOI:10.1002/pola.24069

Synthesis of Novel Tetrahydrofuran-Epichlorohydrin [Poly(THF-b-ECH)]
Macromonomeric Peroxy Initiators by Cationic Copolymerization and
the Quantum Chemically Investigation of Initiation System Effects
MURAT MISIR,1 TEMEL OZTURK,2 MUSTAFA EMIRIK,3 SEVIL S. YILMAZ1
1Department of Chemistry, Karadeniz Technical University, Trabzon 61080, Turkey
2Department of Chemistry, Kafkas University, Kars 36100, Turkey
3Department of Chemistry, Rize University, Rize 53100, Turkey
Received 24 February 2010; accepted 13 April 2010
DOI: 10.1002/pola.24069
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Cationic polymerization of tetrahydrofuran (THF) and
epichlorohydrin (ECH) was performed with peroxy initiators
synthesized from bis (4,40-bromomethyl benzoyl peroxide (BBP)
or bromomethyl benzoyl t-butyl peroxy ester (t-BuBP) and AgSbF6
or ZnCl2 system at 0 ꢀC to obtain the poly(THF-b-ECH) macromo-
nomeric peroxy initiators. Kinetic studies were accomplished for
poly(THF-b-ECH) initiators. Poly(THF-b-ECH-b-MMA) and poly
(THF-b-ECH-b-S) block copolymers were synthesized by bulk
polymerization of methyl methacrylate (MMA) and styrene (S)
with poly(THF-b-ECH) initiators. The quantum chemical
calculations for the block copolymers, the initiating systems of the
cationic polymerization of THF and ECH were achieved using
HYPERCHEM 7.5 program. The optimized geometries of the poly-
mers were investigated with the quantum chemical calculations.
Poly(THF-b-ECH) initiators having peroxygen groups were used
for graft copolymerization of polybutadien (PBd) to obtain
poly(THF-b-ECH-g-PBd) crosslinked graft copolymers. The graft
copolymers were investigated by sol-gel analysis. Swelling ratio
values of the graft copolymers in CHCl3 were calculated. The char-
acterizations of the polymers were achieved by FTIR, 1H NMR,
C
V
GPC, SEM, TEM, and DSC techniques. 2010 Wiley Periodicals,
Inc. J Polym Sci Part A: Polym Chem 48: 2896–2909, 2010
KEYWORDS: block and graft copolymers; cationic polymeriza-
tion; macroperoxy initiators; multicomponent copolymers;
quantum chemical calculations (MM2)
INTRODUCTION Macrointermediates such as macroinitiators,
macromonomers, and macrocrosslinkers are very important
in polymer modification leading to block and graft copoly-
mers.1–4 Macromonomeric initiators which behave as a
macromonomer, macroinitiator, or macrocrosslinker have
attracted a great interest because they lead to be synthesized
crosslinked or branched block copolymers. Macroinitiators
can be divided into two classes, according to the free radical
initiator group: macroazo initiators and macroperoxy initia-
tors. We have recently reported the synthesis of these two
types of macroinitiators.5–7 Polytetrahydrofuran (PTHF) per-
oxy initiators as macroperoxy initiators were previously syn-
thesized by the reaction of PTHF-diol, isophrandiisocyanate,
2,5-dimethyl-2,5-dihydroperoxy hexane, and isocyanatoethyl
methacrylate.6,8 Moreover, we have described the synthesis
of PTHF-peroxy initiators obtained from the cationic poly-
merization of tetrahydofuran (THF) with bromomethyl ben-
zoyl t-butyl peroxy ester (t-BuBP) or bis (4,40-bromomethyl
peroxygen groups do not decompose during the cationic
polymerization, because low reaction temperatures used for
the cationic polymerization such as 0 ꢀC are not enough to
decompose them. Then, these peroxygen groups can lead to
react with a monomer by using appropriate reaction condi-
tions to obtain crosslinked block or graft copolymers.
Although block and graft copolymers have many similar
characteristics, graft copolymers have a branching chain
structure attaching polymer units to another polymer back-
bone.12 Grafting onto a backbone structure such as commer-
cially available natural polypropylene (PP) or polybutadien
(PBd) is important because these graft copolymers can have
excellent mechanical properties.13
This article describes the synthesis of poly(THF-b-ECH) mac-
roperoxy initiators obtained from the cationic polymerization
of THF and epichlorohydrin (ECH) with t-BuBP and BBP in
the presence of AgSbF6 or ZnCl2. Poly(THF-b-ECH) macroper-
oxy initiators had decomposed peroxygen groups and vinyl
end groups, so they could be polymerized with a monomer
to obtain block, graft, or multicomponent copolymers. For
this purpose, poly(THF-b-ECH) macroperoxy initiators with
methyl methacrylate (MMA) and styrene (S) were used to
benzoyl peroxide) (BBP) or bis (3,5-dibromomethyl benzoyl
9,10
peroxide) (BDBP) in the presence of AgSbF6
or ZnCl2.11
The initiators based on t-BuBP, BBP, and BDBP are important
because they have undecomposed peroxygen groups. The
Correspondence to: S. S. Yilmaz (E-mail: sevily@ktu.edu.tr)
C
V
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 48, 2896–2909 (2010) 2010 Wiley Periodicals, Inc.
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ARTICLE
synthesize poly(THF-b-ECH-b-MMA) and poly(THF-b-ECH-b-
S) block copolymers. Then, we synthesized poly(THF-b-ECH-
g-PBd) graft copolymers by the copolymerization of poly
(THF-b-ECH) macroperoxy initiators and PBd. Moreover, we
investigated the effects of t-BuBP, BBP/AgSbF6, ZnCl2 initiat-
ing systems on the cationic copolymerization of THF and
ECH as quantum chemically by using HYPERCHEM 7.5
program.
20,000, 52,000, and 96,400 Da, of low dispersity purchased
from Polyscience. Differential scanning calorimetry (DSC)
measurements were performed using a Setaram DSC-141 se-
ries thermal analysis system. The heating rate was 10 ꢀC/
min. FTIR spectra were recorded using a Perkin–Elmer 1600
Series FTIR Spectrometer. 1H NMR of the products was
recorded using a Varian/Mercury-200 NMR Spectrometer, in
CDCl3 solvent and tetra methylsilane as the internal stand-
ard. Scanning electron micrographs (SEM) were taken on a
Jeol JXA-840A electron microscope. The specimens were fro-
zen under liquid nitrogen, then fractured, mounted, and
coated with gold (300 Å) on an Edwards S 150 B sputter
coater. SEM measurements were operated at 10 kV. The elec-
tron images were recorded directly from the cathode ray
tube onto a Polaroid film. The magnification employed was
varied up to 3000ꢂ. Transmission Electron Microscopy
(TEM) measurements were performed on JEOL-JEM-2100
HRTEM operating at 200 kV (LaB6 filament). Images were
taken by Gatan Model 694 Slow Scan CCD Camera. Very
small drops of samples were dropped onto carbon support
film coated copper TEM grids (Agar).
COMPUTATIONAL METHOD
All calculations were performed using HYPERCHEM 7.5 pro-
gram14 on an IBM PC-Pentium-IV computer. The quantum
chemical properties of t-BuBP/AgSbF6, t-BuBP/ZnCl2, BBP/
AgSbF6, BBP/ZnCl2 initiating systems, poly(THF-b-ECH) mac-
roperoxy initiator chains (degree of polymerization of poly-
styrene (PS); n ¼ 5), and the block copolymer chains (degree
of polymerization of poly(THF-b-ECH); n ¼ 5 and degree of
polymerization of polymethyl methacrylate (PMMA); m ¼ 5)
were calculated. The quantum chemical analyses of the ini-
tiating systems were performed using the Hyperchem 7.5 pa-
rameters for MM2. Full geometry optimization was carried
out employing the Polak-Ribiere conjugate-gradient method
Synthesis of Bromomethyl Benzoyl Peroxides
(t-BuBP and BBP)
until an RMS gradient was reached to 0.0001 kcal (Å mol)ꢁ1
.
The optimized geometries of poly(THF-b-ECH) macroperoxy
initiator chains (n ¼ 5) and the block copolymer chains (n ¼
5 for MMA and m ¼ 5 for S) were performed by molecular
mechanics MM2.15
The mono functional bromomethyl benzoyl t-butyl peroxy
ester (t-BuBP) and bis (4,40-bromomethyl benzoyl peroxide)
(BBP) were synthesized by the reaction of the corresponding
bromomethyl benzoyl bromides with peroxides as in litera-
ture.1,7 Scheme 1 shows the reaction chart for t-BuBP and
BBP.
EXPERIMENTAL
Materials
Synthesis of Poly(THF-b-ECH) Macroperoxy Initiators
Poly(THF-b-ECH) macroperoxy initiator were synthesized by
the cationic polymerization of THF and ECH initiated withꢀt-
BuBP or BBP and AgSbF6 or ZnCl2 initiating systems at 0 C
according to the described procedure.9,10 Initiator (t-BuBP, 1
mmol or BBP, 1 mmol) and monomer (THF, 50 mL) were
added to the flask in cryostat system, respectively. Then the
ECH (Fluka, 99 wt %) was used as received without any pu-
rification. THF (Sigma, 99 wt %) refluxed and distilled over
a sodium and benzophenone mixture after producing a pur-
ple color, just before use. S and MMA (Aldrich, 99 wt %)
were washed with 5 wt % aqueous NaOH solution five times
and then with pure water until the aqueous phase became
neutral. They were dried over anhydrous calcium chloride
(CaCl2, Aldrich) overnight and distilled under reduced pres-
sure. Silver hexafluoroantimonate (AgSbF6, Aldrich, 98 wt
%), zinc chloride (ZnCl2, Aldrich, >99 wt %), PBd (Aldrich,
98 wt % cis, average Mw ¼ 2000,000 g molꢁ1), and N-bro-
mosuccinimide (Aldrich, 99 wt %) were used as received
without any purification. Potassium salt of methacrylic acid
was synthesized by the reaction of equimolar amounts of
methacrylic acid (Aldrich, 99 wt %) and saturated potassium
hydroxide (KOH, Fluka, >86 wt %) solution in methanol. It
was purified by reprecipitation from methanol solution into
excess acetone.16 Chloroform (CHCl3, Technical) was distilled
over anhydrous CaCl2 before using. All other chemicals were
reagent grade and used as received.
ꢀ
flask was immersed in cryostat bath at 0 C temperature. Af-
ter degassing the reaction mixture, catalyst (AgSbF6 or
ZnCl2) was added to the solution. After mixing the reacting
mixture for 2 h at 0 ꢀC, ECH (dried, 20 mL) was added to
this solution and the mixture was mixed for 2 h. At the end
of the desired reaction time, potassium salt of methacrylic
acid was added to the polymerization mixture to have meth-
acrylic acid end groups. The solution was stirred for 3 h and
filtered to remove precipitated AgBr or ZnBr2 salts. Then,
the filtrate was poured on 0.5 L of cold 0.1 M NH3 solution
to purify poly(THF-b-ECH) macroperoxy initiator. Poly(THF-
b-ECH) macroperoxy initiator was precipitated from diethyl
ether:petroleum ether (1:1) solution at room temperature.
Scheme 2 shows the reaction mechanism of poly(THF-b-
ECH) macroperoxy initiator with t-BuBP or BBP (n ¼ 5). The
polymerization conditions and results are listed in Table 1.
Polymer Characterization
Molecular weights (Mn, Mw) and molecular weight distribu-
tions (MWD) were measured with a Knauer GPC using
ChromGate software, a WellChrom Interface Box, RI Detector
K-2301, and WellChrom HPLC pump K-501. CHCl3 was used
as an eluent at a flow rate of 1 mL/min. A calibration curve
was generated with six PS standards: 2500, 2950, 5050,
Copolymerization of MMA with Poly(THF-b-ECH)
Macroperoxy Initiators
Yılmaz et al.1,10 reported the same polymerization procedure
to obtain block copolymers starting from t-BuBP and BBP.
SYNTHESIS OF NOVEL MACROMONOMERIC PEROXY INITIATOR, MISIR ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
SCHEME 1 The reaction mecha-
nism of t-BuBP and BBP. [Color
figure can be viewed in the
online issue, which is available
at www.interscience.wiley.com.]
THE CALCULATIONS FOR THE INITIATING SYSTEMS
The required amount of poly(THF-b-ECH) macroperoxy ini-
tiator and MMA as monomer were put into a Pyrex tube and
stirred until the solution became homogenous. Then, the so-
lution was deoxygenated by bubbling N2 for 10 min. The
tube was covered with a stopper and placed into an oil bath
t-BuBP, BBP/AgSbF6, ZnCl2 initiating systems were investi-
gated using molecular mechanic method (MM2). The distan-
ces between CASb atoms and CACl atoms (rC-Sb and rC-Cl
)
and the strain energies (Estr were calculated for the
)
ꢀ
at 90 C. The reaction continued for 6, 12, and 24 h stirring
t-BuBP/AgSbF6, BBP/AgSbF6, t-BuBP/ZnCl2, and BBP/ZnCl2
during the polymerization. Subsequently, the reaction was
terminated with excess methanol. Poly(THF-b-ECH-b-MMA)
block copolymers were dried at 40 ꢀC under vacuum for
three days. The yield of the polymer was determined gravi-
metrically. The same procedure was carried out with S to
obtain poly(THF-b-ECH-b-S) block copolymers. The condi-
tions and results are given in Tables 2 and 3.
initiating systems. The results obtained are given in Table 5.
The Quantum Chemical Calculations for
the Block Copolymers
Formation of poly(THF-b-ECH) macroperoxy initiators, poly
(THF-b-ECH-b-MMA) and poly(THF-b-ECH-b-S) block copoly-
mers were investigated using molecular mechanic method
(MM2). The internal rotation angle (u) and the strain energy
values (Estr) of poly(THF-b-ECH) macroperoxy initiators and
the block copolymers were calculated by using MM2 method.
The results obtained are given in Table 6. The optimized
geometries of poly(THF-b-ECH) macroperoxy initiators,
poly(THF-b-ECH-b-MMA) and poly(THF-b-ECH-b-S) forms are
given in Figure 1.
Synthesis of Poly(THF-b-ECH-g-PBd) Graft Copolymers
As a typical procedure: 0.5 g of poly(THF-b-ECH) macroper-
oxy initiator, 0.5 g of PBd, and 30 mL of CHCl3 as solvent
were stirred for 24 h at room temperature. This solution
was spread on a glass plate and dried at room temperature
for 2 days to obtain a polymer film. After drying, the poly-
mer film was put into a Pyrex tube. Then, the polymerization
ꢀ
was carried out in an oil bath at 90 C under N2 for 6 h. The
RESULTS AND DISCUSSION
graft copolymer mixture was extracted with CHCl3 for 24 h,
so swollen graft copolymer was obtained. The swollen gels
were filtered off and mixed with methanol to remove homo-
polymers. Then, the poly(THF-b-ECH-g-PBd) graft copolymer
was dried under vacuum at 50 ꢀC for a week. Scheme 3
shows the reaction chart of the crosslinked graft copolymer.
The results are listed in Table 4.
Synthesis of Poly(THF-b-ECH) Macroperoxy Initiators
Mono- and di-functional peroxy esters9,10,17,18 were used for
the synthesis of the living PTHF initiators containing peroxy-
gen groups (active PTHF) in previous articles, which were
terminated by the potassium salt of methacrylic acid to have
vinyl end groups. In this study, the cationic polymerization
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ARTICLE
SCHEME 2 The reaction mechanism of
poly(THF-b-ECH) macroperoxy initiators.
Synthesized by the cationic polymerization
of THF and ECH with t-BuP/AgSbF6 initiat-
ing system. Synthesized by the cationic
polymerization of THF and ECH with BBP/
AgSbF6 initiating system. [Color figure can
be viewed in the online issue, which is
available at www.interscience.wiley.com.]
of THF and ECH was performed using a catalyst mixture
composed of the bromomethyl derivatives of benzoyl perox-
ides, and AgSbF6 or ZnCl2 at 0 C. As a result of the cationic
polymerization of t-BuBP and BBP with THF and ECH, one-
and two-armed poly(THF-b-ECH) macroperoxy initiators
with vinyl end groups were obtained for t-BuBP and BBP,
respectively. Thus, t-BuBP has one bromomethyl group and
consumes 1 mol of silver or zinc salt, while BBP consumes 2
mol of silver or zinc salt. According to Table 1, we see that
the longer polymerization times gave higher molecular
weights and yields as we expected. The average molecular
weight (Mn) and conversion (wt %) values of poly(THF-b-
ECH) macroperoxy initiators with t-BuBP in the presence of
AgSbF6 are bigger than those in the presence of ZnCl2. How-
ever, Mn values with BBP/AgSbF6 initiating system are
smaller than those with BBP/ZnCl2 initiating system. It
means that AgSbF6 is more reactive in the cationic polymer-
ization of t-BuBP, and also ZnCl2 is more reactive for BBP.
The reason may be steric effects between two-armed BBP
and AgSbF6 molecules. Moreover, MWD values of poly(THF-
ꢀ
SYNTHESIS OF NOVEL MACROMONOMERIC PEROXY INITIATOR, MISIR ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
TABLE 1 Cationic Polymerization of THF and ECH with t-BuBP or BBP and AgSbF6 or ZnCl2 at 0 8C (THF 5 50 mL, ECH 5 20 mL)
f (Initiator
Run
no
Polym.
Yield
(g)
Conver.
(wt %)
Efficiency)
n,th/Mn,GPC
DPPTHF/
Initiating System
Time (h)
Mn,th
Mn,GPC
MWD
M
DPPECH
2 ꢂ 10ꢁ2 M t-BuBP þ 2 ꢂ 10ꢁ2 M AgSbF6
1
2
4
24
48
4
0.83
21.46
35.93
0.79
22.10
31.53
52.80
1.16
3,466
4,822
7,882
454
7,338
9,729
11,214
3,522
3,549
3,672
4,426
4,671
4,867
5,550
2,383
2,394
2,652
1.6
1.9
1.8
1.4
1.5
1.4
1.4
1.8
1.7
1.6
1.6
1.7
1.7
0.47
0.50
0.70
0.13
0.16
0.37
0.13
0.65
1.10
1.39
0.21
0.33
0.51
7.53
2.58
0.81
9.25
13.05
1.93
13.22
8.86
2.90
1.62
6.01
7.63
8.22
3
2 ꢂ 10ꢁ2 M t-BuBP þ 2 ꢂ 10ꢁ2 M ZnCl2
2 ꢂ 10ꢁ2 M BBP þ 4 ꢂ 10ꢁ2 M AgSbF6
4
5
12
48
4
1.41
2.07
585
6
5.13
7.54
1,373
569
7
0.67
0.98
8
10
12
48
4
12.40
17.82
34.37
0.38
18.20
34.20
50.50
0.55
3,046
5,347
7,692
507
9
10
11
12
13
2 ꢂ 10ꢁ2 M BBP þ 4 ꢂ 10ꢁ2 M ZnCl2
12
48
1.67
2.45
780
4.43
6.51
1,364
b-ECH) macroperoxy initiators in Table 1 are low (ꢃ1.9).
When MWD values of poly(THF-b-ECH) macroperoxy initia-
tors were compared, it was seen that higher MWD values
were obtained with ZnCl2. These results are in a good agree-
ment with the results obtained by Cai and Yan for the cat-
ionic polymerization of di-, tri-, and tetra-bromomethyl
benzene.19
PTHF content decreased as the polymerization time
increased for poly(THF-b-ECH) macroperoxy initiators syn-
thesized with BuBP/AgSbF6 initiating systems but the PTHF
content increased as the polymerization time increased for
poly(THF-b-ECH) macroperoxy initiators synthesized with
BBP/ZnCl2 initiating systems. These results indicate that the
cationic polymerization can be used to prepare poly(THF-b-
ECH) macroperoxy initiators containing the desired segment
ratio by changing the polymerization conditions.
The degree of polymerization ratios, DPPTHF/DPPECH (m/n),
were determined by comparing the integrated intensities of
AOCH2 of PECH chain at 4.9 ppm to ACH2 protons of PTHF
chains at 1.7 ppm as shown Table 1. Generally, the PTHF
composition of poly(THF-b-ECH) macroperoxy initiators was
more than PECH composition of the initiator. We attributed
that ECH was added to the solution after the reacting mix-
ture including THF was mixed for 2 h. Interestingly, the
Kinetic studies were carried out to investigate controlled cat-
ionic polymerizationꢀof t-BuBP, BBP/AgSbF6, ZnCl2 initiating
systems with S at 0 C. Figure 2(a,b) show the semi logarith-
mic kinetic plots for the polymerization of t-BuBP/AgSbF6—
BBP/AgSbF6 initiating systems (run no 1, 2, 3–7, 8, 9, 10 in
Table 1) and t-BuBP/ZnCl2—BBP/ZnCl2 initiating systems
TABLE 2 Copolymerization of MMA with Poly(THF-b-ECH) Macroperoxy Initiators at 90 8C
Block
Copolymer
Run no
Poly(THF-b-ECH)
Initiator (g)
Polym.
Run no
in Table 1
MMA (g)
Time (h)
(g)
(wt %)
Mn
895,642
Mw
MWD
14
15
16
17
18
19
20
21
22
23
24
2
2
2
2
2
2
8
8
8
8
8
0.205
0.203
0.203
0.202
0.204
0.201
0.209
0.203
0.203
0.201
0.209
1.012
1.001
1.014
1.016
1.008
1.002
1.004
1.006
1.008
1.002
1.012
1
2
3
4
5
6
1
2
3
4
6
0.404
0.789
0.791
0.805
0.801
0.884
0.904
0.910
0.952
1.085
1.099
33.2
65.5
64.9
66.1
66.1
73.5
74.5
75.2
78.6
90.2
90
1,697,865
1,418,918
1,664,386
1,834,975
1,886,978
1,654,366
695,559
1.8
2.5
1.7
1.6
1.5
1.5
2.3
3.3
1.5
1.5
1.6
547,374
971,053
1,087,714
1,192,780
1,041,136
289,901
186,967
629,608
1,225,595
677,628
1,930,930
1,052,280
1,245,830
757,343
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TABLE 3 Copolymerization of S with Poly (THF-b-ECH) Macroperoxy Initiators at 90 8C
Block Copolymer
Run no
Poly(THF-b-ECH)
Polym.
Run no
in Table 1
Initiator (g)
S (g)
Time (h)
(g)
(wt %)
Mn
Mw
MWD
25
26
27
28
29
30
31
32
33
34
2
2
2
2
2
8
8
8
8
8
0.200
0.204
0.206
0.201
0.201
0.205
0.206
0.200
0.206
0.201
1.006
1.004
1.003
1.010
1.009
1.009
1.013
1.011
1.022
1.001
1
2
3
4
6
1
2
3
4
6
0.069
0.139
0.217
0.224
0.249
0.158
0.188
0.191
0.226
0.235
5.7
11.5
17.9
18.5
20.6
13.0
15.4
15.8
18.4
19.5
116,425
131,120
173,001
230,654
270,081
110,697
187,554
195,271
113,081
193,734
173,718
210,896
269,973
353,085
411,604
152,213
241,157
391,374
227,909
355,944
1.4
1.6
1.5
1.5
1.5
1.3
1.2
2.0
2.1
1.8
SCHEME 3 The reaction chart of crosslinked poly(THF-b-ECH-g-PBd) graft copolymer.

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
TABLE 4 The Graft Copolymerization of PBd (ꢄ0.5 g) with Poly(THF-b-ECH) Macroperoxy Initiators (ꢄ0.5 g) at 90 8C
wt % in the Polymer
Graft
Crosslinked
Graft Copolymer
(wt %)
Content
Mixture
Run no
Polym.
Copolymer
(wt %)
of Homo
PBd (wt %)
Run no.
in Table 1
Time (h)
PBd
Poly(THF-b-ECH)
qv (in CHCl3)
35
36
37
38
39
40
41
42
3
3
4
8
4
8
4
8
4
8
49.9
49.8
50.2
50.0
49.4
50.3
50.2
49.9
50.1
50.2
49.8
50.0
50.6
49.7
49.8
50.1
92
91
78
81
94
71
90
84
20.8
35.7
18.9
42.1
25.3
20.5
52.7
48.5
71.2
55.3
59.1
38.9
68.6
50.5
37.3
35.5
2.71
3.06
2.57
3.09
2.28
2.79
2.96
3.05
8
8
9
9
10
10
(run no 4, 5, 6–11, 12, 13 in Table 1), respectively. Mn and
MWD versus conversion (wt %) are shown in Figure 2(c) for
t-BuBP/AgSbF6—BBP/AgSbF6 initiating systems (run no 1,
2, 3–7, 8, 9, 10 in Table 1) and in Figure 2(d) for t-BuBP/
ZnCl2-BBP/ZnCl2 initiating systems (run no 4, 5, 6–11, 12,
13 in Table 1). For all initiating systems, the plots of ln
([Mo]/[Mt]) versus reaction time are linear, corresponding to
first-order kinetics. Moreover, Mn and Mw/Mn-versus-conver-
sion (wt %) plots demonstrate the good control of molecular
weight as a function of conversion for all initiating systems.
ics. The optimized geometries of the structures are given in
Figure 1.
Copolymerization of MMA with Poly(THF-b-ECH)
Macroperoxy Initiators
Copolymerization of MMA with poly(THF-b-ECH) macroper-
oxy initiators demonstrated that poly(THF-b-ECH) macroper-
oxy initiators showed the characteristic macroinitiator
behavior5,8,20 because block copolymers were obtained as a
result of the copolymerization. The yields of block copoly-
mers obtained from MMA and poly(THF-b-ECH) macroperoxy
initiators with t-BuBP/AgSbF6 or ZnCl2 initiating system
were smaller than those obtained from BBP/AgSbF6 or ZnCl2
initiating system (Table 2). Thus, it is clear that BBP/AgSbF6
or ZnCl2 initiating system is more reactive to obtain block
copolymers with MMA because poly(THF-b-ECH) macroper-
oxy initiators of BBP with two end groups have more vinyl
and peroxygen groups than poly(THF-b-ECH) macroperoxy
initiators of t-BuBP with one end group.
The values of rC-Sb distance calculated as quantum chemi-
cally for the t-BuBP/AgSbF6 and BBP/AgSbF6 initiating sys-
tems are 2.1754 Å and 2.1756 Å; the rC-Cl distances for t-
BuBP/ZnCl2 and BBP/ZnCl2 initiating systemsare 1.7964 Å
and 1.7963 Å, respectively, (Table 5). CASb bond in SbF6(Cþ
ion-pair is weaker and more unstable than CACl bond in
ClꢁCþ ion-pair. Since the rC-Sb distances in the t-BuBP/
AgSbF6 and BBP/AgSbF6 initiating systems are bigger than
the rC-Cl distances in the t-BuBP/ZnCl2 and BBP/ZnCl2 initiat-
ing systems, it is easier to break rC-Sb bond than rC-Cl bond.
In the same way, the addition of THF molecules between Sb
and C atoms of SbFꢁ6 Cþ ion-pair is easier than that between
Cl and C atoms of ClꢁCþ ion-pair. It is also found from the
quantum mechanical calculations that the conversion (wt %)
of the cationic polymerization of THF with t-BuBP or BBP in
the presence of AgSbF6 is bigger than that in the presence of
ZnCl2.
Synthesis of Poly(THF-b-ECH-g-PBd) Graft Copolymers
with Poly(THF-b-ECH) Macroperoxy Initiators
The graft copolymerization of poly(THF-b-ECH) macroperoxy
initiators with PBd could be synthesized at 90 ꢀC because
poly(THF-b-ECH) macroperoxy initiators contain both vinyl
and undecomposed peroxygen groups. The conditions and
results of the copolymerization are given in Table 4. The
swelling ratios of poly(THF-b-ECH-g-PBd) crosslinked graft
The internal rotation angle (u) and the strain energy (Estr
)
values of poly(THF-b-ECH) macroperoxy initiators and the
block copolymers are given in Table 6. The internal rotation
angles of poly(THF-b-ECH) macroperoxy initiators and the
block copolymers are almost 180ꢀ. The strain energies were
also calculated for poly(THF-b-ECH) macroperoxy initiators
(n ¼ 5) and the block copolymers (n ¼ 5 and m ¼ 5).
According to Table 6, the strain energy increases with the
variation of the conformational chain. For the sake of the
dependability of the results obtained, conformational analy-
sis of poly(THF-b-ECH) macroperoxy initiators (n ¼ 5) and
the block copolymers (n ¼ 5 and m ¼ 5) with different
steric regularity were performed by the molecular mechan-
TABLE 5 The Strain Energies and the Bond Lengths Between
C-Sb and C-Cl Atoms (rC-Sb and rC-Cl) of t-BuBP-SbF6 and
BBP-SbF6 Initiating Systems at Scheme 2
MM2 Estr
(kcal molꢁ1
)
rC-Sb (A)
rC-Cl (A)
˚
˚
Initiating System
t-BuBP/AgSbF6
t-BuBP/ZnCl2
BBP/AgSbF6
BBP/ ZnCl2
8.788
8.001
9.914
7.556
2.1754
–
–
1.7964
–
2.1756
–
1.7963
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TABLE 6 The Strain Energies and the Internal Rotation Angles of Poly(THF-b-ECH) Initiators and the Block Copolymers According
to MM2 Method
PMMA-PTHF-
Poly
Poly
PTHF-PECH-PMMA PECH-PMMA
PTHF-PECH-PS
PS-PTHF-PECH-PS
(THF-b-ECHa (THF-b-ECH)b (n ¼ 5 and m ¼ 5)
(n ¼ 5 and m ¼ 5) (n ¼ 5 and m ¼ 5) (n ¼ 5 and m ¼ 5)
Mn,th ¼ 825
Mn,th ¼ 825
Mn,th ¼ 1325
Mn,th ¼ 1825
Mn,th ¼ 1345
Mn,th ¼ 1865
Estr (kcal molꢁ1
u (ꢀ)
)
29.775
114.905
176.655
141.136
174.018
276.917
175.550
59.872
125.615
175.451
179.976
173.183
a
b
Synthesized with the cationic polymerization of THF, ECH with t-BuBP/
Synthesized with the cationic polymerization of THF, ECH with BBP/
AgSbF6 initiating system.
AgSbF6 initiating system.
copolymers decrease as the conversions (wt %) of the cross-
linked graft copolymers increase.
of PS, at 1180 cmꢁ1 for CAO peaks of benzoyl groups, at
1450–1600 cmꢁ1 for C¼¼C peaks of aromatic rings, at 1757
cmꢁ1 for C¼¼O peaks of benzoyl peroxide groups, at 2853–
2923 cmꢁ1 for ACHACH2 peaksof PS groups and -CH2 peaks
attached benzoyl peroxide group, and at 3000 cmꢁ1 for over
aromatic ACH peaks of benzoyl peroxide group. FTIR spec-
trum of poly(THF-b-ECH-g-PBd) graft copolymer (run no 36
in Table 4) shows the characteristic peaks at 1720 cmꢁ1 for
AC¼¼O groups attached phenyl group, at 1113 cmꢁ1 for
ACAOA groups of PTHF and PECH, at 2939 cmꢁ1 for alcan
group peaks of PBd, and at 3005 cmꢁ1 for alcen group peaks
of PBd.
Characterization of the Polymers
The characterization of poly(THF-b-ECH) macroperoxy initia-
tors and the block copolymers were achieved by FTIR, 1H
NMR, DSC, and GPC techniques. Figure 3 shows 1H NMR
spectrums of poly(THF-b-ECH) macroperoxy initiators for
t-BuBP/AgSbF6 (run no 3 in Table 1) and BBP/ZnCl2 (run no
21 in Table 1) initiating systems. The most important differ-
ence between Figure 3(a,b) is the peak of t-butyl groups at
1.2 ppm for the t-BuBP/AgSbF6 initiating system. Also, Fig-
ure 3 shows the characteristic peaks at 3.8 and 4.2 ppm for
ACH2 groups of aromatic rings, 3.2 and 3.6 ppm for ACH2O
protons of PTHF and polyepichlorohydrin (PECH) in the
poly(THF-b-ECH) macroperoxy initiator. The signals at 7.8
and 8.0 ppm are the peaks of aromatic ring protons of ben-
zoyl groups. The peaks of poly(THF-b-ECH-b-MMA) block
copolymers adding peaks of poly(THF-b-ECH) macroperoxy
initiator are following: 1.0 ppm for ACH3 protons of MMA,
3.5 ppm for AOCH3 protons of MMA, and 3.6 ppm for ACH2
protons of MMA. The peaks of poly(THF-b-ECH-b-S) block
copolymers appear at 3.3 ppm for ACH2 protons of S, 3.7
ppm for ACH protons of S, 6.8 and 7.1 ppm for aromatic
ring protons of S.
Thermal analysis of poly(THF-b-ECH) macroperoxy initiator,
and the block and graft copolymers were carried out by tak-
ing DSC curves. All samples exhibited glass transition tem-
peratures (Tg). The Tg values reported were obtained from
the second heating curves. Figure 5 shows the second DSC
curves of poly(THF-b-ECH) macroperoxy initiator, the block
copolymer, and the graft copolymer. Peroxygen decomposi-
tion of poly(THF-b-ECH) macroperoxy initiator (run no 4 in
Table 1) was around 140 ꢀC. Tg values are reported in the
literature for homo PMMA, homo PS, homo PTHF, and homo
PECH as 105 ꢀC, 100 ꢀC, ꢁ82 ꢀC, ꢁ22 ꢀC, respectively.21
Tg value of poly(THF-b-ECH) macroperoxy initiator was
ꢁ29.24 ꢀC (run no 8 in Table 1) in Figure 5(a). Tg value of
poly(THF-b-ECH) macroperoxy initiator is ranged between
those of homo PTHF and homo PECH. Tg values of poly(THF-
b-PECH-b-MMA) and poly(THF-b-PECH-b-S) block copolymer
FTIR spectrums of poly(THF-b-ECH) macroperoxy initiators
(run no 3 in Table 1 and run no 21 in Table 1) are shown in
Figure 4. Figure 4(a) shows the characteristic peaks at
2900–3000 cmꢁ1 for ACH3 groups, at 1720 cmꢁ1 for AC¼¼O
groups of t-BuBP, and at 1270 cmꢁ1 for ACAOA groups of
t-BuBP. Also Figure 4(b) shows the characteristic peaks at
3000–3500 cmꢁ1 for ¼¼CHA groups of aromatic rings, at
1730 cmꢁ1 for AC¼¼O of BBP, at 1453 cmꢁ1 for AC¼¼CA
groups of acrylate end-groups, at 1240 cmꢁ1 for ACAOA of
BBP, and at 690–760 cmꢁ1 for mono-substitution of PS. The
etheric CAOAC bonds of PTHF and PECH are shown at 1111
cmꢁ1. The FTIR spectrum of poly(THF-b-ECH-b-MMA) block
copolymer and poly(THF-b-ECH-b-S) block copolymer adding
the peaks of the poly(THF-b-ECH) macroperoxy initiator
show the characteristic peaks at 755 cmꢁ1 for 1,4-disubstitu-
tion of benzoyl peroxide, at 1752 cmꢁ1 for AC¼¼O groups of
MMA, at 2857 cmꢁ1 and 2926 cmꢁ1 for ACH2 and ACH
groups of PMMA, at 666–700 cmꢁ1 monosubstitution peak
ꢀ
was 25.89 C (run no 30 in Table 2) in Figure 5(b) and was
49.67 ꢀC (run no 40 in Table 3) in Figure 5(c), respectively.
Tg values of the block copolymers changed to the values
which were more than the value of poly(THF-b-ECH) initiator
because of PS or PMMA segments. The only one glass transi-
tion temperature for poly(THF-b-ECH) macroperoxy initia-
tors and the block copolymers shows the miscible nature of
the related polymers.
SEM micrographs of the polymers were taken for the surface
morphology characterization of the macroperoxy initiator,
block and graft copolymers. The polymers were coated with
a thin layer of gold on their surfaces to provide electrical
conductivity. All of the polymer samples were characterized
by a morphology consisting of gel sheets or platelets with
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FIGURE 1 The optimized geometry of poly(THF-b-ECH) macroperoxy initiators and the block copolymers. (a) Poly(MMA-b-ECH-b-
THF-b-MMA) block copolymer with poly(THF-b-ECH) (synthesized by the cationic polymerization of S with t-BuP/AgSbF6 initiating
system) macroperoxy initiator; (b) Poly(MMA-b-ECH-b-THF-b-MMA-b-THF-b-ECH-b-MMA) block copolymer; poly(THF-b-ECH) (syn-
thesized by the cationic polymerization of S with BBP/AgSbF6 initiating system) macroperoxy initiator; (c) Poly(S-b-ECH-b-THF-b-S)
block copolymer; (d) Poly(S-b-ECH-b-THF-b-S-b-THF-b-ECH-b-S) block copolymer.
irregular pores. The micrographs were photographed from
different views. Figure 6(a,b) show the SEM micrographs of
poly(THF-b-ECH) macroperoxy initiators (run no 5 and 10 in
Table 1, respectively). According to the SEM micrographs of
the macroperoxy initiators, homogenization of the macroper-
oxy initiators was good. SEM micrographs of impact fracture
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FIGURE 2 From the values in Table 1, first-order plot for the cationic polymerization of (a) t-BuBP/AgSbF6 (^, run no 1, 2, 3) and
BBP/AgSbF6 (~, run no 13, 14, 15) initiating systems, (b) t-BuBP/ZnCl2 (^, run no 7, 8, 9) and BBP/ZnCl2 (~, run no 19, 20, 21) ini-
tiating systems; (c) Mn (^) and MWD (
^
) values of poly(THF-b-ECH) initiators with t-BuBP/AgSbF6 (run no 1, 2, 3), Mn (~) and
) values of poly(THF-b-ECH) macro-
MWD (þ) values of PS initiator with BBP/AgSbF6 (run no 13, 14, 15); (d) Mn (^) and MWD (
^
peroxy initiators with t-BuBP/ZnCl2 (run no 7, 8, 9), Mn (~) and MWD (þ) values of poly(THF-b-ECH) macroperoxy initiators with
BBP/ZnCl2 (run no 19, 20, 21) as a function of conversion (wt %) by 1H NMR and GPC, respectively.
surfaces of the block copolymer have a continuous PTHF ma-
trix and a dispersed PECH domain. Where, PTHF blocks form
a continuous phase. This could possibly be due to low Tg
value of PTHF block compared to PECH blocks. The surface
morphologies of poly(THF-b-ECH-b-MMA) triblock copoly-
mers are shown in Figure 6(c–f) (run no 24, 18, and 23 in
Table 2, respectively). PMMA homopolymer in poly(THF-b-
ECH) exhibits a discontinuous phase as shown in Figure 6(c–
f). Poly(THF-b-ECH) block copolymer forms a continuous
phase. This could possibly be due to low Tg value of PMMA
block compared to poly(THF-b-ECH) blocks. Due to this rea-
son, the PMMA block shows striation (relaxation lines)
because of stretching. With an increase of molecular weight
of PMMA segment, which forms into a continuous phase,
wherein the PTHF-PECH segments are embedded.
The SEM micrograph of poly(THF-b-ECH-b-S) block copoly-
mer shows a smooth surface [Fig. 6(g–i)]. However, the
micrographs of poly(THF-b-ECH) macroperoxy initiators and
poly(THF-b-ECH-b-S) block copolymers are shown in the
structure of the separated phase and an excellent semi-IPN
structure is formed. Figure 6(g–i) shows the SEM micro-
graphs of the poly(THF-b-ECH-b-S) multicomponent copoly-
mers (run no 25, 28, and 30 in Table 3, respectively). The
FIGURE 3 1H NMR spectrum of poly(THF-b-ECH) macroperoxy
initiators (run no 3 and run no 10 in Table 1, Mn ¼ 5550 g
molꢁ1).
poly(THF-b-ECH-b-S) multicomponent copolymer forms con-
tinuous structure with high connectivity. The SEM micro-
graphs in the different size of poly(THF-b-ECH-g-PBd)
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
micrographs depict formation of uniform spherical images
with average diameters of 100 nm and also, irregular non-
spherical particle shapes can be seen in the micrographs.
These clearly suggest that the observed spherical micro-
graphs should be ascribed to a ball shape polymers. Interest-
ingly, the micellar structure of the multiblock copolymer can
be altered by changing the one armed and two armed poly
(THF-b-ECH) macroperoxy initiators network architecture.
While the multiblock copolymer synthesized one armed poly
(THF-b-ECH) macroperoxy initiators has the micellar struc-
ture, the multiblock copolymer synthesized two armed poly
(THF-b-ECH) macroperoxy initiators has spherical beads.
Figure 7(g–i) (run no 25 in Table 3) shows TEM images of
poly(THF-b-ECH-b-S) multicomponent copolymers obtained
from one armed poly(THF-b-ECH) macroperoxy initiator syn-
thesized by using t-BuBP/AgSbF6 initiator system. The
spherical micelles probably composed of a PS segment in the
poly(THF-b-ECH-b-S) multicomponent copolymers. A spheri-
cal micelle forming the poly(THF-b-ECH-b-S) multiblock co-
polymer may become an ellipsoid or disklike structure and
the micelle dimensions between 50 and 100 nm. The TEM
images of the multicomponent copolymer show a typical do-
main structure, that is, bright and dark regions. These
regions dispersed in the polymer matrix. The gel consists of
a dense packing of rather large pores, separated by porous
walls with channels. It can be seen from Figure 7(g–i) that
the dark regions within the cluster aggregate correspond to
the connection nodes consisting of S segments in the poly
(THF-b-ECH-b-S) multicomponent copolymers. TEM images
of one armed the poly(THF-b-ECH-S) is similar that in the
poly(THF-b-ECH-b-MMA).
FIGURE 4 FTIR spectrum of the polymers. (a) Poly(THF-b-ECH)
macroperoxy initiators with t-BuBP/AgSbF6 (run no 3 in Table 1,
Mn
¼
11,214 g
molꢁ1); (b) Poly(THF-b-ECH) macroperoxy
initiators with BBP/AgSbF6 (run no 10 in Table 1, Mn ¼ 5550 g
molꢁ1).
Figure 7(k–n) (run no 30 in Table 3) shows the TEM images
of the two armed poly(THF-b-ECH-b-S) multicomponent
copolymers obtained from two armed poly(THF-b-ECH) mac-
roperoxy initiator synthesized by using BBP/AgSbF6 initiator
system. TEM images revealed the formation of large
croslinked graft copolymers shows pore system and gel net-
work as shown Figure 6(j–l) (run no 40 in Table 4). It can
be seen from Figure 6(j–l) that the gel consists of a dense
packing of rather large pores, separated by porous walls
with channels. The SEM micrograph of the graft copolymer
shows an unsmooth surface [Fig. 6(l)]. The graft copolymer
gels are made of poly(THF-b-ECH) macroperoxy initiator
composed of small primary particles being continuously
interconnected.
Representative TEM micrographs of the block copolymers
are shown in Figure 7. The micrographs illustrate that the
multicomponent copolymers have self-assembled to form
micelles of various sizes and shape. The three multiblock
copolymers used in this study formed micelles with diame-
ters between 0.2 and 5 lm and 50–100 nm. Figure 7(a–c)
(run no 15 in Table 2) shows TEM images of poly(THF-b-
ECH-b-MMA) multicomponent copolymers obtained from one
armed poly(THF-b-ECH) macroperoxy initiator synthesized
by using t-BuBp/AgSbF6 initiator system. A spherical micelle
forming multiblock copolymer may become an ellipsoid or
disklike structure. Figure 7(d–f) (run no 24 in Table 2) rep-
resentative the TEM images of the two armed poly(THF-b-
ECH-b-MMA) multicomponent copolymers obtained from
two armed poly(THF-b-ECH) macroperoxy initiator synthe-
sized by using BBP/AgSbF6 initiator system. The resulting
FIGURE 5 DSC curves of the polymers. (a) Poly(THF-b-ECH)
macroperoxy initiator (run no 10 in Table 1, Mn ¼ 5550 g
molꢁ1); (b) Poly(THF-b-ECH-b-S) block copolymer (run no 30 in
Table 3, Mn ¼ 110,697 g molꢁ1); (c) Poly(THF-b-ECH-b-MMA)
block copolymer (run no 16 in Table 2, Mn ¼ 971,053 g molꢁ1).
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FIGURE 6 SEM micrographs of the polymers. (a) Run no 5 in Table 1, Mn ¼ 3549 g molꢁ1 (ꢂ1000); (b) Run no 10 in Table 1, Mn
¼
5550 g molꢁ1 (ꢂ1000); (c) Run no 24 in Table 2, Mn ¼ 757,343 g molꢁ1 (ꢂ3000); (d) Run no 18 in Table 2, Mn ¼ 1,192,780 g molꢁ1
(ꢂ500); (e) Run no 23 in Table 2, Mn ¼ 677,628 g molꢁ1 (ꢂ3000); (f) Run no 23 in Table 2 (ꢂ1000); (g) Run no 25 in Table 3, Mn
¼
116,425 g molꢁ1 (ꢂ600); (h) Run no 28 in Table 3, Mn ¼ 230,654 g molꢁ1 (ꢂ1000); (i) Run no 30 in Table 3, Mn ¼ 110,697 g molꢁ1
(ꢂ1000); (j) Run no 40 in Table 4 (ꢂ300); (k) Run no 40 in Table 4 (ꢂ600); (l) Run no 40 in Table 4 (ꢂ2000).
CONCLUSION
spherical aggregates of 50–100 nm diameters. The filled
spherical aggregates shown in the TEM image suggest that
these spheres were not vesicles or hollow micelles. The
Poly(THF-b-ECH) macroperoxy initiators were obtained from
the cationic polymerization of THF and ECH with the t-BuBP,
irregular nonspherical particle shapes can be seen in the
micrographs which might be a consequence of the branching
with two armed.
BBP/AgSbF6 and t-BuBP, BBP/ZnCl2 initiating systems. The
poly(THF-b-ECH) macroperoxy initiators did not loose their
peroxygen groups after the cationic polymerization at 0 ꢀC.
SYNTHESIS OF NOVEL MACROMONOMERIC PEROXY INITIATOR, MISIR ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
FIGURE 7 TEM micrographs of
the polymers. (a) Run no 15 in
Table 2, Mn ¼ 547,374 g.molꢁ1
;
(b) Run no 15 in Table 2; (c) Run
no 15 in Table 2; (d) Run no 24
in Table 2, Mn
¼
757,343 g
molꢁ1; (e) Run no 24 in Table 2;
(f) Run no 24 in Table 2; (g) Run
no 25 in Table 3, Mn ¼ 116,425 g
molꢁ1; (h) Run no 25 in Table 3;
(i) Run no 25 in Table 3; (k) Run
no 30 in Table 3, Mn ¼ 110,697 g
molꢁ1; (m) Run no 30 in Table 3;
(n) Run no 30 in Table 3.
It was revealed that the reactivity of poly(THF-b-ECH) mac-
roperoxy initiators was comparable with other common per-
oxide initiators. Poly(THF-b-ECH-b-MMA) block copolymers,
poly(THF-b-ECH-b-S) block copolymers, and poly(THF-b-ECH-
g-PBd) crosslinked graft copolymers could be prepared by
using these macroperoxy initiators. It was found from the
quantum mechanical calculations that the initiator effect in
the cationic polymerization of THF and ECH with t-BuBP or
BBP in the presence of AgSbF6 was bigger than those in the
presence of ZnCl2. For poly(THF-b-ECH) macroperoxy initia-
tor, poly(THF-b-ECH-b-MMA) block copolymer, and poly(THF-
b-ECH-b-S) block copolymer, a single glass transition temper-
ature was determined showing miscible character.
This work was financially supported by Karadeniz Technical
University Research Fund.
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SYNTHESIS OF NOVEL MACROMONOMERIC PEROXY INITIATOR, MISIR ET AL.
2909