A novel fluorine-containing graft copolymer bearing perfluorocyclobutyl aryl ether-based backbone and poly(methyl methacrylate) side chains

Article abstract of DOI:10.1002/pola.24352

A series of novel graft copolymers consisting of perfluorocyclobutyl aryl ether-based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of thermal [2π + 2π] step-growth cycloaddition polymerization of aryl bistrifluorovinyl ether monomer and atom transfer radical polymerization (ATRP) of methyl methacrylate. A new aryl bistrifluorovinyl ether monomer, 2-methyl-1,4-bistrifluorovinyloxybenzene, was first synthesized in two steps from commercially available reagents, and this monomer was homopolymerized in diphenyl ether to provide the corresponding perfluorocyclobutyl aryl ether-based homopolymer with methoxyl end groups. The fluoropolymer was then converted to ATRP macroinitiator by the monobromination of the pendant methyls with N-bromosuccinimide and benzoyl peroxide. The grafting-from strategy was finally used to obtain the novel poly(2-methyl-1,4- bistrifluorovinyloxybenzene)-g-poly(methyl methacrylate) graft copolymers with relatively narrow molecular weight distributions (M_w/M_n ≤ 1.46) via ATRP of methyl methacrylate at 50 °C in anisole initiated by the Br-containing macroinitiator using CuBr/dHbpy as catalytic system. These fluorine-containing graft copolymers can dissolve in most organic solvents. This is the first example of the graft copolymer possessing perfluorocyclobutyl aryl ether-based backbone. Copyright

Full text of DOI:10.1002/pola.24352

A Novel Fluorine-Containing Graft Copolymer Bearing Perfluorocyclobutyl
Aryl Ether-Based Backbone and Poly(methyl methacrylate) Side Chains
HAO LIU,1 YONGJUN LI,1 SEN ZHANG,1 DONG YANG,2 JIANHUA HU,2 XIAOYU HUANG1
1Key Laboratory of Organofluorine Chemistry and Laboratory of Polymer Materials, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People’s Republic of China
2Key Laboratory of Molecular Engineering of Polymers (Ministry of Education), Laboratory of Advanced Materials and
Department of Macromolecular Science, Fudan University, 220 Handan Road, Shanghai 200433, People’s Republic of China
Received 25 August 2010; accepted 27 August 2010
DOI: 10.1002/pola.24352
Published online 13 October 2010 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: A series of novel graft copolymers consisting of per-
fluorocyclobutyl aryl ether-based backbone and poly(methyl
methacrylate) side chains were synthesized by the combination
of thermal [2p þ 2p] step-growth cycloaddition polymerization of
aryl bistrifluorovinyl ether monomer and atom transfer radical
polymerization (ATRP) of methyl methacrylate. A new aryl bis-
trifluorovinyl ether monomer, 2-methyl-1,4-bistrifluorovinyloxy-
benzene, was first synthesized in two steps from commercially
available reagents, and this monomer was homopolymerized in
diphenyl ether to provide the corresponding perfluorocyclobutyl
aryl ether-based homopolymer with methoxyl end groups. The
fluoropolymer was then converted to ATRP macroinitiator by
the monobromination of the pendant methyls with N-bromosuc-
cinimide and benzoyl peroxide. The grafting-from strategy was
finally used to obtain the novel poly(2-methyl-1,4-bistrifluorovi-
nyloxybenzene)-g-poly(methyl methacrylate) graft copolymers
with relatively narrow molecular weight distributions (Mw/Mn
ꢀ
1.46) via ATRP of methyl methacrylate at 50 ꢁC in anisole initi-
ated by the Br-containing macroinitiator using CuBr/dHbpy as
catalytic system. These fluorine-containing graft copolymers can
dissolve in most organic solvents. This is the first example of the
graft copolymer possessing perfluorocyclobutyl aryl ether-based
C
V
backbone.
2010 Wiley Periodicals, Inc. J Polym Sci Part A:
Polym Chem 49: 11–22, 2011
KEYWORDS: atom transfer radical polymerization (ATRP); fluo-
ropolymers; graft copolymers; grafting-from; perfluorocyclobu-
tyl aryl ether
INTRODUCTION High-performance fluoropolymers possess-
ing many advantages1 including the increased thermal and
oxidative stability, optical transparency, solvent compatibility,
and environmental stability have been extensively applied in
many different fields since the first example of fluoropoly-
mer, polytetrafluoroethylene (PTFE), was discovered by Plun-
kett of DuPont in 1938.2 For example, Percec et al.3–15
reported fluorinated liquid crystal molecules with perfluori-
nated alkane chains, which could result in a microsegrega-
tion at the molecular levels, and this process alone could be
responsible for the formation of lamellar thermotropic and
lyotropic mesophases. These unique properties compared
with those of usual carbon–hydrogen–oxygen-containing
polymers originate from the incorporation of fluorocarbon
functionality. However, the solubility and processability of
fluoropolymers are generally low due to the high crystallin-
ity, which certainly limited their applications. Thus, many
partially fluorinated polymers with low crystallinity, such as
polychlorotrifluoroethylene, Teflon-AF, Cytop, and various
copolymers of PTFE, have been developed to improve the
processability.1 In particular, perfluorocyclobutyl (PFCB) aryl
ether polymers have received considerable attention since its
discovery by Babb et al. of Dow Chemical Co. in early
1990s.16,17 They are synthesized by the predominant head-
to-head thermal [2p þ 2p] step-growth cyclopolymerization
ꢁ
of aryl trifluorovinyl ethers (TFVE) above 150 C free of any
initiator and catalyst, which first proceeds to form a stable
diradical intermediate followed by rapid ring closure to pro-
vide a mixture of cis- and trans-1,2-disubstituted perfluoro-
cyclobutanes.18–20 This relatively new class of semifluori-
nated polymers exhibit not only high thermal/oxidative
stability, chemical resistance, and superior electrical insulat-
ing ability but also improved processability compared with
traditional fluoropolymers.21–24 Thus, PFCB-containing poly-
mers are attractive for a multitude of new applications due
to the combination of solution processability and thermal
stability as reviewed by Smith et al.24
Most recent studies of PFCB-based polymers focused on the
thermal polymerization of different bis- and trifunctionalized
aryl TFVE monomers to obtain diverse thermoplastic and
thermoset homopolymers and random copolymers bearing
PFCB aromatic ether linkages,19,20,25–38 in which PFCB con-
nection was used as a way to link different functionalities
Correspondence to: X. Huang (E-mail: xyhuang@mail.sioc.ac.cn) or D. Yang (E-mail: yangdong@fudan.edu.cn)
C
V
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 49, 11–22 (2011) 2010 Wiley Periodicals, Inc.
NOVEL FLUORINE-CONTAINING GRAFT COPOLYMER, LIU ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
for meeting various demands of applications such as hole-
transporting material,25,26 optical waveguide applica-
tions,28,29 curing additive,18 proton exchange membrane,35,36
light emission,37 and light-optic38 applications. However, the
cases about the synthesis of PFCB aryl ether-based copoly-
mers via aryl TFVE and commonly used vinyl monomers are
very limited because of the peculiar radical-mediated poly-
merization mechanism ([2p þ 2p] cycloaddition) and rela-
tively high polymerization temperature (at least >150 ꢁC).39–42
Therefore, to widen the application scope of PFCB aryl ether-
based fluoropolymer, it is necessary to combine the high per-
formance of PFCB aryl ether-based fluoropolymer with other
commercial polymer.
ether-based backbone was prepared by the thermal step-
growth cyclopolymerization of a new aryl bistrifluorovinyl
ether monomer, 2-methyl-1,4-bistrifluorovinyloxybenzene
(MBTVFB). ATRP initiation groups were introduced into the
backbone by the monobromination of the pendant methyls.
The target graft copolymer, poly(2-methyl-1,4-bistrifluorovi-
nyloxybenzene)-g-poly(methyl methacrylate) (PMBTFVB-g-
PMMA), was synthesized via ATRP graft copolymerization of
methyl methacrylate.
EXPERIMENTAL
Materials
Methyl methacrylate (MMA, Aldrich, 99%) was washed with
5% aqueous NaOH solution to remove the inhibitor and then
with water, dried over MgSO4, and distilled twice from CaH2
under reduced pressure prior to use. CuBr (Aldrich, 98%)
was purified by stirring overnight over CH3CO2H at room
temperature, followed by washing the solid with ethanol,
diethyl ether, and acetone prior to drying in vacuo at 40 ꢁC
for 1 day. Granular zinc (Aldrich, 99.99%) was activated by
Graft copolymers with a stable covalent connection between
the backbone and the side chains may be a suitable choice
to implement the above consideration. In general, graft
copolymers are synthesized via three different routes: graft-
ing-through, grafting-onto, and grafting-from strategies.43
The grafting-through strategy is to prepare graft copolymers
via the polymerization of the macromonomers with a poly-
merizable end group; a broad chain length distribution
existed in the graft copolymers yielded by the traditional
free radical polymerization of the macromonomers44 and the
living polymerization of the macromonomers afforded well-
defined graft copolymers with low molecular weights.45 The
grafting-onto technique is based on attaching certain side
chains onto a linear backbone by a coupling reaction,46–51
which requires a high coupling efficiency between the back-
bone and the side chains. The grafting-from approach utilizes
the pendant initiation sites on the backbone, i.e., macroinitia-
tor, which can be obtained directly from the initiation group-
containing monomer or by the introduction of initiating func-
tional groups to a precursor, to initiate the polymerization of
another monomer to form the side chains.52,53 With the
advent of living/controlled polymerization technique, espe-
cially living/controlled radical polymerization including
atom transfer radical polymerization (ATRP),53–57 modified
ATRP,58 single-electron transfer living radical polymerization
(SET-LRP),59–63 and reversible addition fragmentation chain
transfer (RAFT),64,65 this method is considered as a particu-
larly attractive procedure to synthesize well-defined graft
copolymers because low instantaneous propagating species
limit the coupling and termination reactions and the gradual
growth of side chains can effectively decrease the steric
effect that is inevitable for ‘‘grafting-onto’’ and ‘‘grafting-
through’’ strategies. Many graft copolymers with various
backbones and side chains have been prepared by combining
the grafting-from strategy with living polymerization.52,53,66–73
Specifically, the side chains can be formed in a well-defined
way via ATRP through the grafting-from approach and the liv-
ing nature of ATRP enabled it to control both the molecular
weights and molecular weight distributions of the side
chains.52,64–68,71,73
ꢁ
washing in 0.1 M HCl followed by drying in vacuo at 140 C
for 10 h. Toluene (Aldrich, 99%) was dried over CaH2 and
distilled from sodium and benzophenone under N2 prior to
use. Anisole (Aldrich, 99%) and diphenyl ether (Aldrich,
99%) were dried over CaH2 and distilled under reduced
pressure prior to use. N-Bromosuccinimide (NBS, Aldrich,
99%) was recrystallized from water and dried in vacuo at 35
ꢁC for 1 day. Benzoyl peroxide (BPO, Alfa Aesar, 97%) was
purified by dissolving in acetone and precipitating in water
followed by drying in vacuo at room temperature for 1 day.
BrCF2CF2Br was prepared by condensing equimolar amounts
of bromine and tetrafluoroethylene at ꢂ195 ꢁC followed by
74
warming up to 22 C. 4-Methoxytrifluorovinyloxybenzene23
ꢁ
and diheptyl-2,20-bipyridine (dHbpy)75 were prepared
according to previous literatures. 2-Methylhydroquinone
(Aldrich, 99%), CH3CN (Aldrich, 99.8%), CCl4 (Aldrich,
99.5%), dimethyl sulfoxide (DMSO, Aldrich, 99.9%), and KOH
(Aldrich, 90%) were used as received.
Measurements
FT-IR spectra were recorded on a Nicolet AVATAR-360 FT-IR
spectrophotometer with a resolution of 4 cmꢂ1. All NMR
analyses were performed on a Bruker AM-300 spectrometer
(300 MHz) in CDCl3, TMS (1H NMR) and CDCl3 13C NMR)
(
were used as internal standards, and CF3CO2H was used as
external standard for 19F NMR. EI-MS and HRMS were meas-
ured by an Agilent 5937N system and a Waters Micromass
GCT instrument, respectively. The bromine content was
determined by the titration with Hg(NO3)2. Relative molecu-
lar weights and molecular weight distributions were meas-
ured by conventional gel permeation chromatography (GPC)
system equipped with a Waters 1515 Isocratic HPLC pump,
a Waters 2414 refractive index detector, and a set of Waters
Styragel columns [HR3 (500-30,000), HR4 (5000-600,000)
and HR5 (50,000-4,000,000) 7.8 ꢃ 300 mm, particle size:
5 lm]. GPC measurements were carried out at 35 ꢁC using
tetrahydrofuran (THF) as eluent with a flow rate of 1.0 mL/
min. The system was calibrated with linear polystyrene
Until now, none has reported the graft copolymer consisting
of PFCB aryl ether segment. In this work, we present the
first example of PFCB aryl ether-based graft polymer with
poly(methyl methacrylate) (PMMA) side chains. PFCB aryl
12
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ARTICLE
SCHEME 1 Synthesis of PMBTFVB-g-PMMA graft copolymer.
standards. Conversions of MMA were determined by GC
using a HP 6890 system with an SE-54 column, and anisole
was used as internal standard. Differential scanning calorim-
etry (DSC) measurements were run on aꢁTA Q200 system
under N2 purge with a heating rate of 10 C/min. The glass
transition temperature (Tg) was recorded from the second
heating process after a quick cooling from 200 ꢁC, and the
value was determined from the midpoint of Cp curve. Ther-
mogravimetric analysis (TGA) measurements were run on a
TA Q500 system under N2 purge with a heating rate of
10 ꢁC/min. The decomposition temperature (Td) is defined
as the temperature with 10% weight loss.
KOH (12.44 g, 90%, 0.20 mol). The mixture was refluxed at
180 ꢁC to azeotropically remove the water until no more
water was collected in the trap. The solution was then cooled
ꢁ
to below 15 C and BrCF2CF2Br (30 mL, 0.25 mol) was added
dropwise in 1 h. The mixture was warmed to room tempera-
ꢁ
ture for 12 h and heated to 35 C for another 8 h. The reac-
tion was quenched with water and the mixture was extracted
with CH2Cl2. All organic layers were collected and dried over
MgSO4. The intermediate, 19.76 g (40.9%) of 2-methyl-1,4-
bis(2-bromotetrafluoroethoxy)phenyl (clear oil), was obtained
by silica column chromatography. 1H NMR (300 MHz):
d (ppm): 2.24 (3H, CH3), 7.08, 7.13, 7.24 (3H, phenyl). HR-MS:
C11H6O2Br2F8: calcd 479.8607, found 479.8604.
Synthesis of Aryl Bistrifluorovinyl Ether Monomer
MBTVFB 1 was synthesized in two steps using 2-methylhy-
droquinone as starting material (Scheme 1). 2-Methylhydro-
quinone (12.41 g, 0.10 mol), toluene (120 mL), and DMSO
(150 mL) were first introduced to a 500 mL three-neck flask
(flame-dried prior to use) fitted with a N2 inlet and a Barrett
trap topped with a reflux condenser. The solution was deoxy-
genated by introducing N2 for 30 min followed by adding
Zinc (11.44 g, 0.176 mmol) was first introduced to a 250 mL
three-neck flask (flame-dried prior to use) fitted with a
reflux condenser. After three cycles of evacuating and back-
filling with N2, CH3CN (120 mL) was charged via a gastight
syringe and the mixture was refluxed at 110 ꢁC. The above-
prepared intermediate, 2-methyl-1,4-bis(2-bromotetrafluor-
oethoxy)phenyl (24.19 g, 0.05 mmol), was added dropwise
NOVEL FLUORINE-CONTAINING GRAFT COPOLYMER, LIU ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
ꢁ
in 1 h and the mixture was refluxed at 110 C for 10 h. After
white powder, PMBTFVB-Br 3a macroinitiator, was obtained
after drying in vacuo overnight. GPC: Mn ¼ 5700 g/mol, Mw/
Mn ¼ 1.18. EA: Br%: 12.34%. 1H NMR (300 MHz): d (ppm):
1.99, 2.18 (3H, CH3), 3.68 (3H, OCH3), 4.17, 4.34 (2H,
CH2Br), 6.86, 7.04, 7.16 (3H, phenyl). 13C NMR (75 MHz):
d (ppm): 15.3 (CH3), 24.6 (CH2Br), 54.7 (OCH3), 105.0, 107.8,
111.7 (4C, PFCB), 116.5, 118.7, 120.8, 129.3, 148.1 (phenyl).
19F NMR (282 MHz): d (ppm): ꢂ127.1 to ꢂ132.7 (6F, PFCB).
cooling to room temperature, the suspending zinc salt was
removed by the filtration. The filtrate was washed by water
and dried over MgSO4. The crude product was purified by
silica column chromatography to obtain 9.20 g (65.0%) of
MBTFVB 1 (clear oil). FT-IR: m (cmꢂ1): 3045, 2968, 1833,
1600, 1496, 1422, 1315, 1279, 1179, 1157, 1009, 945, 874,
808, 767. 1H NMR (300 MHz): d (ppm): 2.33 (s, 3H, CH3),
6.93 (d, J ¼ 8.8 Hz, 1H, phenyl), 6.97 (s, 1H, phenyl), 7.01 (d,
J ¼ 8.8 Hz, 1H, phenyl). 13C NMR (75 MHz): d (ppm): 15.7
(CH3), 114.3, 115.5, 119.0, 129.9 (phenyl), 132.8, 135.2,
143.9, 144.4, 146.5, 147,1, 149.3, 149.9 (OCF¼¼CF2), 150.3,
151.6 (phenyl). 19F NMR (282 MHz): d (ppm): ꢂ120.3,
ꢂ127.0, ꢂ134.3. EI-MS: m/z (%): 284 ([M]þ, 100.00), 187
(20.49), 159 (11.81), 140 (24.04), 119 (17.50), 109 (32.77),
90 (83.16), 77 (4.09), 51 (7.58). HR-MS: C11H6O2F6: calcd
284.0272, found, 284.0268.
ATRP Graft Copolymerization of MMA
ATRP graft copolymerization of MMA was initiated by
PMBTFVB-Br 3 macroinitiator using CuBr/dHbpy as catalytic
system. In a typical procedure, PMBTFVB-Br 3a (Mn ¼ 5700
g/mol, Mw/Mn ¼ 1.18, Br% ¼ 12.34%, 31.7 mg, 0.0489
mmol Br group), CuBr (7.0 mg, 0.0488 mmol), and dHbpy
(34.4 mg, 0.0976 mmol) were first added to a 25 mL
Schlenk flask (flame-dried under vacuum prior to use) sealed
with a rubber septum for degassing and kept under N2.
Next, MMA (1.30 mL, 12.2 mmol) and anisole (1.30 mL)
were introduced via a gastight syringe. The flask was
degassed by three cycles of freezing–pumping–thawing, and
the mixture was stirred at room temperature for 10 min so
that the mixture became homogeneous. The flask was
immersed into an oil bath preset at 50 ꢁC to start the poly-
merization. The polymerization was terminated by putting
the flask into liquid N2 after 3.5 h. The reaction mixture was
diluted by THF and passed through an Al2O3 column to
remove the residual copper catalyst. The solution was con-
centrated and precipitated into methanol. After repeated pu-
rification by dissolving in THF and precipitating in methanol,
0.2854 g of white powder, PMBTFVB-g-PMMA 4d graft co-
polymer, was obtained after drying in vacuo overnight. GPC:
Mn ¼ 79,500 g/mol, Mw/Mn ¼ 1.29. FT-IR: m (cmꢂ1): 2994,
2951, 2926, 2856, 1730, 1483, 1449, 1388, 1271, 1240,
1191, 1148, 1066, 964, 842, 749. 1H NMR (300 MHz): d
(ppm): 0.84, 1.02, 1.25 (3H, CCH3), 1.45, 1.60, 1.81 (2H, CH2
of PMMA side chain), 1.89 (2H, CH2 connected to the aryl),
2.07, 2.27 (3H, CH3), 3.60 (3H, COOCH3), 3.82 (3H, OCH3),
6.91, 7.02, 7.11 (3H, phenyl). 19F NMR (282 MHz): d (ppm):
ꢂ128.1 to ꢂ132.2 (6F, PFCB).
Thermal Homopolymerization of MBTFVB
PMBTFVB 2 homopolymer was synthesized via the thermal
step-growth cycloaddition polymerization of aryl bistrifluoro-
vinyl ether monomer 1. MBTFVB 1 (8.00 g, 28.16 mmol) and
diphenyl ether (16 mL) were added to a 50 mL Schlenk flask
(flame-dried under vacuum prior to use) sealed with a rub-
ber septum under N2. The flask was degassed by three
cycles of freezing–pumping–thawing followed ꢁby immersing
the flask into an oil bath thermostated at 200 C. 4-Methoxy-
trifluoro-vinyloxybenzene (2.87 g, 14.07 mmol) was charged
via a gastight syringe after 4 h. The polymerization was ter-
minated by putting the flask into liquid N2 after another 6 h.
THF (15 mL) was added to the flask for dilution, and the
resulting solution was precipitated into methanol. After
repeated purification by dissolving in THF and precipitating
in methanol, 4.53 g (56.6%) of white powder, PMBTFVB 2
homopolymer, was obtained after drying in vacuo overnight.
GPC: Mn ¼ 4600 g/mol, Mw/Mn ¼ 1.27, FT-IR: m (cmꢂ1):
3053, 2933, 1599, 1498, 1315, 1267, 1203, 1120, 1009, 962,
1
925, 813, 743. H NMR (300 MHz): d (ppm): 2.06, 2.27 (3H,
CH3), 3.77 (3H, OCH3), 6.97, 7.10 (3H, phenyl). 13C NMR (75
MHz): d (ppm): 16.0 (CH3), 55.4 (OCH3), 105.7, 109.2, 112.7
(4C, PFCB), 116.5, 121.5, 131.0, 148.3 (phenyl). 19F NMR
(282 MHz): d (ppm): ꢂ128.3 to ꢂ132.2 (6F, PFCB).
RESULTS AND DISCUSSION
Monobromination of PMBTFVB
Synthesis of MBTFVB Monomer
The pendant methyls of PMBTFVB 2 homopolymer were
monobrominated by NBS and BPO. In a typical procedure,
PMBTFVB 2 (Mn ¼ 4600 g/mol, Mw/Mn ¼ 1.27, 2.00 g, 7.04
mmol CH3 group), NBS (0.8771 g, 4.93 mmol), BPO (0.3110
g, 1.28 mmol) were first added to a 1000 mL three-neck
flask (flame-dried prior to use) fitted with a reflux condenser
followed by deoxygenating under N2. CCl4 (400 mL) was
charged via a gastight syringe and the solution was refluxed
at 80 ꢁC for 1 day. After filtration, CCl4 was removed from
the filtrate using a rotary evaporator. The obtained solid was
dissolved in ethyl acetate (500 mL), and the resulting solu-
tion was washed with distilled water (200 mL ꢃ2) followed
by drying over MgSO4. The solution was concentrated and
precipitated into methanol. After repeated purification by
dissolving in THF and precipitating in methanol, 0.9467 g of
MBTVFB 1 aryl bistrifluorovinyl ether monomer was synthe-
sized from commercially available 2-methylhydroquinone in
two steps with a total yield of 26.6% via the fluoroalkylation
with BrCF2CF2Br followed by Zn-mediated elimination
according to the conventional approach.76–78 FT-IR, 1H NMR,
19F NMR, and 13C NMR were used to characterize the chemi-
cal structure of this monomer. The characteristic signal of
the trifluorovinyl located at 1833 cmꢂ1 in FT-IR spectrum of
MBTFVB 1 [Fig. 1(A)]. The peaks at 1600, 1496, 808, and
1179 cmꢂ1 were attributed to the benzene ring and the
ether bond, respectively. Figure 2(A) shows 1H NMR spec-
trum of MBTFVB 1 and the typical resonance signal of
the methyl located at 2.33 ppm. A series of peaks around
7.00 ppm corresponded to three protons of the benzene
ring. The singlet at 6.97 ppm belonged to one proton
14
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ARTICLE
accorded with the calculated value (284.0272). Thus, all the
above results confirmed the successful synthesis of bistri-
fluorovinyl-containing monomer 1.
Preparation of PFCB Aryl Ether-Based Backbone
Thermal [2p þ 2p] step-growth cyclopolymerization of
bifunctional MBTFVB 1 monomer was performed in diphenyl
ether at 200 ꢁC to afford PMBTFVB 2 homopolymer. Mono-
functional 4-methoxytrifluorovinyloxybenzene was used as
end-capping agent. This homopolymer was characterized by
1
FT-IR, H NMR, 13C NMR, and 19F NMR. After thermal homo-
polymerization, the typical peak of the trifluorovinyl at 1833
cmꢂ1 in FT-IR spectrum completely disappeared [Fig. 1(B)]
and a new sharp band of PFCB linkage appeared at 962
cmꢂ1 in comparison with that of the monomer [Fig. 1(A)],
which indicated the presence of PFCB linkage in homopoly-
mer. 19F NMR spectrum after thermal homopolymerization
showed the disappearance of the representative signals of
the trifluorovinyl, and new multiplets ranging from ꢂ128.3
to ꢂ132.2 ppm appeared instead, this also illustrating the
existence of PFCB functionality. The singlets at 2.06 and 2.27
FIGURE 1 FT-IR spectra of MBTVFB 1 (A) and PMBTFVB 2 (B).
adjacent to the methyl. The signals of other two protons of
benzene ring appeared at 6.93 and 7.01 ppm as two dou-
blets, respectively. Moreover, the presence of the trifluoro-
vinyl was demonstrated by three typical muitiplets at
ꢂ120.3, ꢂ127.0, and ꢂ134.3 ppm31,76 in 19F NMR spectrum
of MBTFVB 1 as shown in Figure 2(B). 13C NMR spectrum of
MBTVFB 1 is shown in Figure 2(C) and the peaks between
132.8 and 149.9 ppm were attributed to two carbons of the
trifluorovinyl.31,76 The signal at 15.7 ppm corresponded to
the methyl and the peaks at 114.3, 115.5, 119.0, 129.9,
150.3, and 151.6 ppm originated from six carbons of the
benzene ring.31,76 HR-MS result (284.0268) also well
1
ppm in H NMR spectrum after thermal homopolymerization
[Fig. 3(A)] were attributed to three protons of the methyl
and the broad peaks at 6.97 and 7.10 ppm corresponded to
three protons of the benzene ring. Furthermore, the signal of
three protons of terminal methoxyl was found to be located
at 3.77 ppm as a singlet, which verified the effective end-cap-
ping with 4-methoxytrifluorovinyloxybenzene. Figure 4(A)
shows 13C NMR spectrum after thermal homopolymerization,
and the signals of the trifluorovinyl disappeared compared
with that of the monomer [Fig. 2(C)]. Instead, new peaks
between 106.5 and 112.7 ppm attributed to four carbons of
PFCB linkage appeared. Another new peak at 55.4 ppm
belonged to the carbon of terminal methoxyl.
GPC measurement offered the relative molecular weight of
PMBTFVB
2
(Mn
¼
4600 g/mol). Because GPC was
FIGURE 2 1H (A), 13C (B), and 19F NMR (C) spectra of MBTFVB
1 in CDCl3.
FIGURE 3 1H NMR spectra of PMBTFVB 2 (A) and PMBTFVB-Br
3 (B) in CDCl3.
NOVEL FLUORINE-CONTAINING GRAFT COPOLYMER, LIU ET AL.
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JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
form, hexane, cyclohexane, toluene, acetone, ethyl acetate,
and DMF; however, it is insoluble in water and methanol.
Preparation of PMBTFVB-Br ATRP Macroinitiator
The pendant methyls of PMBTFVB 2 homopolymer were
monobrominated by NBS and BPO using CCl4 as solvent so
that PMBTFVB
2 homopolymer was transformed into
PMBTFVB-Br 3 macroinitiator. Two different feeding ratios
of NBS to the methyls were used to tune the degree of bro-
mination, and the bromine content increased with the raising
of the adding amount of NBS as listed in Table 1. The
changes of the bromine content for both samples (0%–
12.34% for 3a and 16.28% for 3b, respectively) showed the
presence of halogen-containing ATRP initiation group in both
samples.79 Both samples’ molecular weights after the reac-
tion with NBS and BPO were higher than that of the homo-
polymer, this also witnessing the occurrence of the bromina-
tion reaction.
The successful bromination was also confirmed by 1H NMR
1
and 13C NMR. H NMR spectrum after the reaction is shown
in Figure 3(B) and two new peaks attributed to two protons
of newly formed CH2Br group appeared at 4.17 and 4.34
ppm. Moreover, a new peak originating from the carbon of
CH2Br group was found to be located at 24.6 ppm in 13C
NMR spectrum after the reaction as shown in Figure 4(B).
The original signals of PMBTFVB 2 homopolymer were kept
in 1H NMR [Fig. 3(B)], 13C NMR [Fig. 4(B)], and 19F NMR
spectra after the reaction, demonstrating that the polymeric
architecture was not affected during the bromination. As we
can see from Figure 5, unimodal and symmetrical GPC
curves were found for both PMBTFVB-Br 3a and 3b macroi-
nitiators, which also verified that the architecture of polymer
chain was not altered during the bromination.80
FIGURE 4 13C NMR spectra of PMBTFVB 2 (A) and PMBTFVB-
Br 3 (B) in CDCl3.
calibrated with linear polystyrene standards, 1H NMR was
used to determine the ‘‘absolute’’ molecular weight of the
homopolymer. The molecular weight of PMBTFVB 2 (Mn,NMR
)
can be estimated according to eq 1 (Sa and Sb are the area of
peak ‘‘a’’ at 3.77 ppm and peaks ‘‘b’’ at 2.06 and 2.27 ppm in
Figure 3(A), respectively; 284 and 204 are the molecular
weights of MBTFVB 1 and 4-methoxytrifluorovinyloxyben-
zene, respectively). The value of Sb/Sa is 15.5 and the molec-
ular weight is calculated to be 9200 g/mol. This result
shows that every PMBTFVB 2 chain possesses 31.0 repeating
units.
From the data of Br% as listed in Table 1, the number of
CH2Br ATRP initiation group (NATRP) can be calculated
according to the following equation set, in which ‘‘x’’ and ‘‘y’’
are the numbers of repeating unit with CH2Br and CH3 group
as shown in Scheme 1, respectively; 80 is the molecular
weight of bromine atom; 363 and 284 are the molecular
weights of repeating unit with CH2Br and CH3 group, respec-
tively; 204 is the molecular weight of 4-methoxytrifluorovi-
nyloxybenzene; 31.0 is the number of repeating unit of
PMBTFVB 2 homopolymer. The values of NATRP are 16.2 and
22.3 for PMBTFVB-Br 3a and 3b, respectively. The grafting
Mn;NMR ¼ 284 ꢃ ð2Sb=SaÞ þ 204 ꢃ 2
(1)
All these evidences confirmed the structure of PMBTFVB 2
homopolymer. In addition, this homopolymer is soluble in
most common organic solvents such as THF, CH2Cl2, chloro-
densities of CH2Br ATRP initiation group (DATRP
) are
TABLE 1 Preparation of PMBTFVB-Br 3 Macroinitiatora
Br%b
Mn,GPC (KDa)
Mw/Mn
Mn,NMR (KDa)
NATRP
DATRP (%)
c
c
d
e
f
Sample
NBS (eq.)
3a
3b
a
0.7
1.0
12.34
16.28
5.7
6.2
1.18
1.14
10.4
10.8
16.2
22.3
52.3
71.9
d
Reaction temperature: 80 ꢁC; reaction time: 24 h; feeding ratio: [methyl]:
Determined by 1H NMR.
e
f
[BPO] ¼ 1:0.2.
The number of ATRP initiation group per chain.
Grafting density of ATRP initiation group.
b
Determined by the titration with Hg(NO3)2.
Measured by GPC in THF at 35 ꢁC.
c
16
WILEYONLINELIBRARY.COM/JOURNAL/JPOLA

ARTICLE
incorporated into the main chain without affecting the poly-
meric architecture, and 16.2 and 22.3 CH2Br groups are
involved in PMBTFVB-Br 3a and 3b macroinitiators,
respectively.
Synthesis of PMBTFVB-g-PMMA Graft Copolymer
PMBTFVB-Br 3 macroinitiator initiated ATRP of MMA at
50 ꢁC using CuBr/dHbpy as catalytic system to provide
PMBTFVB-g-PMMA graft copolymers via the grafting-from
strategy (Table 2). The molecular weights of graft copoly-
mers were all much higher than those of macroinitiators,
which demonstrated ATRP of MMA was performed and they
also increased with the extending of polymerization time,
which is the characteristic of ATRP.53,54 In this case, a high
feed ratio of MMA to the initiation group (250:1) and a rela-
tively low conversion of MMA (<35%) were used to sup-
press the intermolecular coupling reactions according to
previous reports.43,66,79–84 All graft copolymers showed
unimodal and symmetrical GPC curves (Fig. 5) with rela-
tively narrow molecular weight distributions (Mw/Mn
1.46), which indicated that intermolecular coupling reactions
could be neglected.66
ꢀ
FIGURE 5 GPC traces of PMBTFVB-Br
PMMA 4.
3 and PMBTFVB-g-
calculated to be 52.3% ¼ 16.2/31.0 and 71.9% ¼ 22.3/31.0
for 3a and 3b macroinitiators (Table 1), respectively.
FT-IR spectrum of PMBTFVB-g-PMMA 4 graft copolymer is
shown in Figure 6. The sharp band of the carbonyl of PMMA
side chains located at 1730 cmꢂ1. The peaks at 1483 and
1449 cmꢂ1 were attributed to the benzene ring of PMBTFVB
backbone. The characteristic signal of perfluorocyclobutyl
unit appeared at 963 cmꢂ1. Figure 7(A) shows typical 1H
NMR signals of the corresponding protons of PMBTFVB
backbone and PMMA side chains. The strong peak at
3.60 ppm originated from three protons of COOCH3 group of
PMMA side chain. The signal of three protons of CCH3 group
of PMMA side chains appeared at 0.84, 1.02, and 1.25 ppm.
After graft copolymerization, the peaks of two protons of
CH2Br group connected to the benzene ring at 4.17 and 4.34
ppm in Figure 3(B) disappeared, which meant that every
pendant ATRP initiation group initiated the polymerization
of MMA and the signal of two protons of CH2 connected to
the benzene ring appeared at 1.89 ppm instead. The signal
of three protons of terminal methoxyl of the backbone was
still found to be located at 3.82 ppm. In addition, a series of
8
80x
<
¼ Br%
ð2Þ
ð3Þ
363x þ 284y þ 204 ꢃ 2
x þ y ¼ 31:0
:
1H NMR is used to determine the molecular weight of
PMBTFVB-Br 3 macroinitiator (Mn,NMR) according to eq 4, in
which Sa, Sb, and Sc are the area of peak ‘‘a’’ at 3.68 ppm,
peaks ‘‘b’’ at 1.99 and 2.18 ppm, and peaks ‘‘c’’ at 4.17 and
4.34 ppm in Figure 3(B), respectively. The values are 10,400
g/mol for PMBTFVB-Br 3a and 10,800 g/mol for PMBTFVB-
Br 3b, as listed in Table 1.
Mn;NMR ¼ 363 ꢃ ð3Sc=SaÞ þ 284 ꢃ ð2Sb=SaÞ þ 204 ꢃ 2 (4)
Thus, it can be concluded from the above results that halo-
gen-containing ATRP initiation sites have been successfully
TABLE 2 Synthesis of PMBTFVB-g-PMMA 4 Graft Copolymera
Conv.d (%)
Mn,GPC (KDa)
Mw/Mn
NMMA
nMMA
Mn,NMR (KDa)
e
e
f
g
h
Sample
Time (h)
4ab
4bb
4cb
4db
4ec
4fc
4gc
a
0.5
1.5
2.5
3.5
1.5
2.5
3.5
5.25
18.63
22.08
33.96
11.55
23.68
34.13
26.1
54.8
60.1
79.5
57.8
70.3
99.6
1.35
1.30
1.31
1.29
1.24
1.21
1.46
257.5
561.7
961.6
1673.1
543.6
839.3
1694.4
15.9
34.7
59.4
103.3
24.4
37.6
76.0
36.2
66.6
106.6
177.7
65.2
94.7
180.2
e
f
Polymerization temperature: 50 ꢁC; feeding ratio: [MMA]:[CH2Br group]:
Measured by GPC in THF at 35 ꢁC.
Total number of MMA repeating unit obtained from 1H NMR.
[CuBr]:[dHbpy] ¼ 250:1:1:2, VMMA:Vanisole ¼ 1:1.
b
g
Initiated by PMBTFVB-Br 3a.
Initiated by PMBTFVB-Br 3b.
The number of MMA repeating unit per PMMA side chain obtained
c
from 1H NMR.
d
h
Determined by GC using anisole as internal standard.
Determined by 1H NMR.
NOVEL FLUORINE-CONTAINING GRAFT COPOLYMER, LIU ET AL.
17

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
PMMA 4 graft copolymer (Mn,NMR) instead of GPC. The total
number of MMA repeating unit (NMMA), the molecular weight
of the graft copolymer (Mn,NMR), and the number of MMA
repeating unit per PMMA side chain (nMMA) can be calcu-
lated according to eqs 5 (Se and Sa are the area of peaks ‘‘e’’
at 0.84, 1.02, and 1.25 ppm and peak ‘‘a’’ at 3.82 ppm in Fig-
ure 7, respectively; 2 is the number of terminal methoxyl of
the backbone), 6 (Mn,3 is the molecular weight of PMBTFVB-
Br 3 macroinitiator as listed in Table 1 and 100 is the molec-
ular weight of MMA), and 7 (NATRP is the number of grafted
ATRP initiation group per chain as listed in Table 1), respec-
1
tively. Indeed, the molecular weights determined by H NMR
(Table 2) are much higher than those obtained by GPC.
NMMA ¼ 2 ꢃ ðSe=SaÞ
Mn;NMR ¼ Mn;3 þ 100 ꢃ NMMA
nMMA ¼ NMMA=NATRP
(5)
(6)
(7)
FIGURE 6 FT-IR spectrum of PMBTFVB-g-PMMA 4.
peaks between ꢂ128.1 and ꢂ132.2 ppm appeared in 19F
NMR spectrum of PMBTFVB-g-PMMA 4 as shown in Figure
7(B), confirming the existence of PFCB linkage in the graft
copolymer. All these points made sure of the structure of
PMBTFVB-g-PMMA 4 graft copolymer.
The conversions of MMA were measured by GC (Table 2)
and the semilogarithmic plots of Ln([M]0/[M]) versus time
were depicted in Figure 8. It is clear that Ln([M]0/[M]) line-
arly depends on the time, indicating that the apparent poly-
merization rate is first order with respect to the concentra-
tion of MMA and the number of propagating species is
constant during the polymerization. This phenomenon and
seven unimodal and symmetrical GPC curves of PMBTFVB-g-
Because the molecular weight of the graft copolymer meas-
ured by GPC is much lower than the ‘‘real’’ value,85 1H NMR
was used to determine the molecular weight of PMBTFVB-g-
FIGURE 7 1H (A) and 19F (B) NMR
spectra of PMBTFVB-g-PMMA 4
in CDCl3.
18
WILEYONLINELIBRARY.COM/JOURNAL/JPOLA

ARTICLE
FIGURE 8 Kinetic plots for solution
ATRP of MMA initiated by PMBTFVB 3a
and 3b at 50 ꢁC, [MMA]:[CH2Br group]:
[CuBr]:[dHbpy] ¼ 250:1:1:2.
PMMA 4 graft copolymers with relatively narrow molecular
weight distributions (Mw/Mn ꢀ 1.46) in Figure 5 both fit in
with the characteristic of ATRP.54,55 Thus, it can be con-
cluded that a series of PMBTFVB-g-PMMA 4 graft copoly-
mers consisting of a perfluorocyclobutyl aryl ether-based
backbone possessing 31 repeating units and PMMA (15–103
repeating units per chain) side chains were successfully syn-
thesized by the well-controlled ATRP of MMA initiated by
PMBTFVB-Br 3 macroinitiator.
Properties of Graft Copolymer
PMBTFVB-g-PMMA 4 graft copolymers with different molec-
ular weights exhibit excellent solubility in most common
solvents including THF, CH2Cl2, chloroform, acetone, ethyl
FIGURE 9 Third heating DSC scans (in N2) of PMBTFVB 2,
PMBTFVB-Br 3b, and PMBTFVB-g-PMMA 4f with a heating rate
of 10 ꢁC/min.
FIGURE 10 TG (A) and DTG (B) curves (in N2) of PMBTFVB 2,
PMBTFVB-Br 3b, and PMBTFVB-g-PMMA 4f with a heating rate
of 10 ꢁC/min.
NOVEL FLUORINE-CONTAINING GRAFT COPOLYMER, LIU ET AL.
19

JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
3 Percec, V.; Lee, M. J Macromol Sci Pure Appl Chem 1992, 29,
acetate, toluene, and DMF; however, it is insoluble in water
and methanol.
723–740.
4 Percec, V.; Schlueter, D.; Kwon, Y. K.; Blackwell, J.; Moller,
DSC thermogram of PMBTFVB-g-PMMA 4f graft copolymer is
shown in Figure 9 and two Tgs were found to be located at
120.3 and 76.3 ꢁC, respectively. The higher Tg at 120.3 ꢁC
obviously corresponded to PMMA side chains, which was
similar to that of PMMA homopolymer.86,87 The lower Tg at
76.3 ꢁC was attributed to PMBTFVB backbone, which was
much higher than those of PMBTFVB 2 homopolymer (Tg ¼
52.5 ꢁC) and PMBTFVB-Br 3a macroinitiator (Tg ¼ 63.6 ꢁC)
as shown in Figure 9; this can be explained that the free
rotation of PMBTFVB backbone was confined by PMMA
branches. The presence of two different Tgs also indicated
that a bulk microphase separation exist in PMBTFVB-g-
PMMA 4 graft copolymer.88,89
M.; Slangen, P. J. Macromolecules 1995, 28, 8807–8818.
5 Johansson, G.; Percec, V.; Ungar, G.; Zhou, J. P. Macromole-
cules 1996, 29, 646–660.
6 Percec, V.; Johansson, G.; Ungar, G.; Zhou, J. P. J Am Chem
Soc 1996, 118, 9855–9866.
7 Percec, V.; Schlueter, D.; Ungar, G. Macromolecules 1997, 30,
645–648.
8 Johansson, G.; Percec, V.; Ungar, G.; Smith, K. Chem Mater
1997, 9, 164–175.
9 Hudsom, S. D.; Jung, H. T.; Percec, V.; Cho, W. D.; Johans-
som, G.; Ungar, G., Balagurusamy, V. S. K. Science 1997, 248,
449–452.
Thermal stability of the polymers was measured by TGA and
the typical TG (thermogravimetry) and DTG (derivative ther-
mogravimetry) curves are shown in Figure 10. The pyrolysis
of PMBTFVB 2 homopolymer and PMBTFVB-Br 3b macro-
initiator processed in a one-stage decomposition pattern
and Td of PMBTFVB 2 and PMBTFVB-Br 3b are recorded at
431 and 364 ꢁC respectively. However, the thermolysis of
PMBTFVB-g-PMMA 4f graft copolymer shows a multi-step
degradation process around about 169 and 500 ꢁC, which
corresponded to the weight loss of PMMA branches90,91 and
PMBTFVB backbone, respectively.
10 Percec, V.; Glodde, M.; Bera, T. K.; Miura, Y.; Shiyanov-
skaya, I.; Singer, K. D.; Balagurusamy, V. S. K.; Heiney, P. A.;
Schnell, I.; Rapp, A.; Spiess, H. W.; Hudsonk, S. D.; Duank, H.
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11 Dukeson, D. R.; Ungar, G.; Balagurusamy, V. S. K.; Percec,
V.; Johansson, G. A.; Glodde, M. J Am Chem Soc 2003, 125,
15974–15980.
12 Percec, V.; Imam, M. R.; Bera, T. K.; Balagurusamy, V. S. K.;
Peterca, M.; Heiney, P. A. Angew Chem Int Ed 2005, 44,
4739–4745.
13 Percec, V.; Glodde, M.; Peterca, M.; Rapp, A.; Schnell, I.;
Spiess, H. W.; Bera, T. K.; Miura, Y.; Balagurusamy, V. S. K.;
Aqad, E.; Heiney, P. A. Chem Eur J 2006, 12, 6298–6314.
CONCLUSIONS
In summary, we reported the first example of perfluorocyclo-
butyl aryl ether-based graft copolymer with relatively nar-
row molecular weight distributions (Mw/Mn ꢀ 1.46) synthe-
sized by the sequential thermal step-growth cycloaddition
polymerization of 2-methyl-1,4-bistrifluorovinyloxybenzene
and ATRP of MMA. NBS and BPO were used to transform the
pendant methyls on the perfluorocyclobutyl aryl ether-based
backbone into ATRP initiation groups without affecting the
main chain. The graft copolymers were obtained by the com-
bination of the grafting-from strategy and ATRP of methyl
14 Percec, V.; Aqad, E.; Peterca, M.; Imam, M. R.; Glodde, M.;
Bera, T. K.; Miura, Y.; Balagurusamy, V. S. K.; Ewbank, P. C.;
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15 Wilson, C. J.; Wilson, D. A.; Feiring, A. E.; Percec, V.
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18 Smith, D. W.; Babb, D. A. Macromolecules 1996, 29,
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19 Smith, D. W.; Boone, H. W.; Traiphol, R.; Shah, H.; Perahia,
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The authors thank the financial support from National Natural
Science Foundation of China (20674094, 21074145,
50873029, and 51073042), Shanghai Rising Star Program
(07QA14066), and Shanghai Nano-Technology Program
(0952nm05800).
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