Radical polyaddition reaction of bis(α-trifluoromethyl-β,β-difluorovinyl) 2,3,5,6-tetrafluoroterephthalate

Article abstract of DOI:10.1016/j.jfluchem.2003.10.003

To develop the radical polyaddition of bisperfluoroisopropenyl esters to preparation of polymers bearing higher fluorine content, the polyaddition reactivity of bis(α-trifluoromethyl-β,β-difluorovinyl) 2,3,5,6-tetrafluoroterephthalate [CF₂=C(CF

Full text of DOI:10.1016/j.jfluchem.2003.10.003

Journal of Fluorine Chemistry 125 (2004) 381–389
Radical polyaddition reaction of bis(a-trifluoromethyl-b,b-difluorovinyl)
2,3,5,6-tetrafluoroterephthalate
Hirotada Fujiwaraa, Tadashi Naritaa,*, Hiroshi Hamanab, Ryo Kuratab
aDepartment of Materials Science and Engineering, Graduate School of Engineering, Saitama Institute of Technology,
1690 Fusaiji, Okabe, Saitama 369-0293, Japan
bDepartment of Applied Chemistry, Saitama Institute of Technology, 1690 Fusaiji, Okabe, Saitama 369-0293, Japan
Received 10 September 2003; received in revised form 14 October 2003; accepted 16 October 2003
Abstract
To develop the radical polyaddition of bisperfluoroisopropenyl esters to preparation of polymers bearing higher fluorine content, the
polyaddition reactivity of bis(a-trifluoromethyl-b,b-difluorovinyl) 2,3,5,6-tetrafluoroterephthalate [CF2¼C(CF3)OCOC6F4COOC(CF3)¼CF2]
(TFT) with 1,4-dioxane (DOX) and diethoxydimethylsilane (DEOMS) were described. The results of the model reactions of 2-pentafluor-
obenzoxypentafluoropropene [CF2¼C(CF3)OCOC6F5] (PFBP) with THF, DOX and DEOMS showed that the reactions took place almost
quantitatively and the main products were mono-addition compound for THF and di-addition compounds for DOX and DEOMS, respectively.
The polyaddition of TFT with DOX or DEOMS yielded corresponding polymers of about 1 Â 104 as a molecular weight bearing unimodal
molecular weight distribution by the initiation of peroxides such as benzoyl peroxide and di-tert-butyl peroxide. TFT showed the slightly higher
reactivity compared to that of non-fluorinated analogue, bis(a-trifluoromethyl-b,b-difluorovinyl) terephthalate (BFP), by the results of ternary
polyaddition of TFT/BFP/DOX system. Polymers bearing TFT moiety showed the higher thermostability and contact angle.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Bis(a-trifluoromethyl-b,b-difluorovinyl) 2,3,5,6-tetrafluoroterephthalate; Fluoropolymer; Heteroatom-containing polymers; Polyaddition; Radical
polymerization
1. Introduction
development of radical addition reaction of perfluoroiso-
propenyl group (CF2¼CðCF ÞÀ) with the organic com-
pounds possessing carbonÀ3hydrogen bonds enables to
prepare a wide variety of fluorinated polymers from the
compounds which have never been supposed as starting
materials for preparation of polymers. The reaction has been
developed to preparation of polymers with 1,2-dimethoxy-
ethane [3], diformylalkane [4], triethylamine [5] and
dialkoxydialkylsilanes [6].
As has been reported previously, the radical polyaddi
tion of bis(a-trifluoromethyl-b,b-difluorovinyl) terephthalate
[CF2¼C(CF3)OCOC6H4COOC(CF3)¼CF2] (BFP) with 1,4-
dioxane (DOX) yields polymers, as shown in Eq. (1) [1];
which suggests that a wide variety of organic compounds
possessing carbon–hydrogen bonds might be incorporated
into polymer main chains. The 2,5-diaddition on DOX
(1)
was demonstrated by X-ray crystallographic analysis of
the reaction product of 2-benzoxypentafluoropropene
[CF2¼C(CF3)OCOC6H5] (BPFP) with DOX [2]. The
In this report, the preparation of polymers by radical
polyaddition of bis(a-trifluoromethyl-b,b-difluorovinyl)
2,3,5,6-tetrafluoroterephthalate [CF2¼C(CF3)OCOC6F4-
COOC(CF3)¼CF2] (TFT) with DOX and diethoxydimethyl-
silane (DEOMS) is discussed in order to obtain polymers of
higher fluorine content compared to those from BFP with
* Corresponding author. Tel.: þ81-48-585-6836; fax: þ81-48-585-6004.
E-mail address: narita@sit.ac.jp (T. Narita).
0022-1139/$ – see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2003.10.003

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H. Fujiwara et al. / Journal of Fluorine Chemistry 125 (2004) 381–389
Table 1
Radical addition reaction of PFBP
Ether
Conversiona (%)
Addition producta (%)
1:1
1:2
THF
100
81
98
24
32
2
76
68
DOX
DEOMS
80
PFBP: 4.9 mmol; ether: 39.0 mmol; BPO: 0.98 mmol; reaction tempera-
ture: 80 8C; reaction time: 3 days.
a Conversion of PFBP measured by GC.
DOX and DEOMS since the results of detailed study on the
high reactivity of DOX [1] and DEOMS [6] has previously
been reported. The reactivity difference between TFT
and BFP was also examined by the ternary polyaddition
of TFT, BFP and DOX. Prior to the polyaddition of TFT,
the radical addition of 2-pentafluorobenzoxypentafluoro-
propene [CF2¼C(CF3)OCOC6F5] (PFBP) with THF,
DOX and DEOMS was examined as model reactions in
order to confirm that the addition reaction may be applicable
to preparation of polymers and to find out the proper
polyaddition reaction conditions. The comparison of reac-
tivity of PFBP and non-fluorinated analogue, BPFP, was also
studied.
Fig. 1. Time dependency on the yields of mono-addition (a) and di-
addition products (b) of PFBP with DOX.
The information on the yields of di-addition product is
essential to develop the radical addition for preparation of
polymers. The reaction of PFBP with DOX was analyzed by
the relative area ratios of GC peaks assigned to mono- and
di-addition products. The results are shown in Fig. 1. The
concentration of di-addition product increases rapidly with
reaction time while the yield of mono-addition product
scarcely increases. The reactivity of PFBP with DOX is
concluded to be high enough to develop the reaction to
polymer preparation.
2. Results and discussion
The results of the comparison of the reactivity of PFBP to
that of BPFP are depicted in Fig. 2, which shows that slightly
higher reactivity of PFBP is pointed out.
2.1. Addition reaction
In order to clarify the radical addition reactivity of mono-
functional compound, the reactions of PFBP with THF, DOX
and DEOMS in the presence of BPO were examined. The
results are summarized in Table 1. The addition reactions
take place almost quantitatively and the higher yields of di-
addition products of DOX and DEOMS are demonstrated.
The detailed analytical results of the products are described in
Section 4. It turns out that THF performs as a monofunc-
tional, and DOX and DEOMS work as bifunctional com-
pounds. As has been reported that the addition of BPFP onto
DOX takes place at 2- and 6-positions of DOX [2], the
reactions are concluded to proceed by Eqs. (2)–(4):
2.2. Polyaddition reaction
The results of PFBP with DOX indicate that the radical
addition is applicable to preparation of polymers by bifunc-
tional TFT as a starting material. The results of polyaddition
of TFT with DOX are shown in Table 2. The polyaddition
takes place with the oxo-radical initiation as has been
demonstrated in the polyaddition of BFP with DOX [1].
As expected from the results of the model reactions, oxo
radicals derived from BPO and DTBP produce higher
molecular weight polymers in fair yields. No high molecular
weight polymer is yielded in the presence of AIBN though
(2)
(3)
(4)

H. Fujiwara et al. / Journal of Fluorine Chemistry 125 (2004) 381–389
383
24% of TFT is consumed. The analyses of the reaction
products were difficult because the products were hardly
separated. The equimolar reaction of TFT with DOX pro-
duces no polymers of high molecular weights. The excess
amount of DOX in feed is necessary to obtain higher
conversions of TFT and higher yields of polymers of high
molecular weights as has been demonstrated in the reaction
system of BFP with DOX [1]. Polymer obtained was soluble
in toluene, acetone, chloroform and ethyl acetate, and
insoluble in methanol, ethanol and hexane.
3.6–4.4 ppm are assignable to protons of dioxane moiety in
polymer chain. No peaks at À80.7 and À95.6 ppm assign-
able to CF2¼ of TFT are observed in Fig. 3(d), and the
absorptions from À114 to À122 ppm assignable to fluor-
omethylene fluorines are observable. Other assignment of
each peak is depicted in Fig. 3. The complicated splitting of
the peaks might come from the presence of diastereomers of
the addition products. This might be proved by the fact that
the 13C NMR spectrum in Fig. 3(c) is similar to that of
Fig. 3(b) which was measured under decoupled condition of
fluorine resonance. The polyaddition, therefore, is con-
cluded to takes place according to Eq. (5).
The results of 1H, 13C and 19F NMR measurements of the
polymer obtained are illustrated in Fig. 3. TFT units and
(5)
DOX units are observed in the characterization of the
1
The results of the polyaddition of TFT with DEOMS are
summarized in Table 3. The recovery of polymers was
difficult since no proper solvent for reprecipitation was
found out. Polymer obtained was soluble in toluene,
acetone and ethyl acetate, and partially soluble in metha-
nol, ethanol and hexane. Solubility of polymers might
reflect higher contents of fluorines and alkylsilyl groups.
Similar tendency of reactivity to the results of TFT with
DOX is observed since polymers are produced with the
initiation of oxo radicals derived from BPO and DTBP, and
no high molecular weight polymers are obtained in the
presence of AIBN in spite of the high conversion of TFT.
At least four-fold excess amount of DEOMS in feed is
necessary to obtain fairly high yields of polymers by the
initiation of BPO. In the presence of DTBP eight-fold
excess of DEOMS is needed for preparation of high
molecular weight polymers. Longer reaction time is
preferable to obtain suitable yields of polymers and mole-
cular weights. Step-growth polymerization mechanism is
polymer. In H NMR the peak around 6.2 ppm is assigned
to the methine proton of the TFT moiety and the peaks at
Fig. 2. Reactivity comparison of PFBP (a) and BPFP (b) with DOX.
Table 2
Radical polyaddition of TFT with DOX
Conversiona (%)
Mn  103
Mw/Mn
Yieldc (%)
Mn  103
Mw/Mn
b
b
d
d
Initiator
BPO
DOX/TFT (mol/mol)
Temperature (8C)
1
2
4
8
80
80
80
80
31
82
74
95
3.4
2.5
3.1
2.8
1.3
1.6
1.6
2.3
0
44
63
22
3.0
3.3
4.7
1.5
1.7
1.7
DTBP
AIBN
1
2
4
8
120
120
120
120
82
96
2.9
2.2
3.6
2.4
1.6
2.2
5.8
4.0
0
20
22
22
2.8
8.6
3.9
2.2
3.3
4.2
100
100
8
60
24
0
TFT: 4.0 mmol; initiator: 0.8 mmol; reaction time: 7 days.
a Conversion of TFT measured by GC.
b Before reprecipitation.
c Reprecipitated with CH3OH.
d After reprecipitation.

384
H. Fujiwara et al. / Journal of Fluorine Chemistry 125 (2004) 381–389
Fig. 3. 1H (a), 13C {1H, 19F(À85 ppm)} (b), 13C {1H (5 ppm)} (c) and 19F NMR {1H (5 ppm)} (d) of the reaction product of TFT with DOX.

H. Fujiwara et al. / Journal of Fluorine Chemistry 125 (2004) 381–389
385
Table 3
Radical polyaddition of TFT with DEOMS
Conversiona Mn  103
Mw/Mn
Yieldc
(%)
Mn  103
Mw/Mn
b
b
d
d
Initiator
BPO
mmol
DEOMS/TFT
(mol/mol)
Temperature(8C)
Time
(days)
(%)
0.8
0.8
0.8
1
4
8
80
80
80
7
7
7
82
74
95
2.4
3.1
3.3
1.4
1.6
1.8
7
63
22
2.7
3.3
4.6
1.4
1.7
1.6
DTBP
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.4
1.6
1
4
8
8
8
8
8
8
8
8
120
120
120
120
120
120
120
120
120
120
7
7
100
31
42
81
99
98
97
99
96
97
3.0
3.4
3.3
1.3
11
0
7.7
2.2
0.5
1
0
3.2
4.7
4.2
4.1
4.7
3.8
3.8
1.1
3.5
2.7
2.8
2.6
1.9
2.8
0
2
10
20
23
23
23
22
8.6
7.6
6.1
5.6
4.9
6.3
2.9
2.2
2.2
2.2
1.8
2.4
3
7
14
7
7
AIBN
0.8
8
60
7
57
0
TFT: 4.0 mmol.
a Conversion of TFT measured by GC.
b Before reprecipitation.
c Reprecipitated with CH3OH (5% H2O).
d After reprecipitation.
suggested since the molecular weights tends to increase
with the reaction time.
The results of NMR measurements of the polymer
obtained are illustrated in Fig. 4. In H NMR (Fig. 4(a))
the peak around 6.2 ppm is assigned to the methine
proton of the TFT moiety and the absorptions assignable
to the methyl protons bound to silicone atom appear
at 0.1–0.3 ppm. The peaks assignable to the methine
proton of ethylsilyl group in the main chain appear at
4.1–4.4 ppm. Other assignment of each peak is depicted in
Fig. 4. The polyaddition, therefore, is concluded to takes
place by Eq. (6):
1
(6)
Table 4
Ternary polyaddition of TFT/BFP/DOX and TFT/BFP/DEOMS
Compound
DOXa
mmol
Initiatora
BPO
mmol
Temperature (8C)
Yield (%)
Mn  104
Mw/Mn
24
24
24
24
0.6
1.2
0.6
1.2
60
60
80
80
50
91
49
61
0.12
0.43
0.97
1.05
1.6
3.2
5.5
3.7
DTBP
BPO
DEOMSb
24
12
24
48
72
24
24
0.6
1.2
1.2
1.2
1.2
0.6
1.2
60
60
60
60
60
80
80
98
46
0.14
0.21
0.30
0.40
0.37
0.24
0.74
1.5
2.7
4.3
3.8
3.0
3.9
8.5
72
75
83
DTBP
96
107
TFT: 3.0 mmol; BFP: 3.0 mmol; time: 3 days.
a Reprecipitated with CH3OH.
b Vacuum purified.

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H. Fujiwara et al. / Journal of Fluorine Chemistry 125 (2004) 381–389
2.3. Ternary polyaddition reaction
TFT in feed, and those of ordinate show the mole fraction
of TFT moiety in polymer. The reaction should be ceased
under low conversions, preferably lower than 10%, since the
decreases of starting materials scarcely affect kinetics of
polymerization reaction. This method is often adopted in
analyzing a copolymerization reactivity on the binary sys-
tem of vinyl monomers. The compositions of TFT contents
in polymers were calculated of the concentrations of TFT
and BFP measured by GC (Fig. 5(a)) and the area ratios of
NNE 13C NMR measurement of carbonyl carbons (Fig. 5(b))
of the ternary polymers. The results show in good agree-
ment. The slightly higher reactivity of TFT is concluded
since the composition curves are above the diagonal line.
The result agrees with that of the reaction between mono-
functional compounds shown in Fig. 2. The monomer
reactivity ratios of TFT (M1) and BFP (M2) are r1 ¼ 1:19,
As has been mentioned above the slightly higher reac-
tivity of monofunctional PFBP is demonstrated compared
to that of BPFP in Fig. 2. Ternary polyadditions of TFT,
BFP and DOX or DEOMS would offer the information on
the reactivity difference between TFT and BFP. The results
are shown in Table 4. Polymers are produced under all the
conditions examined here and the polymer of the highest
molecular weight is about 1 Â 104. The higher yields
of polymers might come from the lowered solubility of
ternary polymers probably because fluorine contents are
decreased.
The more detailed reactivity comparison between TFT
and BFP was examined by the ternary polyaddition of TFT,
BFP and DOX. The results are depicted in Fig. 5. The
numbers on the abscissa indicate the mole fraction of
Fig. 4. 1H (a), 13C {1H, 19F (À85 ppm)} (b), 13C {1H (5 ppm)} (c) and 19F NMR {1H (5 ppm)} (d) of the reaction product of TFT with DEOMS.

H. Fujiwara et al. / Journal of Fluorine Chemistry 125 (2004) 381–389
387
Fig. 4.. (Continued ).
¨
r2 ¼ 0:78, respectively, calculated with Kelen–Tu¨dos
method. It might then be concluded that the block-type
polymer bearing slightly higher content of TFT moiety is
yielded at the early stage of the ternary polymerization.
The results of surface and thermal character of polymers
are summarized in Table 5. Thermogravimetric analysis of
the polymers bearing TFT units shows that the 5% weight-
loss temperature is about 300 8C. Contact angle measure-
ment of the polymer film prepared by spin-coating method
results 1008 for water and 30.58 for methanol as the highest
values. These results indicate that the fluoroalkyl groups
tend to be on the surface of the film of the air-side and
dioxanyl or alkylsilyl groups may bind to the other side of
the film since dioxanyl or alkylsilyl groups has a strong
affinity for glass surface. The penetration of water droplet
through the film was observed in the case of the ternary
polymer of TFT/BFP/DOX. Detailed study on the surface of
ternary polymers related to the phenomenon of water pene-
tration is under way.
Fig. 5. Ternary polymer composition curves of TFT/BFP/DOX determined
with GC (a) and 13C NMR of oligomer (b) (see text).
Table 5
Surface and thermal character of polymer
Contact anglea,y (8)
Td5 (8C)
b
Polymer
Molecular weight
Film thickness (mm)
H2O
CH3OH
TFT/DOX
Low Mw
High Mw
Low Mw
High Mw
High Mw
High Mw
High Mw
High Mw
9.9
12.0
6.7
96.0
96.4
12.0
10.0
30.5
26.0
22.8
28.6
9.6
190
300
225
300
302
294
275
275
TFT/DOX
TFT/DEOMS
TFT/DEOMS
TFT/BFP/DOX
TFT/BFP/DEOMS
BFP/DOX
99.6
6.5
100.0
90.6
12.1
14.4
3.3
92.3
92.0
100.0
BFP/DEOMS
6.8
21.6
a Liquid drop method.
b 5% weight-loss temperature.

388
H. Fujiwara et al. / Journal of Fluorine Chemistry 125 (2004) 381–389
3. Conclusion
THF was purified by distillation under purified nitrogen
atmosphere after being dried by refluxing with potassium
benzophenone ketyl before use. DOX was dried by reflux-
ing over calcium hydride and distilled under nitrogen
atmosphere. DEOMS was donated by courtesy of Shin-
Etsu Chemical Co. Benzoyl peroxide (BPO) was precipi-
tated from chloroform and then recrystallized in methanol
at 0 8C. Di-tert-butyl peroxide (DTBP) was used as
received.
The radical polyaddition of bis(a-trifluoromethyl-b,b-
difluorovinyl) 2,3,5,6-tetrafluoroterephthalate with 1,4-
dioxane and diethoxydimethylsilane produced successfully
polymers of about 104 as a molecular weight possessing
higher fluorine contents. The slightly higher reactivity of
fluorinated terephthalate is demonstrated compared to that
of non-fluorinated analogue. The high thermostability and
contact angle were proved.
4.2. Addition reaction
4. Experimental
The addition reaction of PFBP with ethers such as THF,
DOX and DEOMS was carried out in sealed glass ampoule
by adding PFBP (4.9 mmol, 1.0 ml), BPO (0.98 mmol) and
ether compound (39.0 mmol) at 80 8C for 3 days. The
reaction was ceased by bubbling oxygen and the concen-
tration of PFBP was measured by vapor-phase chromato-
graphy (GC) by means of tridecane as an external standard.
The reaction system was concentrated by removing low-
boiling materials under reduced pressure, and the reaction
products were roughly separated by the chromatography of
silica gel 60 column with hexane: diethyl ether (20:1 to
5:1 v/v) as an eluent. The addition products were isolated
by preparatory size exclusion chromatography (SEC). The
All experiments related to reaction and polymerization
were carried out under a purified nitrogen atmosphere in
order to preclude oxygen and moisture.
4.1. Reagent
BPFP was synthesized according to the method
reported by Nakai and coworkers [7]. PFBP was synthe-
sized by the reaction of pentafluorobenzoyl chloride with
lithium enolate derived from 1,1,1,3,3,3-hexafluoropro-
pan-2-ol (HFIP) with 2 eq. of butyllithium in THF.
Commercial benzoyl chloride and pentafluorobenzoyl
chloride (64 8C/23 mmHg) were distilled under reduced
pressure before use. Commercial butyllithium in hexane
solution was used after determination of the concentration
by alkalimetry. HFIP (Central Glass Co.) was dried by
refluxing over calcium hydride and distilled under
reduced pressure. TFT was synthesized by 2,3,5,6-tetra-
fluoroterephthaloyl chloride with 2 eq. of lithium enolate
of HFIP according to the modified method of preparation
of BFP [1] (yield: 65%, bp 75 8C/1 mmHg, mp 39–41 8C).
Tetrafluoroterephthaloyl chloride (Showa Denko Co.)
was used as received. TFT: 13C NMR [1H {5 ppm}]:
d ¼ 103:6À104:5 (m, CF2¼C), 113.5 (s, CÀCO), 119.3
(q, J ¼ 272:3 Hz CF3), 145.1 (d, J ¼ 266:0 Hz C6F4),
156.0 (t, J ¼ 298:0 Hz CF2¼), 154 (s, COO). 19F NMR
[1H {5 ppm}]: d ¼ À66:0 (3F, s, CF3), À80.7 (1F, s,
CF2¼ ðcisÞ), À95.6 (1F, s, CF2¼ ðtransÞ), À134.6 (4F,
s, C6F4). MS (EI, m/z): 498 [M]þ, 479 [M À F]þ, 351
[M À ðCF2¼CðCF3ÞOÀÞ]þ, (CI, isobutane m/z): 499
[M þ 1]þ.
1
products were analyzed by GC, mass-spectrum, and H,
13C and 19F NMR.
Mono-addition product of PFBP with THF: H NMR:
1
d ¼ 1:93À2:05 (2H, m, CH2ÀCH2ÀCH2), 2:69À2:24 (2H,
m, CH2ÀCH2ÀCH), 3:81À3:99 (2H, m, OÀCH2ÀCH2),
4:18À4:34 (1H, m, OÀCHÀðCF2ÞCH2), 6:01À6:16
(1H, m, CF2ÀCHÀðCF3ÞO). 13C NMR [1H {5 ppm},
19F{À85 ppm}]: d ¼ 24:4, 25.1 (s, CH2ÀCH2ÀCH2),
25.5, 25.7 (s, CH2ÀCH2ÀCH), 67.9, 68.3 (s, CF2À
CHðCF3ÞO), 69.8, 70.0 (s, OÀCH2ÀCH2), 76.0 (s,
OÀCHÀðCH2ÞCF2), 105.97, 106.06 (s, C6F5 (i)), 117.9
(s, CHÀCF2ÀCH), 118.85, 118.89 (s, CF3), 137.8, 138.3
(s, C6F5 (m)), 144.0, 144.6 (s, C6F5 (o)), 146.1 (s, C6F5 (p)),
156.3, 157.0 (s, COO). 19F NMR [1H {5 ppm}]: d ¼ À71:7,
À72.2 (3F, t, J ¼ 10:0 Hz, CF3), À118.4, À119.7, À122.8,
À125.1 (2F, wq, J ¼ 10:0, 264.9 Hz, CF2), À136.7 (2F, s,
C6F5 (o)), À146.2, À146.5 (1F, t, J ¼ 23:0 Hz, C6F5 (p)),
À160.1, À160.3 (2F, t, J ¼ 3:0 Hz, C6F5 (m)). MS (EI, m/z):
395 [M À F]þ, 219 [M À COC6F5]þ, 195 [C6F5CO]þ, 167
[C6F5]þ, 71 [C4H7O]þ, (CI, isobutane m/z): 415 [M þ 1]þ
195 [C6F5CO]þ.
Di-addition product of PFBP with DOX: 1H NMR:
d ¼ 3:55À3:78, 3:80À4:04 (4H, m, OÀCH2ÀCH),
3:85À4:32 (2H, m, CF2ÀCHÀðCH2ÞO), 6.16 (2H, br,
CF2ÀCHÀðCF3ÞO). 13C NMR [1H {5 ppm}, 19F
{À85 ppm}]: d ¼ 63:8, 64.3 (s, OÀCH2ÀCH), 66.2, 66.8
(s, CF2ÀCHðCF3ÞO), 73.0, 74.9 (s, OÀCHÀðCH2ÞCF2),
105.97, 106.06 (s, C6F5 (i)), 116.6, 117.7 (m,
CHÀCF2ÀCH), 122.0, 122.4 (m, CF3), 1382, 138.9 (s,
C6F5 (m)), 144.4, 145.1 (s, C6F5 (o)), 146.3 (s, C6F5 (p)),
156.7, 157.8, 158.2 (s, COO). 19F NMR [1H {5 ppm}]:
PFBP: 13C NMR [1H {5 ppm}]: d ¼ 103:0À105:0 (m,
CF2¼C), 119.8 (qdd, J ¼ 6:7, 8.6, 271.6 Hz CF3), 155.5 (s,
COO), 156.3 (qt, J ¼ 3:0, 298.2 Hz CF3)), 105.2 (td,
J ¼ 3:8, 14.4 Hz C6F5 (i)), 138.3 (qd, J ¼ 12:0, 253.7 Hz
C6F5 (m)), 145.1 (md, J ¼ 264:3 Hz C6F5 (o)), 146.6 (md,
J ¼ 280:0 Hz C6F5 (p)). 19F NMR [1H {5 ppm}]:
d ¼ À66:1 (3F, s, CF3), À81.3 (1F, s, CF2¼ ðcisÞ),
À90.1 (1F, s, CF2¼ ðtransÞ), À135.2 (2F, s, C6F5 (o)),
À144.1 (1F, s, C6F5 (p)), À159.0 (2F, s, C6F5 (m)). MS (EI,
m/z): 323 [M À F]þ, 279 [CF2¼C(CF3)O]þ, 195
[C6F5COÀ]þ, (CI, isobutane m/z): 342 [M]þ, 343 [M þ 1]þ.

H. Fujiwara et al. / Journal of Fluorine Chemistry 125 (2004) 381–389
389
d ¼ À71:4to À 72:3 (3F, m, CF3), À115:7to À 120:2 (2F,
m, CF2), À136:1to À 136:7 (2F, m, C6F5 (o)), À145:1toÀ
145:5 (1F, m, C6F5 (p)), À159:4to À 159:8 (2F, m, C6F5
(m)). MS (EI, m/z): 769 [M À F]þ, 195 [C6F5CO]þ, 167
[C6F5]þ.
W). The column temperature was programmed from 100
to 300 8C at 20 8C minÀ1. The mass spectra were measured
on a JEOL JMS-SX102. Isobutane was used as a reagent gas
of chemical ionization (CI) method. SEC was measured with
a Tosoh HLC-802A apparatus at 40 8C with a Shodex
KF802.5-KF801(Â2) for low-molecular-weight compounds
and a Shodex KF 805L (Â2) for high-molecular-weight
compounds with THF as an eluent (flow rate: 1.0 ml minÀ1).
The molecular weight measured by SEC was calculated
from the calibration curve for standardized polystyrene.
Preparatory SEC was carried out with an LC-908JAI (Japan
Analytical Ind.) with Gel H1 & H2 column series with
chloroform as an eluent at room temperature (flow rate:
3.8 ml minÀ1). Thermogravimetric analysis was carried out
with a TGA 51 thermogravimeter with a thermal analyst
2000 (TA Instruments) under nitrogen atmosphere with a
heating rate of 10 8C minÀ1. The contact angle was mea-
sured by a liquid drop method with CA-D (Kyowa Kaimen
Kagaku Co.). Film thickness was measured by a Mitutoyo
SURFTEST SV-600 and a Mitutoyo Auto Leveling
Table SV-600.
1
Di-addition product of PFBP with DEOMS: H NMR:
d ¼ À0:01to0:31 (6H, m, SiÀCH3), 1.11–1.29 (6H, m,
CHÀCH3), 4.10–4.21 (2H, m, OÀCHÀðCF2ÞCH3),
4.15 (1H, br, OÀCHÀðCF2ÞCH2), 5.97 (1H, br, CF2À
CHÀðCF3ÞO). 13C NMR [1H {5 ppm}, 19F {À85 ppm}]:
d ¼ À2:5to0:7 (m, SiÀCH3), 14.6–18.0 (m, CHÀCH3),
57:6 ꢀ 57:7 (m, CF2ÀCHðCH3ÞO), 66.9–69.0 (m,
OÀCHÀðCF3ÞCH2), 105.5, 105.4 (s, C6F5 (i)), 118.0 (m,
CF3), 118.1–118.9 (m, CF2), 138.1, (s, C6F5 (m)), 144.4,
144.6(s, C6F5 (o)), 146.1(s, C6F5 (p)), 156.7, 156.9(s, COO).
19F NMR [1H {5 ppm}]: d ¼ À72:3to À 74:0 (3F, m, CF3),
À119:2to À 120:0, À122:2to À 123:6, À127:8to À 128:9
(2F, m, CF2), À138.4 (2F, s, C6F5 (o)), À147.5, À147.7
(2F, t, J ¼ 23:0 Hz, C6F5 (p)), À161.6, À161.8 (1F, t,
J ¼ 23:0 Hz, C6F5 (m)).
The polyaddition reaction was carried out by adding TFT,
ether compound and BPO in sealed ampoule which was
carefully flame dried. After a definite time, the reaction was
ceased by bubbling oxygen and the concentration of TFT
was measured with GC by means of tridecane as an external
standard. The polymer was isolated by reprecipitation and
then dried thoroughly in vacuo. The ternary polymerization
of TFT/BFP/DOX was analyzed by the measurement of the
concentrations of TFTand BFP by GC, and the area ratios of
NNE 13C NMR measurement of carbonyl carbons [8], and
ternary polymer composition curve was analyzed by Kelen–
Acknowledgements
This work was financially supported in part by the High-
Tech Research Center Program of Saitama Institute of
Technology founded in 1999 by the support of the Ministry
of Education, Culture, Sports, Science and Technology of
Japan, which the authors are grateful. The authors also thank
Mr. H. Kobayashi for his experimental assistance.
¨
Tu¨dos method [9] to obtain monomer reactivity ratios. The
molecular weight of the polymer was determined by SEC.
The structure of the resulting reaction product was deter-
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