Synthesis and polymerization of novel fluorinated acrylates and methacrylates bearing alkoxyl groups derived from radical addition reaction of perfluoroisopropenyl ester

Article abstract of DOI:10.1016/j.jfluchem.2007.04.025

Radical addition of 2-benzoxypentafluoropropene [CF₂{double bond, long}C(CF₃)OCOC₆H₅] (BPFP) with alcohols such as ethanol and 2-propanol was investigated to afford fluorinated alcohols. Radical addition of BPFP

Full text of DOI:10.1016/j.jfluchem.2007.04.025

Journal of Fluorine Chemistry 128 (2007) 965–970
www.elsevier.com/locate/fluor
Synthesis and polymerization of novel fluorinated acrylates and
methacrylates bearing alkoxyl groups derived from radical
addition reaction of perfluoroisopropenyl ester
a
b
Tadashi Narita a, , Yoshiomi Sakuragi , Hiroaki Yabata ,
*
Daisuke Kimura b, Hiroshi Hamana b
a Department of Applied Chemistry, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji,
Fukaya 369-0293, Japan
b Department of Life Science and Green Chemistry, Saitama Institute of Technology, 1690 Fusaiji, Fukaya 369-0293, Japan
Received 15 March 2007; received in revised form 24 April 2007; accepted 24 April 2007
Available online 29 April 2007
Abstract
Radical addition of 2-benzoxypentafluoropropene [CF2 C(CF3)OCOC6H5] (BPFP) with alcohols such as ethanol and 2-propanol was
investigated to afford fluorinated alcohols. Radical addition of BPFP with cyclic ethers such as tetrahydrofuran, 1,3-dioxolane and tetrahydropyran
was also achieved to afford addition products followed by hydrolysis to yield fluorinated alcohols possessing cyclic structures. Novel fluoroalkyl
acrylates and methacrylates were synthesized from the fluorinated alcohols with (meth)acryloyl chlorides. Radical polymerization of the
fluoroalkyl (meth)acrylates yielded polymers of 1.2 ꢀ 105 as the highest molecular weight.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Fluoropolymers; Radical polymerization; Perfluoroisopropenyl group; Radical addition; Methacrylate
1. Introduction
afforded novel fluorinated polymers bearing such organic
segments in polymer main chains as 1,4-dioxane, diethyl ether,
dimethoxyethane, 18-crown-6, triethylamine, glutaraldehyde
and alkanes which have never been supposed as direct starting
compounds for preparation of polymers by developing the
radical addition reaction to polyaddition [19].
As has previously been reported the radical addition of 2-
benzoxypentafluoropropene [CF2 C(CF3)OCOC6H5] (BPFP)
with large excess of tetrahydrofuran (THF) in feed affords 1:1
addition product in high yield [1]. 1:2 addition product was
preferable to 1:1 adduct when the addition of BPFP was carried
out with 1,4-dioxane and the structure of the product was
determined by X-ray crystallographic analysis to show 2,6-
diaddition [2]. An easy way of carbon–carbon bond formation
was achieved under mild reaction condition and the reaction was
found to be applicable to wide variety of organic compounds
possessing carbon–hydrogen bonds [3]. The radical addition of
perfluorovinyl compounds are well-known reaction to produce
many fluorinated organic compounds [4–18]. The reaction of
bifunctional compound, bis(a-trifluoromethyl-b,b-difluorovi-
nyl) terephthalate [CF2 C(CF3)OCOC6H4COOC(CF3) CF2],
This report concerns about the syntheses of fluorinated
alcohols by radical addition of BPFP with ethanol and 2-
propanol. Syntheses of acrylates and methacrylates were
carried out by the reaction of acryloyl chloride or
methacryloyl chloride with fluorinated alcohols produced
and the radical polymerization reactivity of these acrylate
derivatives was examined. The fluorinated compounds
derived from BPFP with cyclic ethers such as THF, 1,3-
dioxolane and tetrahydropyran were also synthesized fol-
lowed by hydrolysis to afford fluorinated alcohols from which
fluoroalkyl acrylates and methacrylates bearing cyclic
structures were yielded, and polymerization of the acrylate
derivatives was investigated. A polymer possessing fluor-
oalkyl group with cyclic structures might be applicable to
photoresist lithography [20].
* Corresponding author. Tel.: +81 48 585 6836; fax: +81 48 585 6004.
E-mail address: narita@sit.ac.jp (T. Narita).
0022-1139/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2007.04.025

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T. Narita et al. / Journal of Fluorine Chemistry 128 (2007) 965–970
2. Experimental
d = ꢁ72 (3F, s, CF3), ꢁ119, ꢁ128 (2F, dd, CF2). MS = 298
(electron ionization (EI), m/z): 233 [M–(F)]+, 298 [M]+, 77
[C6H5]+, 105 [C6H5CO]+, 121 [C6H5COO]+; (chemical
ionization (CI), m/z): 299 [M+1]+, 105 [C6H5CO]+.
All experiments related to reaction and polymerization were
carried out under a purified nitrogen atmosphere to preclude
oxygen and moisture.
1,1,1,3,3-Pentafluoro-2-benzoxy-4-methyl-4-pentanol was
yielded by the reaction of BPFP with 2-propanol; bp 153 8C/
0.1 mmHg; yield: 69%. H NMR (in CDCl3): d = 1.3 (3H, s,
1
2.1. Reagents
CH3), 1.4 (3H, s, CH3), 6.2 (1H, m, CH), 7.4 (2H, dt, C6H5), 7.6
(1H, dt, C6H5), 8.1 (2H, dd, C6H5). 13C{1H(5 ppm)} NMR:
d = 23 (s, CH3), 66 (m, CH), 74 (m, C(CH3)2), 117–121 (t, CF2),
119–126 (q, CF3), 127–135 (s, C6H5), 163 (s, COO).
19F{1H(5 ppm)} NMR: d = ꢁ117, ꢁ122 (2F, dd, CF2), ꢁ71
(3F, s, CF3). MS = 312 (EI, m/z): 77 [C6H5]+, 105 [C6H5CO]+,
121 [C6H5COO]+; (CI, m/z): 313 [M+1]+.
BPFP was synthesized by the reaction of benzoyl chloride
with 2 eq. of lithium enolate derived from 1,1,1,3,3,3-
hexafluoropropan-2-ol (HFIP) with butyllithium in THF
described in the literatures [21,22]. HFIP (Central Glass Co.)
was dried by refluxing over calcium hydride and distilled under
reduced pressure. Commercial butyllithium in a hexane
solution was used after determination of concentration by
titration. Commercial ethanol, 2-propanol, THF, 1,3-dioxolane,
tetrahydropyran and toluene were purified by usual methods.
Acryloyl chloride and methacryloyl chloride were used after
distillation. Benzoyl peroxide (BPO) and 2,20-azobisisobutyr-
onitrile (AIBN) were precipitated from chloroform and then
recrystallized in methanol at 0 8C. Di-tert-butyl peroxide
(DTBP) was used as received.
The addition reaction of BPFP with THF was carried out by
adding 123 mmol of THF and 15.4 mmol of BPFP with
6.0 mmol of BPO in glass ampule under 80 8C for 3 days [1].
The product was purified by distillation under reduced pressure
to afford 2-(1,1,3,3,3-pentafluoro-2-benzoxypropyl)tetrahydro-
1
furan; bp 95 8C/0.1 mmHg; yield: 87%. H NMR (in CDCl3):
d = 1.8, 1.9 (2H, m, C4H7O), 2.0, 2.1 (2H, m, C4H7O), 3.8, 3.9
(2H, m, C4H7O), 4.2, 4.3 (1H, m, C4H7O), 6.2 (1H, m,
CF2CHCF3), 7.4 (2H, dt, C6H5), 7.6 (1H, dt, C6H5), 8.1 (2H, dd,
C6H5). 13C{1H(5 ppm)} NMR: d = 24 (s, C4H7O), 25 (s,
C4H7O), 66 (m, C4H7O), 69 (s, CF2CHCF3), 75 (d, C4H7O),
117–121 (t, CF2), 119–126 (q, CF3), 127–135 (s, C6H5), 164 (s,
COO). 19F{1H(5 ppm)} NMR: d = ꢁ71 (3F, s, CF3), ꢁ120,
ꢁ125 (2F, dd, CF2). MS = 324 (EI, m/z): 69 [CF3]+, 71
[C4H7O]+. (CI, m/z): 323 [Mꢁ1]+, 325 [M+1]+.
2.2. Measurements
Measurement of vapor phase chromatography was carried
out with a Hewlett-Packard 6890 equipped with flame
ionization detection with a ZB-2, wide-bore fused silica
capillary column (15 m ꢀ 0.53 mm, film thickness: 1.5 mm).
The column temperature was programmed from 80 to 320 8C at
20 8C minꢁ1. The mass spectra were measured on a JEOL JMS-
SX102. Isobutane was used as a reagent of chemical ionization
(CI). Size exclusion chromatography (SEC) was measured with
a TOSOH HLC-802A apparatus at 40 8C with Shodex KF 805L
(2ꢀ) using THF as an eluent (flow rate 1.0 ml minꢁ1). The
molecular weight measured by SEC was calculated from the
calibration curve for standardized polystyrene. NMR spectra
were recorded on a JEOL JNM-ECP500 Fourier transform
The addition reaction of BPFP with 1,3-dioxolane was
carried out by adding 143 mmol of 1,3-dioxolane and
17.9 mmol of BPFP with 3.6 mmol of BPO in glass ampule
under 80 8C for 3 days [1]. The product was purified by
distillation under reduced pressure to afford 2-(1,1,3,3,3-
pentafluoro-2-benzoxypropyl)-1,3-dioxolane; bp 111 8C/
1
0.1 mmHg; yield: 56%. H NMR (in CDCl3): d = 4.2 (4H,
m, C3H5O2), 5.2 (1H, m, C3H5O2), 6.2 (1H, m, CF2CH(CF3)O),
7.4 (2H, dt, C6H5), 7.6 (1H, dt, C6H5), 8.1 (2H, dd, C6H5).
13C{1H(5 ppm)} NMR: d = 66 (s, C3H5O2), 67 (m,
CF2CH(CF3)O), 102 (t, C3H5O2), 114 (t, CF2), 122 (q, CF3),
127–135 (s, C6H5), 164 (s, COO). 19F{1H(5 ppm)} NMR:
d = ꢁ71, ꢁ72 (3F, s, CF3), ꢁ117, ꢁ118, ꢁ119, ꢁ122 (2F, d,
CF2).
1
NMR spectrometer at 500 MHz for H, 125 MHz for 13C and
470 for 19F NMR using deuterated chloroform as a solvent. 13
C
and 19F NMR spectra were measured under proton decoupling
conditions. Chemical shift of 19F NMR was determined based
on absolute magnetic field intensity.
The addition reaction of BPFP with tetrahydropyran was
carried out by adding 102 mmol of tetrahydropyran and
12.8 mmol of BPFP with 5.1 mmol of DTBP in glass ampule
under 120 8C for 3 days. The product was purified by
distillation under reduced pressure to afford 2-(1,1,3,3,3-
pentafluoro-2-benzoxypropyl)tetrahydropyran; bp 118 8C/
0.1 mmHg; yield: 55%. 1H NMR (in CDCl3): d = 1.4–2.0
(m, 6H, C5H9O), 3.0–4.0 (m, 3H, C5H9O), 6.2, 6.3 (1H, m,
CF2CH(CF3)), 7.4 (2H, dt, C6H5), 7.6 (1H, dt, C6H5), 8.1
(2H, dd, C6H5). 13C{1H(5 ppm)} NMR: d = 22, 23, 28 (s,
C5H9O), 66, 68 (m, C5H9O), 72 (m, CF2CH(CF3)O), 114 (t,
CF2), 122 (q, CF3), 127–135 (s, C6H5), 164 (s, COO).
19F{1H(5 ppm)} NMR: d = ꢁ71, ꢁ72 (3F, s, CF3), ꢁ117,
ꢁ121 (2F, s, CF2).
2.3. Procedures
The addition reaction of BPFP with ethanol was carried out
by adding 171 mmol of ethanol and 21 mmol of BPFP with
4.0 mmol of DTBP in glass ampule under 120 8C for 3 days.
The product was purified by distillation under reduced pressure
to afford 1,1,1,3,3-pentafluoro-2-benzoxy-4-pentanol; bp
140 8C/0.03 mmHg; yield: 65%. 1H NMR (in CDCl3):
d = 1.3 (3H, dd, CH3), 3.9–4.4 (1H, m, CF2CHCH3), 6.0–6.2
(1H, m, CF3CHCF2), 7.4 (2H, dt, C6H5), 7.6 (1H, dt, C6H5), 8.1
(2H, dd, C6H5). 13C{1H(5 ppm)} NMR: d = 14 (s, CH3), 66 (s,
CF2CHCF3), 68 (s, CF3CHCF2), 117–121 (t, CF2), 119–126 (q,
CF3), 127–135 (s, C6H5), 164 (s, COO). 19F{1H(5 ppm)} NMR:

T. Narita et al. / Journal of Fluorine Chemistry 128 (2007) 965–970
967
Hydrolysis of 2-(1,1,3,3,3-pentafluoro-2-benzoxypropyl)te-
trahydrofuran was carried out by adding 28.3 mmol of 2-
(1,1,3,3,3-pentafluoro-2-benzoxypropyl)tetrahydrofuran,
33.9 mmol of methanol and 33.9 mmol of sodium hydroxide
under refluxing for 24 h. After the reaction the product was
extracted by diethyl ether followed by washing with saturated
water solution of sodium chloride and then distilled under
reduced pressure to afford 1,1,3,3,3-pentafluoro-1-tetrahydro-
furanyl-2-propanol; bp 73 8C/0.1 mmHg; yield, 63%. 1H NMR
(in CDCl3): d = 1.8, 1.9 (2H, m, C4H7O), 2.0, 2.1 (2H, m,
C4H7O), 3.8, 3.9 (2H, m, C4H7O), 4.2, 4.3 (1H, m, C4H7O), 6.2
(1H, m, CF2CHCF3). 13C{1H(5 ppm)} NMR: d = 24 (s,
C4H7O), 25 (s, C4H7O), 66 (m, C4H7O), 69 (s, CF2CHCF3),
75 (d, C4H7O), 117–121 (t, CF2), 119–126 (q, CF3).
19F{1H(5 ppm)} NMR: d = ꢁ71 (3F, s, CF3), ꢁ120, ꢁ125
(2F, dd, CF2).
(1H, m, CH2 CH), 6.2 (1H, m, CH), 7.4 (2H, dt, C6H5), 7.6
(1H, dt, C6H5), 8.1 (2H, dd, C6H5). 13C{1H(5 ppm)} NMR:
d = 20 (s, CH3), 66 (m, CH), 82 (m, C(CH3)2), 115–120 (t, CF2),
120–125 (q, CF3), 126–130 (s, C6H5), 131 (s, CH2 ), 134 (s,
CH2 CH), 163 (s, COO), 163 (s, CH2 CHCOO).
19F{1H(5 ppm)} NMR: d = ꢁ71 (3F, s, CF3), ꢁ122, ꢁ117
(2F, dd, CF2).
1,1,3,3,3-Pentafluoro-1-tetrahydrofuranyl-2-propyl acrylate
1
(TFA); yield: 69%. H NMR (in CDCl3): d = 1.8, 1.9 (2H, m,
C4H7O), 2.0, 2.1 (2H, m, C4H7O), 3.8, 3.9 (2H, m, C4H7O), 4.2,
4.3 (1H, m, C4H7O), 5.6, 6.3 (2H, dd, CH2 ), 5.8 (1H, m,
CH2 CH), 5.9 (1H, m, CF2CHCF3). 13C{1H(5 ppm)} NMR:
d = 24 (s, C4H7O), 25 (s, C4H7O), 66 (m, C4H7O), 69 (s,
CF2CHCF3), 75 (d, C4H7O), 117–121 (t, CF2), 119–126 (q,
CF3), 134 (s, CH2 ), 135 (s, CH2 CH), 164 (s, COO), 164 (s,
CH2 CHCOO). 19F{1H(5 ppm)} NMR: d = ꢁ63 (3F, s, CF3),
ꢁ110, ꢁ118 (2F, dd, CF2).
Hydrolysis of 2-(1,1,3,3,3-pentafluoro-2-benzoxypropyl)-
1,3-dioxolane was carried out by adding 26.2 mmol of 2-
(1,1,3,3,3-pentafluoro-2-benzoxypropyl)-1,3-dioxolane,
31.4 mmol of methanol and 31.4 mmol of sodium hydroxide to
afford 1,1,3,3,3-pentafluoro-1-(2-dioxolanyl)-2-propanol; bp
92 8C/3 mmHg; yield: 52%, 1H NMR (in CDCl3): d = 4.2
(4H, m, C3H5O2), 5.2 (1H, m, C3H5O2), 6.2 (1H, m,
CF2CH(CF3)O). 13C{1H(5 ppm)} NMR: d = 66 (s, C3H5O2),
67 (m, CF2CH(CF3)O), 102 (t, C3H5O2), 114 (t, CF2), 122 (q,
CF3). 19F{1H(5 ppm)} NMR: d = ꢁ71, ꢁ72 (3F, s, CF3), ꢁ117
to ꢁ122 (2F, d, CF2).
1,1,3,3,3-Pentafluoro-1-(2-dioxolanyl)-2-propyl acrylate
1
(DLA); yield: 79%. H NMR (in CDCl3): d = 4.2 (4H, m,
C3H5O2), 5.2 (1H, m, C3H5O2), 5.6, 6.3 (2H, dd, CH2 ), 5.8
(1H, m, CH2 CH), 5.9 (1H, m, CF2CH(CF3)O).
13C{1H(5 ppm)} NMR: d = 66 (s, C3H5O2), 67 (m,
CF2CH(CF3)O), 102 (t, C3H5O2), 114 (t, CF2), 122 (q, CF3),
134 (s, CH2 ), 135 (s, CH2 CH), 164 (s, COO), 164 (s,
CH2 CHCOO). 19F{1H(5 ppm)} NMR: d = ꢁ63 (3F, s, CF3),
ꢁ110, ꢁ118 (2F, dd, CF2).
1,1,3,3,3-Pentafluoro-1-(2-pyranyl)-2-propyl acrylate
(TPA); yield: 62%. 1H NMR (in CDCl3): d = 1.4–2.0 (m,
6H, C5H9O), 3.0–4.0 (m, 3H, C5H9O), 5.6, 6.3 (2H, dd, CH2 ),
5.8 (1H, m, CH2 CH), 5.9 (1H, m, CF2CH(CF3)).
13C{1H(5 ppm)} NMR: d = 22, 23, 28 (s, C5H9O), 66, 68
(m, C5H9O), 72 (m, CF2CH(CF3)O), 114 (t, CF2), 122 (q, CF3),
134 (s, CH2 ), 135 (s, CH2 CH), 164 (s, COO), 164 (s,
CH2 CHCOO). 19F{1H(5 ppm)} NMR: d = ꢁ64 (3F, s, CF3),
ꢁ112, ꢁ120 (2F, dd, CF2).
The hydrolysis of 2-(1,1,3,3,3-pentafluoro-2-benzoxypro-
pyl)tetrahydropyran was carried out by adding 28.3 mmol of 2-
(1,1,3,3,3-pentafluoro-2-benzoxypropyl)tetrahydropyran,
33.9 mmol of methanol and 33.9 mmol of sodium hydroxide to
afford 1,1,3,3,3-pentafluoro-1-(2-pyranyl)-2-propanol; bp
110 8C/0.1 mmHg; yield: 62%. 1H NMR (in CDCl3):
d = 1.4–2.0 (m, 6H, C5H9O), 3.0–4.0 (m, 3H, C5H9O), 6.2–
6.3 (1H, m, CF2CH(CF3)). 13C{1H(5 ppm)} NMR: d = 22–28
(m, C5H9O), 66–68 (m, C5H9O), 72 (m, CF2CH(CF3)O), 114 (t,
CF2), 122 (q, CF3). 19F{1H(5 ppm)} NMR: d = ꢁ71, ꢁ72 (3F,
s, CF3), ꢁ117, ꢁ121 (2F, s, CF2).
1,1,1,3,3-Pentafluoro-2-benzoxy-4-pentyl methacrylate
1
(EtMA); yield: 54%. H NMR (in CDCl3): d = 1.4 (3H, d,
CH3), 1.9 (3H, s, CH2 C(CH3)), 5.2 (1H, m, CH3CHCF2), 5.9
(1H, m, CF3CHCF2), 5.6, 6.1 (2H, s, CH2 ), 7.4 (2H, dt, C6H5),
7.6 (1H, dt, C6H5), 8.1 (2H, dd, C6H5). 13C{1H(5 ppm)} NMR:
d = 12 (s, CH3), 18 (s, CH2 C(CH3)), 66 (s, CF2CHCF3), 67 (s,
CF3CHCF2), 118–121 (t, CF2), 119–126 (q, CF3), 127–135 (s,
C6H5), 134, 135 (s, CH2 ), 164 (s, COO), 165 (s,
CH2 C(CH3)COO). 19F{1H(5 ppm)} NMR: d = ꢁ121, ꢁ118
(2F, dd, CF2), ꢁ70 (3F, s, CF3).
Acrylate and methacrylate derivatives were produced by the
reaction of acryloyl chloride or methacryloyl chloride with
alcohols obtained as mentioned above in the presence of
triethylamine as a hydrochloric acid capture. Products were
isolated by silica gel column chromatography by using hexane:
ethyl acetate (20:1, v/v) as an eluent.
1,1,1,3,3-Pentafluoro-2-benzoxy-4-pentyl acrylate (EtA);
1
yield: 36%. H NMR (in CDCl3): d = 1.4 (3H, d, CH3), 5.2,
1,1,1,3,3-Pentafluoro-2-benzoxy-4-methyl-4-pentyl metha-
crylate (IPMA); yield: 20%. 1H NMR (in CDCl3): d = 1.6 (3H,
s, CH3), 1.7 (3H, s, CH3), 1.8 (3H, s, CH2 C(CH3)), 5.8, 6.2
(2H, s, CH2 ), 6.3 (1H, m, CH), 7.4 (2H, dt, C6H5), 7.6 (1H, dt,
C6H5), 8.1 (2H, dd, C6H5). 13C{1H(5 ppm)} NMR: d = 14 (s,
CH3), 19, 20 (s, CH2 C(CH3)), 66 (m, CH), 82 (m, C(CH3)2),
115–120 (t, CF2), 120–126 (q, CF3), 127–135 (s, C6H5), 134,
136 (s, CH2 ), 163 (s, COO), 165 (s, CH2 C(CH3)COO).
19F{1H(5 ppm)} NMR: d = ꢁ117, ꢁ122 (2F, dd, CF2 ), ꢁ71
(3F, s, CF3).
5.3 (1H, m, CH3CHCF2), 5.6, 6.3 (2H, dd, CH2 ), 5.8 (1H, m,
CH2 CH), 6.0 (1H, m, CF3CHCF2), 7.4 (2H, dt, C6H5), 7.6
(1H, dt, C6H5), 8.1 (2H, dd, C6H5). 13C{1H(5 ppm)} NMR:
d = 12 (s, CH3), 66 (s, CF2CHCF3), 67 (s, CF3CHCF2), 118–
121 (t, CF2), 119–125 (q, CF3), 127–135 (s, C6H5), 134 (s,
CH2 ), 135 (s, CH2 CH), 164 (s, COO), 164 (s,
CH2 CHCOO). 19F{1H(5 ppm)} NMR: d = ꢁ73 (3F, s,
CF3), ꢁ122, ꢁ124 (2F, dd, CF2 ).
1,1,1,3,3-Pentafluoro-2-benzoxy-4-methyl-4-pentyl acry-
1
late (IPA); yield: 35%. H NMR (in CDCl3): d = 1.7 (3H, s,
CH3), 1.8 (3H, s, CH2 C(CH3)), 5.6, 6.3 (2H, dd, CH2 ), 5.8
1,1,3,3,3-Pentafluoro-1-tetrahydrofuranyl-2-propyl metha-
1
crylate (TFMA); yield: 25%. H NMR (in CDCl3): d = 1.8,

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T. Narita et al. / Journal of Fluorine Chemistry 128 (2007) 965–970
1.9 (2H, m, C4H7O), 2.0, 2.1 (2H, m, C4H7O), 2.0 (3H, s,
CH2 C(CH3)), 3.8, 3.9 (2H, m, C4H7O), 4.2, 4.3 (1H, m,
C4H7O), 5.8, 6.3 (2H, s, CH2 ), 5.9 (1H, m, CF2CHCF3).
13C{1H(5 ppm)} NMR: d = 18 (s, CH2 C(CH3)), 24 (s,
C4H7O), 25 (s, C4H7O), 66 (m, C4H7O), 69 (s, CF2CHCF3),
75 (d, C4H7O), 117–121 (t, CF2), 119–126 (q, CF3), 134, 135 (s,
CH2 ), 164 (s, COO), 165 (s, CH2 C(CH3)COO).
19F{1H(5 ppm)} NMR: d = ꢁ63 (3F, s, CF3), ꢁ110, ꢁ118
(2F, dd, CF2).
3.2. Addition reaction of BPFP with cyclic ethers
As has previously been reported the radical addition of BPFP
with THF affords the 1:1 adduct in high yield [1]. The addition
reaction has been reported to take place at 2-position of THF
moiety. Similar reactions are found to take place in the case of
1,3-dioxolane and tetrahydropyran in high yields as mentioned
in the experimental part. The reaction of BPFP with 1,3-
dioxolane might take place at 2-position since the absorption at
1
1,1,3,3,3-Pentafluoro-1-(2-dioxolanyl)-2-propyl methacry-
1
late (DLMA); yield: 30%. H NMR (in CDCl3): d = 2.0 (3H,
5.2 ppm in H NMR is assignable to methine hydrogen at 2-
position of 1,3-dioxolane moiety (Fig. 1). The reactions are
then illustrated in Eqs. (2) and (3).
s, CH2 C(CH3)), 4.2 (4H, m, C3H5O2), 5.2 (1H, m, C3H5O2),
5.8, 6.3 (2H, s, CH2 ), 5.9 (1H, m, CF2CH(CF3)O).
13C{1H(5 ppm)} NMR: d = 18 (s, CH2 C(CH3)), 66 (s,
C3H5O2), 67 (m, CF2CH(CF3)O), 102 (t, C3H5O2), 114 (t,
CF2), 122 (q, CF3), 134, 135 (s, CH2 ), 164 (s, COO), 165 (s,
CH2 C(CH3)COO). 19F{1H(5 ppm)} NMR: d = ꢁ63 (3F, s,
CF3), ꢁ110, ꢁ118 (2F, dd, CF2).
(2)
1,1,3,3,3-Pentafluoro-1-(2-pyranyl)-2-propyl methacrylate
1
(TPMA); yield: 20%. H NMR (in CDCl3): d = 1.4–2.0 (m,
6H, C5H9O), 2.0 (3H, s, CH2 C(CH3)), 3.0–4.0 (m, 3H,
C5H9O), 5.8, 6.3 (2H, s, CH2 ), 5.9 (1H, m, CF2CH(CF3)).
13C{1H(5 ppm)} NMR: d = 18 (s, CH2 C(CH3)), 22, 23, 28 (s,
C5H9O), 66, 68 (m, C5H9O), 72 (m, CF2CH(CF3)O), 114 (t,
CF2), 122 (q, CF3), 134, 135 (s, CH2 ), 164 (s, COO), 165 (s,
CH2 C(CH3)COO). 19F{1H(5 ppm)} NMR: d = ꢁ64 (3F, s,
CF3), ꢁ112, ꢁ120 (2F, dd, CF2).
(3)
3.3. Hydrolysis of addition product
Hydrolysis of addition products of BPFP with cyclic ethers
was carried out in order to obtain fluorinated alcohols. The
yields of fluorinated alcohols are 63%, 52% and 61% from the
adducts of THF, 1,3-dioxolane and tetrahydropyran, respec-
tively, to afford pentafluoro-2-propanol derivatives having
Radical polymerization of fluoroalkyl acrylates and metha-
crylates was carried out by adding monomer, BPO or AIBN as
an initiator in glass ampule. Polymer was isolated by
reprecipitation with large excess amount of methanol and
dried thoroughly. The molecular weight of the polymer was
determined by SEC. The structure of the resulting polymer was
1
cyclic structures. The absorption at 5.2 ppm in H NMR of
1,1,3,3,3-pentafluoro-1-(2-dioxolanyl)-2-propanol was also
1
confirmed by H, 13C and 19F NMR.
3. Results and discussion
3.1. Addition reaction of BPFP with alcohols
Radical addition of polyfluorinated vinyl compounds with
alcohol is well-known reaction as mentioned in introduction
part. BPFP also affords addition products with ethanol and 2-
propanol in the yields of 65% and 69%, respectively, as
described in the Section 2. The product of BPFP with ethanol
might be 1,1,1,3,3-pentafluoro-2-benzoxy-4-pentanol since the
absorption of 3.9–4.4 ppm in 1H NMR is assignable to methine
hydrogen of sec-alcohol structure; which is in accord with the
results of the reaction of perfluoropropene with alcohols [17].
The reaction was then concluded to take place as shown in
Eq. (1).
Fig. 1. (a) 1H NMR, (b) fluorine-decoupled 1H NMR and (c) proton-decoupled
13C NMR of the product of BPFP with 1,3-dioxolane.
(1)

T. Narita et al. / Journal of Fluorine Chemistry 128 (2007) 965–970
969
observed, which gives the confirmation of 2-substituted 1,3-
dioxolane derivative produced, as shown in Eq. (4).
(4)
3.4. Synthesis of acrylate and methacrylate
EtA, IPA, TFA, DLA, TPA, EtMA, IPMA, TFMA, DLMA
and TPMA were synthesized from fluorinated alcohols with
acryloyl chloride or methacryloyl chloride, respectively, in
fairly high yields as stated in Section 2. No boiling points were
determined since these compounds were purified by column
chromatography. The detailed analytical data are also shown in
Section 2.
3.5. Radical polymerization of fluoroalkyl acrylate and
methacrylate
The results of radical polymerization of fluoroalkyl acrylates
and methacrylates synthesized here are summarized in Table 1.
The structures of monomers are illustrated in Scheme 1. The
yields of polymers produced are found to be fairly low
Table 1
Radical polymerization of fluorine-containing acrylates and methacrylates
Initiatora
Solvent
Yield
(%)
b
b
¯
¯
Mw/Mn
¯
Run
Monomer
Mn
(ꢀ105)
1
2
EtA
BPO
30
39
45
76
46
40
–
0.31
0.66
0.10
0.34
1.24
0.11
0.01
0.08
–
2.1
2.7
1.3
9.0
3.2
1.4
–
AIBN
AIBN
BPO
3
Toluene
Toluene
4
IPA
Scheme 1. Monomers appeared in Table 1.
5
AIBN
AIBN
BPO
6
7
TFA
DLA
compared to those of methyl acrylate or methyl methacrylate.
This is probably because low-molecular weight polymers
would be soluble in methanol as a reprecipitation solvent since
the solubility of fluorine-containing acrylate polymers are
higher than that of non-fluorinated ones [23]. Gel formation in
the case of acrylate derivatives took place, presumably because
radical chain transfer reaction frequently took place at the
protons of acrylate moiety and cyclic groups in ester groups.
8
AIBN
AIBN
BPO
34
0
6.9
–
9
Toluene
Toluene
Toluene
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Gel
62
Gel
66
Gel
48
11
47
0
–
–
BPO
0.06
–
–
AIBN
AIBN
BPO
–
0.08
–
–
TPA
–
AIBN
BPO
0.45
0.69
0.12
–
2.2
3.9
2.0
–
EtMA
BPO
Toluene
Toluene
AIBN
BPO
4. Conclusion
IPMA
66
61
67
48
73
14
49
45
54
70
0
0.82
0.74
0.53
0.85
0.46
0.23
0.05
0.17
0.51
0.68
–
4.1
2.2
2.6
4.3
2.1
2.7
–
BPO
Facile method to prepare polymers of fluoroalkyl acrylates
and methacrylates was developed by starting from syntheses of
fluorinated alcohols derived from radical addition of perfluor-
oisopropenyl ester with alcohols followed by the reaction with
acryloyl chloride or methacryloyl chloride and then polymer-
ization under radical conditions. Fluorinated alcohols posses-
sing cyclic structures were also obtained by the reaction of
BPFP with cyclic ethers followed by hydrolysis. Polyacrylates
and polymethacrylates possessing cyclic structures in fluor-
oalkyl groups were easily obtained. The reaction may be
applicable to syntheses of a-trifluoromethylacrylate derivatives
AIBN
BPO
TFMA
DLMA
TPMA
AIBN
AIBN
BPO
Toluene
AIBN
AIBN
BPO
–
Toluene
Toluene
1.3
6.2
–
BPO
AIBN
15
0.11
1.6
a
Reaction temp.: AIBN 60 8C; BPO 80 8C.
Estimated by SEC (PSt standards, eluent: THF).
b

970
T. Narita et al. / Journal of Fluorine Chemistry 128 (2007) 965–970
[7] R.D. Chambers, B. Grievson, J. Chem. Soc., Perkin. Trans. 1 (1985) 2215–
2218.
possessing cyclic structures in ester alkyl groups which would
be one of the leading candidates for resist material for
lithography [24].
[8] R.D. Chambers, S.L. Jones, S.J. Mullins, A. Swales, P. Telford, M.L.H.
West, in: J.C. Welch (Ed.), ACS Symposium Series 456, ACS, Washington
DC, 1991, Chapter 5.
Acknowledgments
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1309.
This work was financially supported in part by the ‘‘High-
Tech Research Center’’ Project, 1999–2008, of Saitama
Institute of Technology: matching fund subsidy founded
partially supported by the Ministry of Education, Culture,
Sports, Science and Technology of Japan, which the authors are
grateful. Technical support from Hirotada Fujiwara on his
excellent contribution in experiments is also acknowledged.
[12] H. Muramatsu, K. Inukai, T. Ueda, Bull. Chem. Soc. Jpn. 40 (1967) 903–
907.
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