U.S. patent application number 13/302824 was filed with the patent office on 2012-03-15 for fluorocompound having highly fluorinated norbornane structure, fluoropolymer, and their production processes.
This patent application is currently assigned to ASAHI GLASS COMPANY LIMITED. Invention is credited to Yasuhisa MATSUKAWA, Eisuke MUROTANI, Daisuke SHIRAKAWA, Naoko SHIROTA, Yoko TAKEBE.
Application Number | 20120065347 13/302824 |
Document ID | / |
Family ID | 38923156 |
Filed Date | 2012-03-15 |
United States Patent
Application |
20120065347 |
Kind Code |
A1 |
MATSUKAWA; Yasuhisa ; et
al. |
March 15, 2012 |
FLUOROCOMPOUND HAVING HIGHLY FLUORINATED NORBORNANE STRUCTURE,
FLUOROPOLYMER, AND THEIR PRODUCTION PROCESSES
Abstract
The present invention provides novel polymers obtained by
polymerizing a compound of formula (1) which has a highly
fluorinated norbornane structure. The invention also provides
compounds represented by formulas (3) and (3A-1) below, as
##STR00001## well as the following compounds: ##STR00002##
Inventors: |
MATSUKAWA; Yasuhisa;
(Chiyoda-ku, JP) ; SHIRAKAWA; Daisuke;
(Chiyoda-ku, JP) ; MUROTANI; Eisuke; (Chiyoda-ku,
JP) ; SHIROTA; Naoko; (Chiyoda-ku, JP) ;
TAKEBE; Yoko; (Chiyoda-ku, JP) |
Assignee: |
ASAHI GLASS COMPANY LIMITED
Tokyo
JP
|
Family ID: |
38923156 |
Appl. No.: |
13/302824 |
Filed: |
November 22, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12351905 |
Jan 12, 2009 |
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13302824 |
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PCT/JP07/63401 |
Jul 4, 2007 |
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12351905 |
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Current U.S.
Class: |
526/245 ;
560/120; 562/849; 568/374 |
Current CPC
Class: |
C07C 29/143 20130101;
C07C 69/753 20130101; C07C 29/143 20130101; C07C 29/143 20130101;
C07C 29/147 20130101; C07C 67/14 20130101; C07C 31/44 20130101;
C08F 220/24 20130101; C07C 29/147 20130101; C07C 29/147 20130101;
C07C 45/54 20130101; C07C 67/14 20130101; C07C 31/44 20130101; C07C
35/52 20130101; C07C 31/44 20130101; C07C 49/477 20130101; C07C
35/52 20130101; C07C 35/52 20130101; C07C 49/477 20130101; C07C
61/40 20130101; C07C 69/653 20130101; C07C 2602/42 20170501; C07C
45/54 20130101; C07C 69/653 20130101 |
Class at
Publication: |
526/245 ;
568/374; 560/120; 562/849 |
International
Class: |
C08F 120/68 20060101
C08F120/68; C07C 69/753 20060101 C07C069/753; C07C 53/50 20060101
C07C053/50; C07C 49/477 20060101 C07C049/477 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 11, 2006 |
JP |
2006-190484 |
Claims
1. A polymer obtained by polymerizing a compound of formula (1):
##STR00040## wherein: Z.sup.A, Z.sup.B, Z.sup.C, Z.sup.D, and
Z.sup.E each independently represent --CH(--OC(O)CT=CH.sub.2)--,
--CF (--CHOC(O)CT=CH.sub.2)-- or --CR.sup.AR.sup.B--, provided that
at least one of Z.sup.A to Z.sup.E is --CH(--OC(O)CT=CH.sub.2)-- or
--CF(--CH.sub.2OC(O)CT=CH.sub.2)--, and at least one of Z.sup.A to
Z.sup.E is --CR.sup.AR.sup.B--, wherein T is a hydrogen atom, a
fluorine atom, a C.sub.1-3 alkyl group or a C.sub.1-3 fluoroalkyl
group, and each of R.sup.A and R.sup.B is independently a fluorine
atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group comprising an etheric oxygen atom; W.sup.A and
W.sup.B each independently represent a fluorine atom, a C.sub.1-16
perfluoroalkyl group or a C.sub.1-16 perfluoroalkyl group
comprising an etheric oxygen atom; and n is 0, 1 or 2.
2. The polymer of claim 1, wherein a molecular weight of the
polymer is from 1.times.10.sup.3 to 1.times.10.sup.7.
3. The polymer of claim 1, wherein the polymer is a copolymer
obtained by copolymerizing the compound of formula (1) with at
least one other monomer.
4. The polymer of claim 3, wherein the polymer comprises from 0.1
to 99.9 mol % of repeating units of the compound of formula (1) and
from 0.1 to 99.9 mol % of repeating units of the at least one other
monomer, based on an entirety of repeating units.
5. The polymer of claim 3, wherein the polymer comprises at least
50 to 99.9 mol % of repeating units of the compound of formula (1)
and less than 0.1 to 50 mol % of repeating units of the at least
one other monomer, based on an entirely of repeating units.
6. The polymer of claim 3, wherein the at least one other monomer
is at least one selected from the group consisting of a
(meth)acrylate, an unsaturated carboxylic amide, a styrene, a
vinylsilane, an olefin, a fluoroolefin, a chloroolefin, a vinyl
ester, a vinyl ether, (meth)acrylic acid, and acrylonitrile.
7. The polymer of claim 1, wherein the polymer is a homopolymer
made of only repeating units of the compound of formula (1) and
having a weight average molecular weight of from 1,000 to
50,000.
8. A compound of formula (3): ##STR00041## wherein: X.sup.A,
X.sup.B, X.sup.C, X.sup.D and X.sup.E each independently represent
--C(O)--, --CF(C(O)G)- or --CR.sup.AR.sup.B--, provided that at
least one of X.sup.A to X.sup.E is --C(O)-- or --CF(--C(O)G)-, and
at least one of X.sup.A to X.sup.E is --CR.sup.AR.sup.B--, wherein
G is a halogen atom or a C.sub.1-10 alkoxy group, and each of
R.sup.A and R.sup.B is independently a fluorine atom, a C.sub.1-16
perfluoroalkyl group or a C.sub.1-16 perfluoroalkyl group
comprising an etheric oxygen atom; W.sup.A and W.sup.B each
independently represent a fluorine atom, a C.sub.1-16
perfluoroalkyl group or a C.sub.1-16 perfluoroalkyl group
comprising an etheric oxygen atom; and n is 0, 1 or 2.
9. The compound of claim 8, wherein each of X.sup.C, X.sup.D and
X.sup.E represent --CR.sup.AR.sup.B-- or each of XB, XD and XE
represent --CR.sup.AR.sup.B--.
10. The compound of claim 8, wherein X.sup.A is --C(O)-- and each
of X.sup.B, X.sup.C, X.sup.D and X.sup.E is
--CR.sup.AR.sup.B--.
11. The compound of claim 8, wherein X.sup.A is --CF(--C(O)G)- and
each of X.sup.B, X.sup.C, X.sup.D and X.sup.E is
--CR.sup.AR.sup.B--.
12. The compound of claim 8, wherein G is a fluorine atom or a
methoxy group.
13. The compound of claim 8, wherein R.sup.A and R.sup.B are both
fluorine atoms or C.sub.1-16 perfluoroalkyl groups, or one of them
is a fluorine atom and the other is a C.sub.1-16 perfluoroalkyl
group.
14. The compound of claim 8, wherein when Z.sup.E is
--CR.sup.AR.sup.B-- then Z.sup.E is --CF.sub.2-- or
--C(CF.sub.3).sub.2--.
15. The compound of claim 8, wherein W.sup.A and W.sup.B are both
fluorine atoms, or one of them is a fluorine atom and the other is
a trifluoromethyl group.
16. A compound of formula (3A-1): ##STR00042## wherein: X is
--C(O)--, --CF(C(O)F)-- or --CF(C(O)OCH.sub.3)--; R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 each independently represent a fluorine atom or
a C.sub.1-16 perfluoroalkyl group; and W.sup.1 and W.sup.2 each
independently represent a fluorine atom or a trifluoromethyl
group.
17. The compound of claim 16, wherein R.sup.3 and R.sup.4 each
represent a fluorine atom, or one of them is a fluorine atom and
the other is a fluorine atom or a C.sub.1-16 perfluoroalkyl
group.
18. The compound of claim 16, wherein W.sup.1 and W.sup.2 each
represent a fluorine atom, or one of them is a fluorine atom and
the other is a trifluoromethyl group.
19. A compound selected from the group consisting of ##STR00043##
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 12/351,905 filed Jan. 12, 2009, which is a continuation of
PCT/JP2007/063401 filed Jul. 4, 2007 and claims priority from
Japanese Application No. 2006-190484 filed Jul. 11, 2006.
BACKGROUND OF THE INVENTION TECHNICAL FIELD
[0002] The present invention relates to a novel compound having a
highly fluorinated norbornane structure, a fluoropolymer obtained
from the compound, and their production processes.
BACKGROUND ART
[0003] A polymerizable fluorocompound is useful as a monomer for
producing a fluoropolymer excellent in physical properties such as
transparency, water and oil repellency, heat resistance, mold
releasability or chemical resistance. For example, a (meth)acrylate
(in the present specification, a (meth)acrylate is a collective
term of an acrylate and a methacrylate) having a polyfluoroalkyl
group is useful as a monomer for producing a fluoropolymer to be
used as an antifouling agent, a water and oil repellent, a mold
lubricant, etc.
[0004] In order to improve the physical properties of the above
fluoropolymer, various polymerizable fluorocompounds are reported.
For example, the following compound wherein an acyclic
perfluoroalkyl group portion and a CH.sub.2.dbd.CClC(O)O-- portion
are connected via a norbornane structure, is reported (cf. Patent
Document 1):
##STR00003## [0005] Patent Document 1: JP-A-2005-272741
OBJECT OF THE INVENTION
[0006] However, a polymerizable fluorocompound having a highly
fluorinated norbornane structure and its production process have
been unknown. Further, a polymer obtained from such a
fluorocompound and physical properties of such a polymer have also
been unknown.
[0007] The object of the present invention is to provide a novel
polymerizable polyfluoronorbornane derivative and its production
process, a novel polymer obtained by polymerizing the polymerizable
polyfluoronorbornane derivative, and an intermediate useful for the
production of the fluorocompound.
BRIEF SUMMARY OF THE INVENTION
[0008] The present invention has been made as a result of extensive
studies to accomplish the above object, and it provides the
followings:
1. A compound represented by the following formula (1):
##STR00004##
wherein the symbols in the formula have the following meanings:
[0009] Z.sup.A, Z.sup.B, Z.sup.C, Z.sup.D, and Z.sup.E: each of
them is independently --CH(--OC(O)CT=CH.sub.2)--,
--CF(--CH.sub.2OC(O)CT=CH.sub.2)-- or --CR.sup.AR.sup.B--, provided
that at least one of Z.sup.A to Z.sup.E is
--CH(--OC(O)CT=CH.sub.2)-- or --CF(--CH.sub.2OC(O)CT=CH.sub.2)--,
and at least one of Z.sup.A to Z.sup.E is --CR.sup.AR.sup.B--
(wherein each of R.sup.A and R.sup.B is independently a fluorine
atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group containing an etheric oxygen atom, T is a
hydrogen atom, a fluorine atom, a C.sub.1-3 alkyl group or a
C.sub.1-3 fluoroalkyl group);
[0010] W.sup.A and W.sup.B: each of them is independently a
fluorine atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group containing an etheric oxygen atom; and
[0011] n: 0, 1 or 2.
2. A compound represented by the following formula (1A-1):
##STR00005##
wherein the symbols in the formula have the following meanings:
[0012] Z: --CH(--OC(O)CT.sup.1=CH.sub.2)-- or
--CF(--CH.sub.2OC(O)CT.sup.1=CH.sub.2)-- (wherein T.sup.1 is a
hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl
group);
[0013] W.sup.1 and W.sup.2: each of them is independently a
fluorine atom or a trifluoromethyl group; and
[0014] R.sup.1, R.sup.2, R.sup.3 and R.sup.4: each of them is
independently a fluorine atom or a C.sub.1-16 perfluoroalkyl
group.
3. A compound selected from either one of compounds represented by
the following formulae:
##STR00006##
wherein T.sup.1 represents a hydrogen atom, a fluorine atom, a
methyl group or a trifluoromethyl group. 4. A process for producing
a compound represented by the following formula (1), which
comprises reacting a compound represented by the following formula
(2) with a compound represented by CH.sub.2.dbd.CTC(O)J:
##STR00007##
wherein the symbols in the formulae have the following
meanings:
[0015] Y.sup.A, Y.sup.B, Y.sup.C, Y.sup.D, and Y.sup.E: each of
them is independently --CH(--OH)--, --CF(CH.sub.2OH)-- or
--CR.sup.AR.sup.B--, provided that at least one of Y.sup.A to
Y.sup.E is --CH(OH)-- or --CF(CH.sub.2OH)--, and at least one of
Y.sup.A to Y.sup.E is --CR.sup.AR.sup.B--; and
[0016] Z.sup.A, Z.sup.B, Z.sup.C, Z.sup.D, and Z.sup.E: each of
them is independently --CH(--OC(O)CT=CH.sub.2)--, --CF
(--CHOC(O)CT=CH.sub.2)-- or --CR.sup.AR.sup.B--, provided that at
least one of Z.sup.A to Z.sup.E is --CH(--OC(O)CT=CH.sub.2)-- or
--CF(--CH.sub.2OC(O)CT=CH.sub.2)--, and at least one of Z.sup.A to
Z.sup.E is --CR.sup.AR.sup.B--; wherein Y.sup.A corresponds to
Z.sup.A, Y.sup.B to Z.sup.B, Y.sup.C to Z.sup.c, Y.sup.D to Z.sup.D
and Y.sup.E to Z.sup.E, respectively; when each of Z.sup.A to
Z.sup.E is --CH(--OC(O)CT=CH.sub.2)--, each of Y.sup.A to Y.sup.E
is --CH(OH)--; when each of Z.sup.A to Z.sup.E is
--CF(--CH.sub.2OC(O)CT=CH.sub.2)--, each of Y.sup.A to Y.sup.E is
--CF(CH.sub.2OH)--; and when each of Z.sup.A to Z.sup.E is
--CR.sup.AR.sup.B--, each of Y.sup.A to Y.sup.E is
--CR.sup.AR.sup.B--; each of R.sup.A and R.sup.B is independently a
fluorine atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group containing an etheric oxygen atom; and T is a
hydrogen atom, a fluorine atom, a C.sub.1-3 alkyl group or a
C.sub.1-3 fluoroalkyl group;
[0017] W.sup.A and W.sup.E: each of them is independently a
fluorine atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group containing an etheric oxygen atom;
[0018] J: a halogen atom; and
[0019] n: 0, 1 or 2.
5. A polymer which is obtained by polymerizing a compound
represented by the formula (1). 6. The polymer according to 5,
wherein its molecular weight is from 1.times.10.sup.3 to
1.times.10.sup.7. 7. A compound represented by the following
formula (2):
##STR00008##
wherein the symbols in the formula have the following meanings:
[0020] Y.sup.A, Y.sup.B, Y.sup.C, Y.sup.D, and Y.sup.E: each of
them is independently --CH(OH)--, --CF(CH.sub.2OH)-- or
--CR.sup.AR.sup.B--, provided that at least one of Y.sup.A to
Y.sup.E is --CH(OH)-- or --CF(CH.sub.2OH)--, and at least one of
Y.sup.A to Y.sup.E is --CR.sup.AR.sup.E-- (wherein each of R.sup.A
and R.sup.B is independently a fluorine atom, a C.sub.1-16
perfluoroalkyl group or a C.sub.1-16 perfluoroalkyl group
containing an etheric oxygen atom);
[0021] W.sup.A and W.sup.E: each of them is independently a
fluorine atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group containing an etheric oxygen atom; and
[0022] n: 0, 1 or 2.
8. A compound represented by the following formula (2A-1):
##STR00009##
wherein the symbols in the formula have the following meanings:
[0023] Y: --CH(OH)-- or --CF(--CH.sub.2OH)--;
[0024] R.sup.1, R.sup.2, R.sup.3 and R.sup.4: each of them is
independently a fluorine atom or a C.sub.1-16 perfluoroalkyl group;
and
[0025] W.sup.1 and W.sup.2: each of them is independently a
fluorine atom or a trifluoromethyl group.
9. A compound selected from compounds represented by the following
formulae:
##STR00010##
10. A process for producing a compound represented by the following
formula (2), which comprises subjecting a compound represented by
the following formula (3) to a reduction reaction:
##STR00011##
wherein the symbols in the formulae have the following
meanings:
[0026] X.sup.A, X.sup.B, X.sup.D and X.sup.E: each of them is
independently --C(O)--, --CF(C(O)G)- or --CR.sup.AR.sup.B--,
provided that at least one of X.sup.A to X.sup.E is --C(O)-- or
--CF(--C(O)G)-, and at least one of X.sup.A to X.sup.E is
--CR.sup.AR.sup.B--;
[0027] Y.sup.A, Y.sup.B, Y.sup.C, Y.sup.D, and Y.sup.E: each of
them is independently --CH(--OH)--, --CF (CH.sub.2OH)-- or
--CR.sup.AR.sup.B--, provided that at least one of Y.sup.A to
Y.sup.E is --CH(OH)-- or --CF(CH.sub.2OH)--, and at least one of
Y.sup.A to Y.sup.E is --CR.sup.AR.sup.B--; wherein X.sup.A
corresponds to Y.sup.A, X.sup.B to Y.sup.B, X.sup.C to Y.sup.C,
X.sup.D to Y.sup.D and X.sup.E to Y.sup.E, respectively; when each
of Y.sup.A to Y.sup.E is --CH(OH)--, each of X.sup.A to X.sup.D is
--C(O)--; when each of Y.sup.A to Y.sup.E is --CF(--CH.sub.2OH)--,
each of X.sup.A to X.sup.D is --CF(--C(O)G)-; and when each of
Y.sup.A to Y.sup.E is --CR.sup.AR.sup.B--, each of X.sup.A to
X.sup.D is --CR.sup.AR.sup.B--; each of R.sup.A and R.sup.B is
independently a fluorine atom, a C.sub.1-16 perfluoroalkyl group or
a C.sub.1-16 perfluoroalkyl group containing an etheric oxygen
atom; G is a halogen atom or a C.sub.1-10 alkoxy group;
[0028] W.sup.A and W.sup.B: each of them is independently a
fluorine atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group containing an etheric oxygen atom; and
[0029] n: 0, 1 or 2.
11. A compound represented by the following formula (3):
##STR00012##
wherein the symbols in the formula have the following meanings:
[0030] X.sup.A, X.sup.B, X.sup.C, X.sup.D and X.sup.E: each of them
is independently --C(O)--, --CF(C(O)G)- or --CR.sup.AR.sup.B--,
provided that at least one of X.sup.A to X.sup.E is --C(O)-- or
--CF(--C(O)G)-, and at least one of X.sup.A to X.sup.E is
--CR.sup.AR.sup.B-- (wherein G is a halogen atom or a C.sub.1-10
alkoxy group; and each of R.sup.A and R.sup.B is independently a
fluorine atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group containing an etheric oxygen atom);
[0031] W.sup.A and W.sup.B: each of them is independently a
fluorine atom, a C.sub.1-16 perfluoroalkyl group or a C.sub.1-16
perfluoroalkyl group containing an etheric oxygen atom; and
[0032] n: 0, 1 or 2.
12. A compound represented by the following formula (3A-1):
##STR00013##
wherein the symbols in the formula have the following meanings:
[0033] X: --C(O)--, --CF(C(O)F)-- or --CF(C(O)OCH.sub.3)--;
[0034] R.sup.1, R.sup.2, R.sup.3 and R.sup.4: each of them is
independently a fluorine atom or a C.sub.1-16 perfluoroalkyl group;
and
[0035] W.sup.1 and W.sup.2: each of them is independently a
fluorine atom or a trifluoromethyl group.
13. A compound selected from compounds represented by the following
formulae.
##STR00014##
EFFECTS OF THE INVENTION
[0036] According to the present invention, a novel polymerizable
polyfluoronorbornane derivative is provided. Further, by
polymerizing the polyfluoronorbornane derivative, it is possible to
obtain a polymer excellent in heat resistance, mold releasability,
chemical resistance, transparency, light resistance, water and oil
repellency, low refractive index property, etc. Particularly, it is
possible to obtain a fluoropolymer excellent in dynamic water and
oil repellency. Further, according to the present invention, a
novel alcohol compound and a novel carbonyl compound useful as an
intermediate for production of the polyfluoronorbornane derivative
and for other applications, are provided.
BEST MODE FOR CARRYING OUT THE INVENTION
[0037] In the present specification, a compound represented by the
formula (1) is shown as a compound (1). A group represented by
--CH(--OC(O)CT=CH.sub.2)-- is simply shown as
--CH(--OC(O)CT=CH.sub.2)--. Compounds and groups represented by
other formulae are shown in the same manner. Further, the meanings
of the symbols in a group are the same as the previous ones unless
otherwise specified.
[0038] Further, when a compound in the present invention has an
asymmetric carbon atom, the steric configuration of the carbon atom
is not particularly limited. With respect to a crosslinked cyclic
compound in the present invention, the steric configuration of the
asymmetric center on the main ring may be endo or exo. When a
carbon atom on a main bridge of the crosslinked cyclic compound of
the present invention forms an asymmetric center, the steric
configuration of the asymmetric center may be syn or anti.
[0039] The present invention provides the following novel compound
(1):
##STR00015##
[0040] Each of Z.sup.A to Z.sup.E is a divalent linking group
selected from --CH(--OC(O)CT=CH.sub.2)--,
--CF(--CH.sub.2OC(O)CT.+-.CH.sub.2)-- and --CR.sup.AR.sup.B--. Each
of 1 to 4 groups selected from Z.sup.A to Z.sup.E is
--CH(--OC(O)CT=CH.sub.2)-- or --CF(--CH.sub.2OC(O)CT=CH.sub.2)--,
and each of 1 to 4 groups selected from the rest of Z.sup.A to
Z.sup.E is --CR.sup.AR.sup.B--. Further, each of Z.sup.A to Z.sup.E
is an independent group, and they may be the same or different. For
example, when at least two of Z.sup.A to Z.sup.E are
--CH(--OC(O)CT=CH.sub.2)--, the two --CH(--OC(O)CT=CH.sub.2)-- may
be the same groups or different groups.
[0041] Further, when at least two Z.sup.Es are present in the
formula (e.g. when n is 1 or 2), Z.sup.Es may be the same or
different, and they are preferably the same.
[0042] T is preferably a hydrogen atom, a fluorine atom, a methyl
group or a trifluoromethyl group. T is particularly preferably a
hydrogen atom or a methyl group, especially preferably a methyl
group.
[0043] Each of R.sup.A and R.sup.B is independently preferably a
fluorine atom or a C.sub.1-16 perfluoroalkyl group. The C.sub.1-16
perfluoroalkyl group is preferably a C.sub.1-6 linear
perfluoroalkyl group, particularly preferably a trifluoromethyl
group. Further, it is particularly preferably a C.sub.1-16
perfluoroalkyl group wherein both of R.sup.A and R.sup.B are
fluorine atoms or C.sub.1-16 perfluoroalkyl groups, or one of them
is a fluorine atom and the other is a C.sub.1-16 perfluoroalkyl
group. That is, --CR.sup.AR.sup.B-- is preferably --CF.sub.2--,
--C(R.sup.E).sub.2-- or --CFR.sup.F--. R.sup.F means a C.sub.1-16
perfluoroalkyl group (the same applies hereinafter).
[0044] With respect to Z.sup.A to Z.sup.E, one or two of them are
preferably groups selected from --CH(--OC(O)CT=CH.sub.2)-- and
--CF(--CH.sub.2OC(O)CT=CH.sub.2)--, and the rest of three or four
of them are preferably --CR.sup.AR.sup.B--. Particularly preferred
is that one of them is --CH(--OC(O)CT=CH.sub.2)-- or
--CF(--CH.sub.2OC(O)CT=CH.sub.2)--, and the rest of four are
--CR.sup.AR.sup.B--.
[0045] Further, as Z.sup.A to Z.sup.E, the following modes are
preferred.
[0046] Z.sup.A is --CH(--OC(O)CT=CH.sub.2)-- or
--CF(--CH.sub.2OC(O)CT=CH.sub.2)--, and each of Z.sup.B to Z.sup.E
is --CR.sup.AR.sup.B--; each of Z.sup.A and Z.sup.B is
--CH(--OC(O)CT=CH.sub.2)-- or --CF(--CH.sub.2OC(O)CT=CH.sub.2)--,
and each of Z.sup.C to Z.sup.E is --CR.sup.AR.sup.B--; each of
Z.sup.A and Z.sup.C is --CH (--OC(O)CT=CH.sub.2)-- or --CF
(--CHOC(O)CT=CH.sub.2)--, and each of Z.sup.B, Z.sup.D and Z.sup.E
is --CR.sup.AR.sup.B--.
[0047] With respect to Z.sup.A to Z.sup.E, particularly preferred
is that Z.sup.A is --CH(--OC(O)CT=CH.sub.2)-- or --CF
(--CHOC(O)CT=CH.sub.2)--, and each of Z.sup.B to Z.sup.E is
--CR.sup.AR.sup.B--.
[0048] Especially, when Z.sup.E is --CR.sup.AR.sup.B--, Z.sup.E is
preferably --CF.sub.2-- or --C(R.sup.F).sub.2--, particularly
preferably --CF.sub.2-- or --C(CF.sub.3).sub.2--.
[0049] W.sup.A and W.sup.B are preferably such that each of them is
a fluorine atom, or one of them is a fluorine atom and the other is
a trifluoromethyl group.
[0050] n shows a repeating number of the structural unit enclosed
by parenthesis [ ]. When n is 0, the compound (1) is the following
compound (1A), and when n is 1, the compound (1) is the following
compound (1B). When n is 2, the compound (1) is the following
compound (1C).
[0051] n is preferably 0. That is, the compound (1) of the present
invention is preferably the following compound (1A).
##STR00016##
[0052] The steric configuration of the asymmetric center on the
main ring of the compound (1), is not particularly limited, and it
may be endo or exo. When a carbon atom on the main bridge (a carbon
atom in a group represented by Z.sup.E) of the compound (1) forms
the asymmetric center, the steric configuration of the asymmetric
center is not particularly limited, and it may be syn or anti.
[0053] Further, the compound (1A) is preferably the following
compound (1A-1), the following compound (1A-2) or the following
compound (1A-3), particularly preferably the following compound
(1A-1).
##STR00017##
[0054] Z may be --CH(--OC(O)CT.sup.1=CH.sub.2)-- or
--CF(--CH.sub.2OC(O)CT.sup.1=CH.sub.2)--. Further, two Z in the
compound (1A-2) or the compound (1A-3) may be the same or
different.
[0055] When at least two R.sup.1 and R.sup.2 are respectively
present in the formula, they may be the same or different, and they
are preferably the same. Each of R.sup.1 and R.sup.2 is preferably
a fluorine atom or a trifluoromethyl group.
[0056] R.sup.3 and R.sup.4 are preferably such that each of them is
a fluorine atom, or one of them is a fluorine atom and the other is
a fluorine atom or a C.sub.1-16 perfluoroalkyl group.
[0057] W.sup.1 and W.sup.2 are preferably such that each of them is
a fluorine atom, or one of them is a fluorine atom and the other is
a trifluoromethyl group.
[0058] T.sup.1 is preferably a hydrogen atom or a methyl group.
[0059] Specific examples of the compound (1) may be the following
compounds:
##STR00018##
[0060] The compound (1) can be produced by reacting the following
compound (2) with a compound represented by CH.sub.2.dbd.CTC(O)J.
The compound (2) will be described later.
##STR00019##
[0061] J is preferably a chlorine atom or a bromine atom.
[0062] Specific examples of the compound represented by
CH.sub.2.dbd.CTC(O)J may be CH.sub.2.dbd.CHC(O)Cl,
CH.sub.2.dbd.CHC(O)Br, CH.sub.2.dbd.C(CH.sub.3)C(O)Cl,
CH.sub.2.dbd.C(CH.sub.3)C(O)Br, CH.sub.2.dbd.CFC(O)Cl,
CH.sub.2.dbd.CFC(O)Br, CH.sub.2.dbd.C(CF.sub.3)C(O)Cl and
CH.sub.2.dbd.C(CF.sub.3)C(O)Br.
[0063] In the production of the compound (1), it is preferred to
react from 1 k to 2 k mol of the compound represented by
CH.sub.2.dbd.CTC(O)J with 1 mol of the compound (2) having k number
in total of --CH(--OH)-- and --CF(--CH.sub.2OH)-- per molecule. k
is an integer of from 1 to (4+n) (the same applies
hereinafter).
[0064] The reaction conditions (reaction temperature, reaction
pressure, reaction time, etc.) for the above reaction are not
particularly limited, and it is preferred to follow a method and
conditions known for an esterification reaction.
[0065] The compound (1) is a polymerizable compound having
--CH(--OC(O)CT=CH.sub.2)-- or --CF(--CH.sub.2OC(O)CT=CH.sub.2)--
and having a highly fluorinated norbornane structure. Therefore, a
polymer can be produced by polymerizing the compound (1).
[0066] Further, the present invention provides a polymer obtained
by polymerizing the compound (1). The polymer of the present
invention may be a homopolymer obtained by homopolymerizing the
compound (1) alone and may be a copolymer obtained by
copolymerizing the compound (1) with another monomer (hereinafter
referred to as another monomer) copolymerizable with the compound
(1). In the latter case, the polymer of the present invention
preferably contains from 0.1 to 99.9 mol % of repeating units of
the compound (1) and from 0.1 to 99.9 mol % of repeating units of
another monomer, based on the entire repeating units. Further, the
copolymer preferably contains at least 50 to 99.9 mol % of
repeating units of the compound (1) and less than 0.1 to 50 mol %
of repeating units of another monomer.
[0067] Such another monomer is not particularly limited, and it
may, for example, be a (meth)acrylate, an unsaturated carboxylic
amide, a styrene, a vinylsilane, an olefin, a fluoroolefin, a
chloroolefin, a vinyl ester, a vinyl ether, (meth)acrylic acid or
acrylonitrile.
[0068] Specific examples of the (meth)acrylate may be an acyclic
alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl
(meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
isooctyl (meth)acrylate, isononyl (meth)acrylate, decyl
(meth)acrylate, octadecyl (meth)acrylate, diethylaminoethyl
(meth)acrylate, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl
(meth)acrylate; and an acyclic alkyl (meth)acrylate such as
1-adamantyl (meth)acrylate, 3-hydroxyl-1-adamantyl (meth)acrylate,
2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl
(meth)acrylate, 2-propyl-2-adamantyl (meth)acrylate,
2-butyl-2-adamantyl (meth)acrylate, 2-oxotetrahydrofuran-3-yl
(meth)acrylate, glycidyl (meth)acrylate or benzyl
(meth)acrylate.
[0069] Specific examples of the unsaturated carboxylic amide may be
acrylamide, diamide itaconate, .alpha.-ethyl acrylamide, amide
crotonate, diamide fumarate, diamide maleate, N-buthoxymethyl
acrylamide and N-methylol-acrylamide.
[0070] Specific examples of the styrene may be styrene,
.alpha.-methylstyrene, chlorostyrene and hydroxystyrene.
[0071] Specific examples of the vinylsilane may be vinyl methyl
dimethoxysilane, vinyl methyl diethoxysilane, vinyl methyl
dichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane and
vinyl trichlorosilane.
[0072] Specific examples of the olefin may be ethylene, propylene
and isobutylene.
[0073] Specific examples of the fluoroolefin may be an acyclic
fluoromonoene such as vinyl fluoride, vinylidene fluoride,
tetrafluoroethylene or hexafluoropropylene; a cyclic fluoromonoene
such as perfluoro(2,2-dimethyl-1,3-dioxole) or
perfluoro(2-methylene-1,3-dioxolane); and a fluorodiene such as
CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CF.dbd.CF.sub.2,
CF.sub.2.dbd.CFOCF.sub.2CF(CF.sub.3)CF.dbd.CF.sub.2,
CF.sub.2.dbd.CFOCF(CF.sub.3)CF.sub.2CF.dbd.CF.sub.2,
CF.sub.2.dbd.CFCF.sub.2C(CF.sub.3)(OH)CH.sub.2CH.dbd.CH.sub.2 or
CF.sub.2.dbd.CFCH.sub.2CH(C(CF.sub.3).sub.2OH)CH.sub.2CH.dbd.CH.sub.2.
[0074] Specific examples of the chloroolefin may be vinyl chloride,
vinylidene chloride and chloroprene.
[0075] Specific examples of the vinyl ester may be vinyl acetate
and vinyl propionate.
[0076] Specific examples of the vinyl ether may be 2-hydroxyvinyl
ether and aminoethyl vinyl ether.
[0077] The polymerization of the compound (1) is preferably carried
out in the presence of a polymerization initiator. Specific
examples of the polymerization initiator may be an organic peroxide
such as (C.sub.6H.sub.5C(O)O--).sub.2,
(C.sub.6F.sub.5C(O)O--).sub.2, (C.sub.3F.sub.7C(O)O--).sub.2,
((CH.sub.3).sub.3CC(O)--).sub.2r ((CH.sub.3).sub.2CHC(O)O--).sub.2,
((CH.sub.3).sub.3C(O)C(O)O--).sub.2, ((CH.sub.3).sub.3C
(O)--).sub.2, ((CH.sub.3).sub.2CHOC(O)O--).sub.2 or
((CH.sub.3).sub.3CC.sub.6H.sub.10OC(O)O--).sub.2, an azo compound
such as azobisisobutyronitrile, and an inorganic peroxide.
[0078] The polymerization conditions (polymerization temperature,
polymerization pressure, etc.) in the polymerization of the
compound (1) are not particularly limited. The polymerization
temperature is preferably from 0 to 200.degree. C. The
polymerization pressure is preferably from atmospheric pressure to
10 MPa (gauge pressure).
[0079] The weight average molecular weight of the polymer of the
present invention is preferably from 1.times.10.sup.3 to
1.times.10.sup.7, more preferably from 1.times.10.sup.3 to
1.times.10.sup.5.
[0080] The polymer of the present invention is a polymer excellent
in transparency, water and oil repellency, heat resistance, mold
releasability, chemical resistance and particularly dynamic water
repellency. The polymer of the present invention is useful as an
antifouling agent, a water and oil repellent, a mold lubricant, an
optical fiber material, a pellicle material, a lens material, a
surface protecting material for a display.
[0081] Further, the preferred mode of the polymer of the present
invention may be a polymer which is obtained by homopolymerizing
the compound (1) alone, and which is made of only repeating units
of the compound (1) and has a weight average molecular weight of
from 1,000 to 50,000. The repeating units in the present
specification mean units formed by polymerization of a
polymerizable compound such as the compound (1).
[0082] The following compound (2) as an intermediate for production
of the compound (1) is a novel compound having a hydroxyl group or
a hydroxymethyl group and having a highly fluorinated norbornane
structure. In addition to being useful as an intermediate for
production of the compound (1), the compound (2) can be converted
to various derivatives by utilizing the reactivity of hydroxyl
groups in Y.sup.A to Y.sup.E. Since every converted compound has a
highly fluorinated norbornane structure, the compound exhibits
performance such as water and oil repellency, which is derived from
the structure. That is, the present invention provides the
following novel compound (2).
##STR00020##
[0083] Y.sup.A, Y.sup.B, Y.sup.C, Y.sup.D and Y.sup.E are as
defined above, and their preferred modes are as follows.
[0084] Y.sup.A is --CH(OH)-- or --CF(--CH.sub.2OH)--, and each of
Y.sup.B, Y.sup.C, Y.sup.D and Y.sup.E is --CR.sup.AR.sup.B--; each
of Y.sup.A and Y.sup.B is --CH(--OH)-- or --CF (--CH.sub.2OH)--,
and each of Y.sup.C, Y.sup.D and Y.sup.E is --CR.sup.AR.sup.B--;
and each of Y.sup.A and Y.sup.C is --CH(--OH)-- or --CF
(--CH.sub.2OH)--, and each of Y.sup.B, Y.sup.D and Y.sup.E is
--CR.sup.AR.sup.B--.
[0085] Further, it is particularly preferred that Y.sup.A is
--CH(OH)-- or --CF(--CH.sub.2OH)--, and each of Y.sup.B, Y.sup.C,
Y.sup.D and Y.sup.E is --CR.sup.AR.sup.B--.
[0086] Here, R.sup.A and R.sup.B are as defined above, and they may
be the same or different. Each of R.sup.A and R.sup.B is
independently preferably a fluorine atom or a C.sub.1-16
perfluoroalkyl group. Particularly preferred is that both of them
are fluorine atoms or C.sub.1-16 perfluoroalkyl groups, or that one
of them is a fluorine atom, and the other is a C.sub.1-16
perfluoroalkyl group. That is, --CR.sup.AR.sup.B-- is preferably
--CF.sub.2--, --C(R.sup.F).sub.2-- or --CFR.sup.F--.
[0087] When Z.sup.E is --CR.sup.AR.sup.B--, Z.sup.E preferably
--CF.sub.2-- or --C(R.sup.F).sub.2--, particularly preferably
--CF.sub.2-- or --C(CF.sub.3).sub.2--.
[0088] W.sup.A and W.sup.B are independent of each other, and they
may be the same or different. When at least two W.sup.As are
present in a molecule, they may be the same or different. The same
applies to W.sup.B. W.sup.A and W.sup.B are preferably such that
each of them is a fluorine atom, or one of them is a fluorine atom
and the other is a trifluoromethyl group.
[0089] n has the same meaning as above, and n is preferably 0. When
n is 0, the compound (2) is the following compound (2A), and when n
is 1, the compound (2) is the following compound (2B). When n is 2,
the compound (2) is the following compound (2C).
##STR00021##
[0090] The steric configuration of the asymmetric center on the
main ring of the compound (2) is not particularly limited, and it
may be endo or exo. When a carbon atom on the main bridge (a carbon
atom in a group represented by Y.sup.E) of the compound (2) forms
the asymmetric center, the steric configuration of the symmetric
center is not particularly limited, and it may be syn or anti.
[0091] The compound (2) is preferably the following compound
(2A-1), the following compound (2A-2) or the following compound
(2A-3), particularly preferably the following compound (2A-1).
##STR00022##
[0092] Y is --CH(OH)-- or --CF(--CH.sub.2OH)--. Two Ys in the
compound (2A-2) or the compound (2A-2) may be the same or
different.
[0093] Each of R.sup.1 and R.sup.2 is preferably a fluorine atom or
a trifluoromethyl group.
[0094] R.sup.3 and R.sup.4 are preferably such that each of them is
a fluorine atom, or one of them is a fluorine atom and the other is
a fluorine atom or a C.sub.1-16 perfluoroalkyl group.
[0095] W.sup.1 and W.sup.2 are preferably such that each of them is
a fluorine atom, or one of them is a fluorine atom and the other is
a trifluoromethyl group.
[0096] Specific examples of the compound (2) may be the following
compounds.
##STR00023##
[0097] The compound (2) can be produced by subjecting the following
compound (3) to a reduction reaction. The detail of the compound
(3) will be described later.
##STR00024##
[0098] The reduction reaction of the compound (3) is preferably
carried out by a reaction between the compound (3) with a reducing
agent. The reducing agent is not particularly limited, and it is
preferably NaBH.sub.4, a tetrahydrofuran solution of
B.sub.2H.sub.6, a hexane solution of
((CH.sub.3).sub.2CHCH.sub.2).sub.2AlH, or LiAlH.sub.4.
[0099] The reduction reaction is preferably carried out by reacting
from 1 k to 2 k mol of the reducing agent with 1 mol of the
compound (3) having k number in total of --C(O)-- and
--CF(--C(O)G)- in one molecule.
[0100] The reaction conditions (reaction temperature, reaction
pressure, reaction time, etc.) for the reduction reaction are not
particularly limited. For example, it is preferably carried out in
accordance with a method described in a paragraph 0021 of
JP-A-10-72568, wherein acyl fluoride (--COF) is esterified to
methyl ester (--COOCH.sub.3) or the like, followed by reduction
with NaBH.sub.4, to obtain an alcohol (--CH.sub.2OH).
[0101] The compound (3) is a novel compound having --C(O)-- or
--CF(--C(O)G)- and a highly fluorinated norbornane structure. The
compound (3) is useful e.g. as an intermediate for production of
the compound (2). That is, the present invention provides the
following novel compound (3).
##STR00025##
[0102] X.sup.A, X.sup.B, X.sup.C, X.sup.D and X.sup.E are as
defined above, and the following modes are preferred. That is,
X.sup.A is --C(O)-- or --CF(--C(O)G)-, and each of X.sup.B,
X.sup.C, X.sup.D and X.sup.E is --CR.sup.AR.sup.B--; each of
X.sup.A and X.sup.B is --C(O)-- or --CF(--C(O)G)-, and each of
X.sup.C, X.sup.D and X.sup.E is --CR.sup.AR.sup.B--; each of
X.sup.A and X.sup.C is --C(O)-- or --CF(--C(O)G)-, and each of
X.sup.B, X.sup.D and X.sup.E is --CR.sup.AR.sup.B--. Further,
particularly preferred is that X.sup.A is --C(O)-- or
--CF(--C(O)G)-, and that each of X.sup.B, X.sup.C, X.sup.D and
X.sup.E is --CR.sup.AR.sup.B--.
[0103] G is preferably a fluorine atom or a C.sub.1-10 alkoxy
group, particularly preferably a fluorine atom or a methoxy
group.
[0104] Each of R.sup.A and R.sup.B is independently preferably a
fluorine atom or a C.sub.1-16 perfluoroalkyl group. Particularly
preferred is that both of them are fluorine atoms or C.sub.1-16
perfluoroalkyl groups, or that one of them is a fluorine atom, and
the other is a C.sub.1-16 perfluoroalkyl group. That is,
--CR.sup.AR.sup.B-- is preferably --CF.sub.2--,
--C(R.sup.F).sub.2-- or --CFR.sup.F--. Here, R.sup.F means a
C.sub.1-16 perfluoroalkyl group.
[0105] When Z.sup.E is --CR.sup.AR.sup.B--, Z.sup.E is preferably
--CF.sub.2-- or --C(R.sup.F).sub.2--, particularly preferably
--CF.sub.2-- or --C(CF.sub.3).sub.2--.
[0106] W.sup.A and W.sup.B are preferably such that each of them is
a fluorine atom, or one of them is a fluorine atom and the other is
a trifluoromethyl group.
[0107] n has the same meaning as above. n is preferably 0. When n
is 0, the compound (3) is the following compound (3A), and when n
is 1, the compound (3) is the following compound (3B). When n is 2,
the compound (3) is the following compound (3C).
##STR00026##
[0108] The steric configuration of the asymmetric center on the
main ring of the compound (3) is not particularly limited, and it
may be endo or exo. When a carbon atom on the main bridge (a carbon
atom in a group represented by X.sup.E) of the compound (3) forms
the asymmetric center, the steric configuration of the symmetric
center is not particularly limited, and it may be syn or anti.
[0109] The compound (3) is preferably the following compound
(3A-1), the following compound (3A-2) or the following compound
(3A-3), particularly preferably the following compound (3A-1).
##STR00027##
[0110] X is --C(O)--, --CF(--C(O)F)-- or --CF(--C(O)OCH.sub.3)--.
Two Xs in the compound (3A-2) or in the compound (3A-3) may be the
same or different.
[0111] Each of R.sup.1 and R.sup.2 is preferably a fluorine atom or
a trifluoromethyl group.
[0112] R.sup.3 and R.sup.4 are preferably such that each of them is
a fluorine atom, or one of them is a fluorine atom and the other is
a fluorine atom or a C.sub.1-16 perfluoroalkyl group.
[0113] W.sup.1 and W.sup.2 are preferably such that each of them is
a fluorine atom, or one of them is a fluorine atom and the other is
a trifluoromethyl group.
[0114] Specific examples of the compound (3) may be the following
compounds.
##STR00028##
[0115] The compound (3) can be produced in such a manner that the
following compound (6) and a compound represented by R.sup.f--C(O)F
are subjected to an esterification reaction to obtain the following
compound (5), and then, the compound (5) is subjected to a
fluorination reaction to obtain the following compound (4),
followed by a thermal decomposition reaction of the compound (4),
in the presence of an alkali metal fluoride. Further, it can also
be produced by reacting the compound (4) with a C.sub.1-10
alkanol.
##STR00029##
wherein the symbols in the formulae have the following
meanings:
[0116] Each of X.sup.FA, X.sup.FB, X.sup.FC, X.sup.FD and X.sup.FE:
--CF(--OC(O)R.sup.f)--, --CF(--CF.sub.2OC(O)R.sup.f)-- or
--CR.sup.AR.sup.B--. However, X.sup.FA is a group corresponding to
X.sup.A, X.sup.FB to X.sup.B, X.sup.FC to X.sup.C, X.sup.FD to
X.sup.D and X.sup.FE to X.sup.E, respectively; a group
corresponding to --C(O)-- is --CF(--OC(O)R.sup.f)--, a group
corresponding to --C(--C(O)G)- is --CF(--CF.sub.2OC(O)R.sup.f)--,
and a group corresponding to --CR.sup.AR.sup.B-- is
--CR.sup.AR.sup.B--.
[0117] Each of X.sup.HA, X.sup.HB, X.sup.HC, X.sup.HD and X.sup.HE:
--CH(OC(O)R.sup.f)--, --CH (--CH.sub.2OC(O)R.sup.f-- or
--CR.sup.HAR.sup.HB--. However, X.sup.HA is a group corresponding
to X.sup.FA, X.sub.HB to X.sup.FB. X.sup.HC to X.sup.FC, X.sup.HD
to X.sup.FD and X.sup.HE to X.sup.FE, respectively; a group
corresponding to --CF(--OC(O)R.sup.f)-- is --CH(--OC(O)R.sup.f)--,
a group corresponding to --CF(CF.sub.2OC(O)R.sup.f)-- is
--CH(--CH.sub.2OC(O)R.sup.f)--, and a group corresponding to
--CR.sup.HAR.sup.HB-- is --CR.sup.HAR.sup.HB--. Further, between
X.sup.HC and X.sup.HD, a carbon atom-carbon atom double bond may be
formed.
[0118] Each of X.sup.LA, X.sup.LB, X.sup.LC, X.sup.LD and X.sup.LE:
--CH(--OH)--, --CH(--CH.sub.2OH)-- or --CR.sup.HAR.sup.HB--.
However, X.sup.LA is a group corresponding to X.sup.HA, X.sup.LB to
X.sup.HB, X.sup.LC to X.sup.HC, X.sup.LD to X.sup.HD and X.sup.LE
to X.sup.HE, respectively; a group corresponding to
--CH(--OC(O)R.sup.f)-- is --CH(OH)--, a group corresponding to
--CH(--CH.sub.2OC(O)R.sup.f)-- is --CH(--CH.sub.2OH)-- and a group
corresponding to --CR.sup.HAR.sup.HB-- is --CR.sup.HAR.sup.HA--.
Further, a carbon-carbon bond between X.sup.LC and X.sup.LD may be
a double bond.
[0119] Each of W.sup.HA and W.sup.HB: a hydrogen atom, a C.sub.1-16
alkyl group or a C.sub.1-16 alkyl group containing an etheric
oxygen atom. However, W.sup.HA is a group corresponding to WA,
W.sup.HB to W.sup.B; a group corresponding to a fluorine atom is a
hydrogen atom; a group corresponding to a C.sub.1-16 perfluoroalkyl
group is a C.sub.1-16 alkyl group; a group corresponding to a
C.sub.1-16 perfluoroalkyl group containing an etheric oxygen atom
is a C.sub.1-16 alkyl group containing an etheric oxygen atom.
[0120] Each of R.sup.HA and R.sup.HB: a hydrogen atom, a C.sub.1-16
alkyl group or a C.sub.1-16 alkyl group containing an etheric
oxygen atom. However, R.sup.HA is a group corresponding to R.sup.A,
R.sup.HB to R.sup.B, R.sup.HC to R.sup.C, R.sup.HD to R.sup.D and
R.sup.ED to R.sup.E, respectively; a group corresponding to a
fluorine atom is a hydrogen atom; a group corresponding to a
C.sub.1-16 perfluoroalkyl group is a C.sub.1-16 alkyl group; and a
group corresponding to a C.sub.1-16 perfluoroalkyl group containing
an etheric oxygen atom is a C.sub.1-16 alkyl group containing an
etheric oxygen atom.
[0121] R.sup.f: a C.sub.1-20 perfluoroalkyl group or a C.sub.1-20
perfluoroalkyl group containing an etheric oxygen atom.
[0122] Specific examples of the compound (6) may be the following
compounds. The compound (6) is a known compound or a compound
obtainable by a known method.
##STR00030##
[0123] Specific examples of the compound represented by
R.sup.f--C(O)F may be CF.sub.3C(O)F, (CF.sub.3).sub.2CFC(O)F, F
(CF.sub.2).sub.3OCF (CF.sub.3)C(O)F and F (CF.sub.2).sub.3OCF
(CF.sub.3)CF.sub.2OCF(CF.sub.3)C(O)F.
[0124] Specific examples of the compound (5) may be the following
compounds.
##STR00031##
[0125] Specific examples of the compound (4) may be the following
compounds.
##STR00032##
[0126] The respective reaction conditions for an esterification
reaction of the compound (6) with the compound represented by
R.sup.f--C(O)F, a fluorination reaction of the compound (5) and a
thermal decomposition reaction of the compound (4), are preferably
the reaction conditions described in WO00/56694, WO02/18314,
etc.
[0127] According to the present invention, a novel polymerizable
compound and polymer can be provided. The polymer of the present
invention has a structure wherein a highly fluorinated norbornane
structure is hanged on a side chain, whereby the polymer exhibits
excellent water and oil repellency, heat resistance, mold
releasability, chemical resistance, transparency, durability, light
resistance and low refractive index property. The polymer provided
by the present invention is particularly excellent in dynamic water
and oil repellency, especially excellent in dynamic water
repellency, and that is, it is a polymer having an excellent
property such that the contact angle with water is at least
80.degree., and the sliding angle is at most 20.degree.. The
polymer of the present invention is useful for various
applications, in which such properties are required.
EXAMPLES
[0128] In Examples, 1,1,2-trichloro-1,2,2-trifluoroethane is shown
as R113, dichloropentafluoropropane as R225, tetrahydrofuran as
THF, and tetramethylsilane as TMS. As R225, a mixture of
CF.sub.3CF.sub.2CHCl.sub.2 and CF.sub.2ClCF.sub.2CHFCl, was
used.
Example 1
Production Example of Compound (31)
[0129] By following a production route represented by the following
formula, a compound (31) was produced from the following compound
(61). Here, a compound represented by R.sup.f1--COF is
F(CF.sub.2).sub.3OCF (CF.sub.3)CF.sub.2OCF(CF.sub.3)C(O)F.
##STR00033##
[0130] Into a flask under a nitrogen gas atmosphere, 15 g of the
compound (61), 100 g of chloroform and 7.02 g of NaF were
introduced, and while inside of the flask was cooled with ice and
was stirred, 79 g of the compound represented by R.sup.f1--COF was
dropwise added thereto. After inside of the flask was further
stirred, an insoluble solid in the content of the flask was removed
by pressure filtration. Into the content of the flask, 103 g of
saturated sodium hydrogen carbonate aqueous solution was added. An
organic layer of the formed two-layer separated liquid was
recovered. The recovered organic layer was concentrated to obtain
74 g of a compound (51).
[0131] Then, into an autoclave (made of nickel, inner volume: 500
mL) having a NaF pellet packed bed set at a gas outlet, 313 g of
R113 was added, and while stirring inside of the autoclave at
25.degree. C., nitrogen gas was blown into the autoclave for 1
hour. Further, fluorine gas diluted to 20% volume with nitrogen gas
(hereinafter referred to as 20% fluorine gas) was blown
therein.
[0132] While the 20% fluorine gas was continuously blown therein,
under a pressure of 0.1 MPa (gauge pressure), a solution having 67
g of the compound (51) dissolved in 299 g of R113, was introduced
in the autoclave. After completion of the introduction, nitrogen
gas was blown into the autoclave. Then, the content in the
autoclave was recovered and concentrated to obtain a compound
(41).
[0133] Then, into a flask under a nitrogen gas atmosphere, 80 g of
the compound (41) and 0.7 g of a KF powder were introduced, and
while the inner temperature of the flask was raised to from 80 to
120.degree. C., the flask was heated for 6 hours. The content of
the flask was purified by using a distillation method using a cold
trap and a recrystallization method, to obtain 38 g of white solid
compound (31).
[0134] The NMR data of the compound (31) are shown as follows.
[0135] .sup.19F-NMR (282.7 MHz, solvent: CDCl.sub.3, standard:
CFCl.sub.3) .delta. (ppm): -116.8 (1F), -118.2 (1F), -122.9 (1F),
-123.3 (1F), -125.4 (1F), -127.3 (1F), -130.6 (1F), -134.6 (1F),
-219.4 (1F), -227.5 (1F).
Example 2
Production Example of Compound (21)
[0136] Into a round-bottom flask (inner volume: 100 mL) under a
nitrogen gas atmosphere, 1.1 g of NaBH.sub.4 and 30 g of THF were
introduced. While the flask was cooled with ice and was stirred, 48
g of an R225 solution containing 22 mass % of the compound (31) was
dropwise added into the flask, over 1.5 hours. After completion of
the dropwise addition, inside of the flask was stirred for further
30 minutes. Further, while keeping the inner temperature of the
flask at 25.degree. C., inside of the flask was stirred for 12
hours. Then, the liquid content of the flask was neutralized with
0.1 mol/L of a hydrochloric acid aqueous solution (150 mL),
followed by washing with water. The resultant was distilled and
purified to obtain the following compound (21).
##STR00034##
[0137] The NMR data of the compound (21) are shown as follows.
[0138] .sup.1H-NMR (300.4 MHz, solvent: CDCl.sub.3, standard: TMS)
.delta. (ppm): 4.89 to 4.57 (2H).
[0139] .sup.19F-NMR (282.7 MHz, solvent: CDCl.sub.3, standard:
CFCl.sub.3) .delta. (ppm): -105.0 (1F), -119.7 (1F), -124.0 (1F),
-124.3 (1F), -125.7 (1F), -126.8 (1F), -133.2 (2F), -216.6 (1F),
-223.5 (1F).
Example 3
Production Example of Compound (11)
[0140] Into a flask, 2.2 g of the compound (21), 10 g of THF, 2 mg
of an aluminum salt of N-nitrosophenyl hydroxyamine and 1.2 g of
triethylamine were introduced. The flask was cooled with ice, and
with stirring, 7.3 g of a THF solution of a compound represented by
CH.sub.2.dbd.C(CH.sub.3)C(O)Cl (1.2 g) was slowly dropwise added
into the flask. After completion of the dropwise addition, inside
of the flask was stirred for 2 hours, and then, 30 mL of a sodium
hydrogencarbonate aqueous solution was added thereto.
[0141] The extraction liquid obtained by extracting the liquid
content of the flask with R225, was dried over anhydrous sodium
sulfate, and then, concentrated to obtain a concentrated liquid.
The concentrated liquid was purified by a silica gel column
chromatography to obtain 2.7 g of the following compound (11).
##STR00035##
[0142] The NMR data of the compound (11) are shown as follows.
[0143] .sup.1H-NMR (300.4 MHz, solvent: CDCl.sub.3, standard: TMS)
.delta. (ppm): 6.31 (1H), 5.88 (1H), 5.84 (1H), 2.01 (3H).
[0144] .sup.19F-NMR (282.7 MHz, solvent: CDCl.sub.3, standard:
CFCl.sub.3) .delta. (ppm): -104.6 (1F), -120.5 (1F), -122.4 (1F),
-124.2 (1F), -124.6 (1F), -126.5 (1F), -132.7 to -132.8 (2F),
-214.8 (1F), -223.2 (1F).
Example 4
Production Example of Compound (32.sup.M)
[0145] By following the production route represented by the
following formula, a compound (32.sup.M) was produced from the
following compound (62). Here, a compound represented by
R.sup.f2--C(O)F is a compound represented by
F(CF.sub.2).sub.3OCF(CF.sub.3)C(O)F.
##STR00036##
[0146] Into a flask under a nitrogen gas atmosphere, 26 g of the
compound (62) and 100 g of R225 were introduced. With cooling with
ice, 91 g of the compound represented by R.sup.f2--C(O)F was
dropwise added thereto while stirring inside of the flask. Inside
of the flask was further stirred, and then, the content was
concentrated and filtrated to obtain 88 g of compound (52).
[0147] Then, into an autoclave (made of nickel, inner volume: 500
mL) having a NaF pellet packed bed set at a gas outlet, 326 g of
R113 was added, and while stirring inside of the autoclave at
25.degree. C., a nitrogen gas was blown into the autoclave for 1
hour. Further, 20% fluorine gas was blown therein.
[0148] While the 20% fluorine gas was continuously blown therein,
under a pressure of 0.1 MPa (gauge pressure), a solution having 75
g of the compound (52) dissolved in 346 g of R113, was introduced
in the autoclave. After completion of the introduction, a nitrogen
gas was blown into the autoclave. Then, the autoclave content was
recovered and concentrated to obtain a compound (42).
[0149] Under cooling with ice, 20 g of methanol was dropwise added
to a solution obtained by dissolving 106 g of the compound (42)
into 100 mL of R225. After completion of the dropwise addition, at
a solution temperature of 25.degree. C., the solution was stirred
for 12 hours. R225 and F(CF.sub.2).sub.3OCF(CF.sub.3)COOCH.sub.3
were distilled from the solution to obtain 42 g of a compound
(32.sup.M).
[0150] The NMR data of the compound (32.sup.M) are shown as
follows.
[0151] .sup.1H-NMR (300.4 MHz, solvent: CDCl.sub.3, standard: TMS)
.delta. (ppm): 3.97 (3H).
[0152] .sup.19F-NMR (282.7 MHz, solvent: CDCl.sub.3, standard:
CFCl.sub.3) .delta. (ppm): -116.4 to -132.2 (8F), -174.3 (1F),
-219.1 (1F), -227.0 (1F).
Example 5
Production Example of Compound (32.sup.F)
[0153] Into a flask having a simple distillation apparatus set on
its upper part, 100 g of the compound (42) obtained in the same
manner as in Example 4 and 1.7 g of a KF powder were introduced.
When the inner temperature of the flask was adjusted to be at
80.degree. C. and inside of the flask was stirred, reflux of the
liquid content of the flask was observed. While having
F(CF.sub.2).sub.3OCF(CF.sub.3)COF distilled by the simple
distillation apparatus, inside of the flask was stirred for 5
hours. After completion of the distillation to the simple
distillation apparatus, the flask was gradually cooled, and R225
and R113 were introduced in the flask. Then, as a result of
analyzing the reaction product obtained by removing KF in the
liquid content of the flask by pressure filtration, the formation
of the following compound (32.sup.F) was confirmed. The yield
calculated from .sup.19F-NMR was 96%.
[0154] The NMR data of the compound (32.sup.F) are as follows.
[0155] .sup.19F-NMR (282.7 MHz, solvent: CDCl.sub.3, standard:
CFCl.sub.3) .delta. (ppm): +39.3 to +35.6 (1F), -117.5 to -132.0
(8F), -178.8 (1F), -218.0 to -226.2 (2F).
##STR00037##
Example 6
Production Example of Compound (22)
[0156] Into an ice-cooled solution obtained by dissolving 42 g of
the compound (32.sup.M) into 100 mL of THF, 20 g of a hexane
solution containing 79 mass % of
((CH.sub.3).sub.2CHCH.sub.2).sub.2AlH was dropwise added. After
completion of the dropwise addition, the solution was stirred at
25.degree. C. for 12 hours, and then, the solution was neutralized
with 0.2 mol/L hydrochloric aqueous solution (150 mL) to obtain a
reaction crude liquid.
[0157] The reaction crude liquid was extracted with R225 to obtain
an extraction liquid, and a low-boiling component of the extraction
liquid was distilled to obtain 31 g of a white solid reaction
product. The reaction product was recrystallized in hexane to
obtain the following compound (22) of a capillary crystal
(colorless).
##STR00038##
[0158] The NMR data of the compound (22) are as follows.
[0159] .sup.1H-NMR (300.4 MHz, solvent: CDCl.sub.3, standard: TMS)
.delta. (ppm): 4.20 (2H, dd, j=24.9 and 6.6 Hz), 2.15 (1H, m).
[0160] .sup.19F-NMR (282.7 MHz, solvent: CDCl.sub.3, standard:
CFCl.sub.3) S (ppm): -119.3 (1F), -121.3 (1F), -123.5 (1F), -123.6
(1F), -124.6 (1F), -125.0 (1F), -128.7 (1F), -131.6 (1F), -183.2
(1F), -220.2 (1F), -227.1 (1F).
Example 7
Production Example of Compound (12)
[0161] Into a flask, 16.3 g of the compound (22), 82 mL of
tert-butyl methyl ether, 5 mg of hydroquinone and 8.1 g of
triethylamine were introduced. While cooling inside of the flask
with ice and stirring, 8.4 g of CH.sub.2.dbd.C(CH.sub.3)C(O)Cl was
dropwise added into the flask. After completion of the dropwise
addition, inside of the flask was further stirred for 17 hours, and
then, 50 mL of pure water was introduced in the flask. The salt
precipitated in the flask was dissolved to obtain a two-layer
separated liquid.
[0162] The upper layer (a tert-butyl methyl ether layer) of the
content of the flask was recovered, and the recovered liquid was
dried over anhydrous sodium sulfate and was concentrated to obtain
a concentrated liquid. The concentrated liquid was purified by a
silica gel column chromatography to obtain 14 g of the following
compound (12).
##STR00039##
[0163] The NMR data of the compound (12) are as follows.
[0164] .sup.1H-NMR (300.4 MHz, solvent: CDCl.sub.3, standard: TMS)
.delta. (ppm): 6.20 (1H), 5.70 (1H), 4.75 (2H), 1.98 (3H).
[0165] .sup.19F-NMR (282.7 MHz, solvent: CDCl.sub.3, standard:
CFCl.sub.3) .delta. (ppm): -118.6 (1F), -120.6 (1F), -123.8 (2F),
-124.5 (1F), -124.9 (1F), -128.6 (1F), -131.4 (1F), -179.1 (1F),
-219.8 (1F), -227.0 (1F).
Example 8
Polymerization Example of Compound (11)
[0166] Into a pressure-proof reactor (inner volume: 30 mL), 3.0 g
of the compound (11), 11.3 g of R225 and 1.5 g of
diisopropylperoxycarbonate which was diluted to 50 mass % by R225,
were introduced. Inside of the reactor was frozen and degassed, and
then, the inner temperature of the reactor was adjusted to
40.degree. C., and a polymerization reaction was carried out for 18
hours. After the polymerization reaction, the content liquid of the
reactor was dropwise added to methanol, the formed solid product
was recovered, and the solid product was vacuum dried at 90.degree.
C. for 15 hours. As a result, 2.2 g of a polymer formed by
polymerization of the compound (11) (hereinafter referred to as a
polymer (11)) was obtained. The formation of the polymer can be
confirmed according to the fact that the compound (11) could hardly
be detected by an NMR measurement of the liquid content, and there
was no absorption based on a methacryloyl group in IR of the
product. The polymer (11) was a white solid polymer at 25.degree.
C.
[0167] The molecular weight of the polymer (11) was measured by a
gel permeation chromatography method wherein a solvent mixture made
of 99 vol % of R225 and 1 vol % of hexafluoropropanol, was referred
to as a mobile phase, and polymethyl methacrylate was referred to
as an inner standard. The number average molecular weight of the
polymer (11) was 4,600, and the weight average molecular weight was
8,800. Further, the contact angle of the polymer (11) to water was
107.degree., and its sliding angle was 9.degree..
[0168] The measurements of the contact angle and the sliding angle
were carried out by the following process.
[0169] That is, a solution having the polymer (11) dissolved in
1,3-bis(trifluoromethyl)benzene, was prepared. The solution was
filtrated to obtain a solution containing 4 mass % of the polymer
(11) based on the total mass of 1,3(trifluoromethyl)benzene. Then,
the solution was applied on a surface of a silicon substrate by
carrying out a spin coating method (rotation condition: 2,000 rpm
for 30 seconds). Further, by heating the substrate at least to the
boiling point of the solvent, the solvent was removed, and a film
of the polymer (11) was formed on the surface of the silicon
substrate. Then, a droplet of water (2 .mu.L) was placed on the
film, and in a state of keeping the substrate in horizontal, the
contact angle of the droplet of water to the film, was measured.
Further, a droplet of water (50 .mu.L) at 25.degree. C. was placed
on the film, and by declining the substrate, the inclination angle
of the substrate immediately before the droplet of water fell, was
measured. Such value was referred to as a sliding angle. Such
measurements were carried out by using a contact angle meter
(tradename: DropMaster700, manufactured by Kyowa Interface Science
Co., Ltd.).
Example 9
Polymerization Example of Compound (12)
[0170] Into a pressure-proof reactor (inner volume: 30 mL), 2.0 g
of the compound (12), 10.7 g of R225 and 1.3 g of
diisopropylperoxycarbonate which was diluted to 50 mass % by R225,
and 0.35 g of isopropyl alcohol, were introduced. Inside of the
reactor was frozen and degassed, and then, the inner temperature of
the reactor was adjusted to 40.degree. C., and a polymerization
reaction was carried out for 18 hours. After the polymerization
reaction, the liquid content of the reactor was dropwise added to
methanol to recover the formed solid product, and the solid product
was vacuum dried at 90.degree. C. for 15 hours. As a result, 1.2 g
of a polymer formed by polymerization of the compound (12)
(hereinafter referred to as a polymer (12)), was obtained. The
polymer (12) was a white solid polymer at 25.degree. C.
[0171] As a result of measuring the molecular weight of the polymer
(12) in the same manner as in Example 8, the number average
molecular weight of the polymer (12) was 4,300, and the weight
average molecular weight was 8,800. Further, the contact angle of
the polymer (12) to water was 106.degree., and the sliding angle
was 11.degree..
INDUSTRIAL APPLICABILITY
[0172] According to the present invention, a novel fluorocompound
having a highly fluorinated norbornane structure, is provided. A
polymer obtained by polymerizing the polymerizable compound having
the fluorinated norbornane structure, of the present invention, is
excellent in water and oil repellency, heat resistance, mold
releasability, chemical resistance, transparency, durability and
light resistance and low refractive index property, and it is a
polymer particularly excellent in dynamic water and oil repellency.
The polymer of the present invention is useful as an antifouling
agent, a water and oil repellent, a mold lubricant, an optical
fiber material, a pellicle material, a lens material, a display
surface protection film, etc.
[0173] The entire disclosure of Japanese Patent Application No.
2006-190484 filed on Jul. 11, 2006 including specification, claims
and summary is incorporated herein by reference in its
entirety.
* * * * *