U.S. patent application number 10/002140 was filed with the patent office on 2002-04-11 for fluorine-containing organic silicon compound and method for its production.
This patent application is currently assigned to Asahi Glass Company, Limited. Invention is credited to Furukawa, Yutaka, Yoneda, Takashige.
Application Number | 20020042532 10/002140 |
Document ID | / |
Family ID | 18619942 |
Filed Date | 2002-04-11 |
United States Patent
Application |
20020042532 |
Kind Code |
A1 |
Furukawa, Yutaka ; et
al. |
April 11, 2002 |
Fluorine-containing organic silicon compound and method for its
production
Abstract
A fluorine-containing organic silicon compound represented by
the following formula (1): (1) provided that the symbols in the
formula (1) have the following meanings: R.sup.1 and R.sup.2:
respectively independently monovalent hydrocarbon groups; A.sup.f:
a group represented by the following formula (2), (3), (4) or (5):
A.sup.1--X.sup.1-- (2) A.sup.2--X.sup.2--O--X.sup.1-- (3)
A.sup.1--X.sup.2--O--X.sup.1-- (4) A.sup.2--X.sup.1-- (5) provided
that the symbols in the formulae (2), (3), (4) and (5) have the
following meanings: A.sup.1: a monovalent polyfluorohydrocarbon
group; A.sup.2: a monovalent polyfluorohydrocarbon group containing
an etheric oxygen atom; X.sup.1: --(CH.sub.2).sub.a-- (a is an
integer of at least 3); X.sup.2: a bivalent hydrocarbon group.
Inventors: |
Furukawa, Yutaka;
(Yokohama-shi, JP) ; Yoneda, Takashige;
(Yokohama-shi, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
Asahi Glass Company,
Limited
Tokyo
JP
|
Family ID: |
18619942 |
Appl. No.: |
10/002140 |
Filed: |
December 5, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10002140 |
Dec 5, 2001 |
|
|
|
PCT/JP01/02779 |
Mar 30, 2001 |
|
|
|
Current U.S.
Class: |
556/445 |
Current CPC
Class: |
C09K 3/18 20130101; C07F
7/0836 20130101 |
Class at
Publication: |
556/445 |
International
Class: |
C07F 007/08 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 7, 2000 |
JP |
2000-106835 |
Claims
What is claimed is:
1. A fluorine-containing organic silicon compound represented by
the following formula (1): 7provided that the symbols in the
formula (1) have the following meanings: R.sup.1 and R.sup.2:
respectively independently monovalent hydrocarbon groups; A.sup.f:
a group represented by the following formula (2), (3), (4) or
(5):A.sup.1--X.sup.1-- (2)A.sup.2--X.sup.2--O--X.sup.1--
(3)A.sup.1--X.sup.2--O--X.sup.1-- (4)A.sup.2--X.sup.1-- (5)provided
that the symbols in the formulae (2), (3), (4) and (5) have the
following meanings: A.sup.1: a monovalent polyfluorohydrocarbon
group; A.sup.2: a monovalent polyfluorohydrocarbon group containing
an etheric oxygen atom; X.sup.1: --(CH.sub.2).sub.a-- (a is an
integer of at least 3); X.sup.2: a bivalent hydrocarbon group.
2. The fluorine-containing organic silicon compound according to
claim 1, which satisfies any one of the conditions that the formula
(2) is a group represented by the following formula (6), the
formula (3) is a group represented by the following formula (7),
the formula (4) is a group represented by the following formula
(8), and the formula (5) is a group represented by the following
formula (9):C.sub.nF.sub.2n+1--X.sup.1--
(6)F[CF(CF.sub.3)CF.sub.2O].sub.mCF(CF.sub.3)--X.sup.2--O--X.sup.1--
(7)C.sub.kF.sub.2k+1--X.sup.2--O--X.sup.1--
(8)F[CF(CF.sub.3)CF.sub.2O].- sub.vCF
(CF.sub.3)--CF.sub.2OCF.sub.2CF.sub.2--X.sup.1-- (9)provided that
the symbols in the formulae (6), (7), (8) and (9) have the
following meanings: n: an integer of from 1 to 18; m: an integer of
from 1 to 10; k: an integer of from 1 to 18; v: an integer of at
least 0; X.sup.1 and X.sup.2: the same meanings as in the formula
(2), (3), (4) or (5).
3. The fluorine-containing organic silicon compound according to
claim 1, wherein X.sup.2 is represented by --(CH.sub.2).sub.p-- (p
is an integer of from 1 to 10).
4. A method for producing a fluorine-containing organic silicon
compound represented by the above formula (1), which comprises
hydrolyzing a fluorine-containing organic silicon compound
represented by the following formula (10), wherein the hydrolysis
is carried out while neutralizing hydrogen halide formed during the
hydrolysis with a base: 8provided that the symbols in the formula
(10) have the following meanings: X: a halogen atom; R.sup.1,
R.sup.2 and A.sup.f: the same meanings as the meanings in the
formula (1).
5. The method for producing a fluorine-containing silicon compound
according to claim 4, wherein the base is an inorganic base
dispersed or suspended in water.
6. The method for producing a fluorine-containing silicon compound
according to claim 5, wherein the hydrolysis is carried out in the
presence of the inorganic base dispersed or suspended in water, in
the reaction system, from the beginning of the reaction.
7. A surface treating agent comprising a fluorine-containing
organic silicon compound as defined in claim 1, as an essential
component.
Description
TECHNICAL FIELD
[0001] The present invention relates to a novel fluorine-containing
organic silicon compound and a method for its production.
Particularly, it relates to a fluorine-containing organic silicon
compound having a hydroxyl group directly bonded to a silicon atom,
and a method for its production.
BACKGROUND ART
[0002] An organic silicon compound having fluorine atoms is
excellent in e.g. lubricating properties, water and oil repellency
and oil and chemical resistance and thus is applied to various
industrial fields. For example, when it is used as an additive to a
surface treating agent or a resin, it is possible to impart the
above-mentioned properties to the surface of a substrate or a
molded product of the resin. As a specific example of such a
fluorine-containing organic silicon compound, a fluorine-containing
silane coupling agent made of a compound represented by the
following formula (11) may be mentioned.
ASiY.sub.3 (11)
[0003] (In the formula (11), A represents R(CH.sub.2).sub.2-- (R is
a perfluoroalkyl group), Y represents a hydrolysable group such as
a halogen atom or an alkoxy group.)
[0004] Further, in a method of hydrolyzing a non-fluorine type
silicon compound having a Si--Y moiety to produce a corresponding
compound having a Si--OH moiety, a method of reacting while
dropwise adding ammonia to the reaction system, is known.
[0005] However, in a case where the surface of a substrate was
treated with a fluorine-containing silane coupling agent made of a
compound represented by the formula (11), there was a problem that
attached water remained on the surface, although the surface showed
water and oil repellency and oil and chemical resistance.
[0006] Further, in the method of reacting while dropwise adding
ammonia, the reaction operation was cumbersome, and it was
necessary to control the flow rate in order to maintain the pH in
the reaction system within a predetermined range. Further, use of
ammonia brought about a problem from the viewpoint of working
environment or a problem of odor.
[0007] The present invention has an object to provide a novel
fluorine-containing organic silicon compound excellent in e.g.
lubricating properties, water and oil repellency, and oil and
chemical resistance. Namely, it has an object to provide a
fluorine-containing organic silicon compound useful as an additive
to be added to a surface treating agent and various resin
compositions. A surface treating agent containing the compound as
an essential component, is capable of imparting to the surface of a
substrate a nature of readily removing water attached to the
surface of the substrate.
DISCLOSURE OF THE INVENTION
[0008] The present invention provides a fluorine-containing organic
silicon compound represented by the following formula (1): 1
[0009] provided that the symbols in the formula (1) have the
following meanings:
[0010] R.sup.1 and R.sup.2: respectively independently monovalent
hydrocarbon groups;
[0011] A.sup.f: a group represented by the following formula (2),
(3), (4) or (5):
A.sup.1--X.sup.1-- (2)
A.sup.2--X.sup.2--O--X.sup.1-- (3)
A.sup.1--X.sup.2--O--X.sup.1-- (4)
A.sup.2--X.sup.1-- (5)
[0012] provided that the symbols in the formulae (2), (3), (4) and
(5) have the following meanings:
[0013] A.sup.1: a monovalent polyfluorohydrocarbon group;
[0014] A.sup.2: a monovalent polyfluorohydrocarbon group containing
an etheric oxygen atom;
[0015] X.sup.1: --(CH.sub.2).sub.a-- (a is an integer of at least
3);
[0016] X.sup.2: a bivalent hydrocarbon group. Further, the present
invention provides a method for producing a fluorine-containing
silicon compound represented by the above formula (1), which
comprises hydrolyzing a fluorine-containing silicon compound
represented by the following formula (10). Namely, it provides a
method for producing a fluorine-containing organic silicon
compound, wherein the hydrolysis is carried out while neutralizing
hydrogen halide formed during the hydrolysis with a base. 2
[0017] provided that the symbols in the formula (10) have the
following meanings:
[0018] X: a halogen atom;
[0019] R.sup.1, R.sup.2 and A.sup.f: the same meanings as the
meanings in the formula (1).
BEST MODE FOR CARRYING OUT THE INVENTION
[0020] The fluorine-containing organic silicon compound of the
present invention is represented by the following formula (1):
3
[0021] In the following, the meanings of the symbols in the formula
(1) will be explained.
[0022] In the present invention, "a hydrocarbon group" means a
group comprising carbon atoms and hydrogen atoms unless otherwise
specified. The hydrocarbon group may be an aromatic hydrocarbon
group or an aliphatic hydrocarbon group, but it is preferably an
aliphatic hydrocarbon group. As a monovalent aliphatic hydrocarbon
group, an alkyl group is preferred. As a bivalent aliphatic
hydrocarbon group, an alkylene group is preferred, and a
polymethylene group is more preferred. The number of carbon atoms
in an alkyl group and in an alkylene group is preferably from about
1 to 10, particularly preferably from 1 to 4. Further, the alkyl
group and the alkylene group are preferably of a straight chain
structure.
[0023] R.sup.1 and R.sup.2 respectively independently represent
monovalent hydrocarbon groups, preferably methyl groups.
[0024] A.sup.f is a group represented by the following formula (2),
(3), (4) or (5):
A.sup.1--X.sup.1-- (2)
A.sup.2--X.sup.2--O--X.sup.1-- (3)
A.sup.1--X.sup.2--O--X.sup.1-- (4)
A.sup.2--X.sup.1-- (5)
[0025] Here, A.sup.1 represents a monovalent polyfluorohydrocarbon
group. The "monovalent polyfluorohydrocarbon group" means a group
having at least two hydrogen atoms of a monovalent hydrocarbon
group substituted by fluorine atoms. As such a group, a
polyfluoroalkyl group is preferred.
[0026] The number of fluorine atoms in the polyfluorohydrocarbon
group is preferably at least 60%, more preferably at least 80%,
when it is represented by (the number of fluorine atoms in the
polyfluorohydrocarbon group)/(the number of hydrogen atoms in a
hydrocarbon group having the same number of carbon atoms
corresponding to the polyfluorohydrocarbon group).times.100(%).
Particularly preferred is a perfluorohydrocarbon group wherein it
is substantially 100% (a group having substantially all of hydrogen
atoms of a hydrocarbon group substituted by fluorine atoms).
[0027] The structure of the monovalent polyfluorohydrocarbon group
may be a straight chain or branched structure, but a straight chain
structure is preferred. In the case of a branched structure, the
branched moiety is preferably a short chain having from about 1 to
3 carbon atoms, and it is preferably a structure wherein the
branched moiety is present at a terminal portion of A.sup.1.
[0028] A.sup.1 is particularly preferably a perfluoroalkyl
group.
[0029] The following examples may be mentioned as specific examples
of A.sup.1. Further, structurally isomeric groups other than the
following are included in A.sup.1.
[0030] C.sub.4F.sub.9-- (including structural isomeric groups such
as CF.sub.3(CF.sub.2).sub.3--, (CF.sub.3).sub.2CFCF.sub.2--,
(CF.sub.3).sub.3C-- and CF.sub.3CF.sub.2CF(CF.sub.3)--),
C.sub.5F.sub.11-- (including structural isomeric groups such as
CF.sub.3(CF.sub.2).sub.4--, (CF.sub.3).sub.2CF(CF.sub.2).sub.2--,
(CF.sub.3)3CCF.sub.2-- and CF.sub.3(CF.sub.2).sub.2CF (CF.sub.3)
--), C.sub.6F.sub.13-- (including structural isomeric groups such
as CF.sub.3(CF.sub.2).sub.2C(CF.sub.3).sub.2--), C.sub.8F.sub.17--,
C.sub.10F.sub.21--, C.sub.12F.sub.25--, C.sub.14F.sub.29--,
C.sub.16F.sub.33--, C.sub.18F.sub.37--, C.sub.20F.sub.41-- and
(CF.sub.3).sub.2CF(CF.sub.2).sub.s-- (s is an integer of 0 or at
least 1).
[0031] A.sup.2 represents a monovalent polyfluorohydrocarbon group
containing an etheric oxygen atom. The "polyfluorohydrocarbon group
containing an etheric oxygen atom" means a group having one or at
least two etheric oxygen atoms inserted between a carbon-carbon
bond of the above-mentioned polyfluorohydrocarbon group. As such a
group, a group containing a polyfluorooxyalkylene moiety is
preferred.
[0032] A.sup.2 is particularly preferably a group containing
perfluorooxyalkylene, more preferably a group containing
perfluorooxyalkylene and having a perfluoroalkyl group at the
terminal. As such a perfluorooxyalkylene, perfluorooxymethylene,
perfluorooxyethylene, perfluorooxypropylene or perfluorooxybutylene
may, for example, be mentioned.
[0033] Specific examples of A.sup.2 may be
CF.sub.3(CF.sub.2).sub.4OCF(CF.- sub.3)--,
F[CF(CF.sub.3)CF.sub.2O].sub.uCF(CF.sub.3)CF.sub.2CF.sub.2-- (u is
an integer of at least 1),
F[CF(CF.sub.3)CF.sub.2O].sub.rCF(CF.sub.3)-- - (r is an integer of
at least 1), F(CF.sub.2CF.sub.2CF.sub.2O).sub.vCF.su- b.2CF.sub.2--
(v is an integer of at least 1), F(CF.sub.2CF.sub.2O).sub.wC-
F.sub.2CF.sub.2-- (w is an integer of at least 1), and
F[CF(CF.sub.3)CF.sub.2O].sub.z
CF(CF.sub.3)CF.sub.2OCF.sub.2CF.sub.2-- (z is an integer of at
least 1).
[0034] X.sup.1 represents --(CH2).sub.a-- (a is an integer of at
least 3). a is preferably an integer of from 3 to 6, particularly
preferably 3 or 4.
[0035] X.sup.2 is a bivalent hydrocarbon group. As such a group, an
alkylene group is preferred. X.sup.2 may have a straight chain or
branched structure, and a straight chain structure is preferred.
Particularly preferred is a straight chain alkylene group
represented by --(CH.sub.2).sub.p-- (p is an integer of from 1 to
10). Especially preferred is a straight chain alkylene group
wherein p is an integer of from 2 to 4. In the case of a branched
structure, the branched moiety is preferably a short chain wherein
the number of carbon atoms is from about 1 to 3.
[0036] In the fluorine-containing organic silicon compound of the
present invention, the above formula (2) is preferably a group
represented by the following formula (6).
C.sub.nF.sub.2n+1--X.sup.1-- (6)
[0037] In the formula (6), n represents an integer of from 1 to 18.
Preferably, n is an integer of from 4 to 12. X.sup.1 is as defined
above.
[0038] Specific examples of the group represented by the above
formula (6) may be C.sub.4F.sub.9--(CH.sub.2).sub.3--,
C.sub.4F.sub.9--(CH.sub.2).sub- .4,
C.sub.5F.sub.11--(CH.sub.2).sub.3,
C.sub.5F.sub.11--(CH.sub.2).sub.4--- ,
C.sub.6F.sub.13--(CH.sub.2).sub.3--,
C.sub.6F.sub.13--(CH.sub.2).sub.4--- ,
C.sub.7F.sub.15--(CH.sub.2).sub.3--,
C.sub.7F.sub.15--(CH.sub.2).sub.4--- ,
C.sub.8F.sub.17--(CH.sub.2).sub.3,
C.sub.8F.sub.17--(CH.sub.2).sub.4--,
C.sub.9F.sub.19--(CH.sub.2).sub.3--,
C.sub.9F.sub.19--(CH.sub.2).sub.4--,
C.sub.10F.sub.21--CH.sub.2).sub.3-- and
C.sub.10F.sub.21--(CH.sub.2).sub.- 4.
[0039] Further, as the perfluoroalkyl groups in the above specific
examples, structurally isomeric groups may be mentioned, and a
straight chain perfluoroalkyl group is preferred.
[0040] Further, in the fluorine-containing organic silicon compound
of the present invention, the above formula (3) is preferably a
group represented by the following formula (7):
F[CF(CF.sub.3)CF.sub.2O].sub.mCF(CF.sub.3)--X.sup.2--O--X.sup.1--
(7)
[0041] In the formula (7), m is an integer of from 1 to 10. m is
preferably an integer of from 1 to 5. X.sup.1 and X.sup.2 are as
defined above, and X.sup.2 is preferably a straight chain alkylene
group.
[0042] Specific examples of the group represented by the above
formula (7) may be
F[CF(CF.sub.3)CF.sub.2O].sub.2CF(CF.sub.3)CH.sub.2O(CH.sub.2).sub.-
3--, and
F[CF(CF.sub.3)CF.sub.2O]CF(CF.sub.3)CH.sub.2O(CH.sub.2).sub.3--.
[0043] Further, in the fluorine-containing organic silicon compound
of the present invention, the above formula (4) is preferably a
group represented by the following formula (8):
C.sub.kF.sub.2k+1--X.sup.2--O--X.sup.1-- (8)
[0044] In the formula (8), k is an integer of from 1 to 18. k is
preferably an integer of from 4 to 12. X.sup.1 and X.sup.2 are as
defined above, and X.sup.2 is preferably a straight chain alkylene
group.
[0045] Specific examples of the group represented by the above
formula (8) may be
C.sub.4F.sub.9--(CH.sub.2).sub.2--O--(CH.sub.2).sub.3--,
C.sub.6F.sub.13--(CH.sub.2).sub.2--O--(CH.sub.2).sub.3--,
C.sub.8F.sub.17--(CH.sub.2).sub.3--O--(CH.sub.2).sub.3-- and
C.sub.8F.sub.17--(CH.sub.2).sub.2--O--(CH.sub.2).sub.3--. Further,
the above specific examples include structural isomeric groups.
[0046] Further, in the fluorine-containing organic silicon compound
of the present invention, the above formula (5) is preferably a
group represented by the following formula (9):
F[CF(CF.sub.3)CF.sub.2O].sub.vCF(CF.sub.3)--CF.sub.2OCF.sub.2CF.sub.2--X.s-
up.1-- (9)
[0047] In the formula (9), v is an integer of at least 0. v is
preferably an integer of from 1 to 3. X.sup.1 is as defined above,
preferably --(CH.sub.2).sub.3--.
[0048] A specific example of the group represented by the above
formula (9) may be
F[CF(CF.sub.3)CF.sub.2O]CF(CF.sub.3)CF.sub.2OCF.sub.2CF.sub.2--
-CH.sub.2CH.sub.2CH.sub.2--.
[0049] The following compounds may be mentioned as specific
preferred examples of the fluorine-containing organic silicon
compound of the present invention. Further, the following specific
examples include structural isomeric groups.
[0050] C.sub.4F.sub.9(CH.sub.2).sub.3Si(CH.sub.3).sub.2OH,
[0051] C.sub.8F.sub.17(CH.sub.2).sub.3Si(CH.sub.3).sub.2OH,
[0052] C.sub.8F.sub.17(CH.sub.2).sub.4Si(CH3).sub.2OH,
[0053] C.sub.10F.sub.21(CH.sub.2).sub.3Si(CH.sub.3).sub.2OH,
[0054]
C.sub.8F.sub.17(CH.sub.2).sub.2--O--(CH.sub.2).sub.3Si(CH.sub.3).su-
b.2OH,
[0055]
C.sub.8F.sub.17(CH.sub.2).sub.3--O--(CH.sub.2).sub.3Si(CH.sub.3).su-
b.2OH,
[0056]
F[CF(CF.sub.3)CF.sub.2O]CF(CF.sub.3)CH.sub.2O(CH.sub.2).sub.3Si(CH.-
sub.3).sub.2OH,
[0057]
F[CF(CF.sub.3)CF.sub.2O].sub.2CF(CF.sub.3)CH.sub.2O(CH.sub.2).sub.3-
Si(CH.sub.3).sub.2OH,
[0058]
F[CF(CF.sub.3)CF.sub.2O]CF(CF.sub.3)CF.sub.2OCF.sub.2CF.sub.2(CH.su-
b.2).sub.3Si(CH.sub.3).sub.2OH.
[0059] As a method for producing the fluorine-containing organic
silicon compound of the present invention, a method of hydrolyzing
a fluorine-containing organic silicon compound represented by the
following formula (10) for the production, is preferred. Namely, it
is preferred to carry out the hydrolysis while neutralizing
hydrogen halide (HX) formed during the hydrolysis, with a base.
4
[0060] In the formula (10), X represents a halogen atom. As X, a
chlorine atom is preferred. R.sup.1, R.sup.2 and A.sup.f are as
defined above.
[0061] Specific examples of the fluorine-containing organic silicon
compound represented by the above formula (10) may be compounds
having hydroxyl groups of the compounds described above as specific
preferred examples of the fluorine-containing organic silicon
compound of the present invention, substituted by chlorine atoms or
bromine atoms. The method of obtaining the fluorine-containing
organic silicon compound represented by the above formula (10) is
not particularly limited. For example, it can be synthesized by a
reaction (hereinafter referred to also as "hydrosililation")
wherein a H--Si moiety of a compound represented by the following
formula (16) is added to a fluorine-containing unsaturated compound
represented by the following formula (12), (13), (14) or (15):
A.sup.1--X.sup.6--(CH.sub.2).sub.rCH.sub.2CH.dbd.CH.sub.2 (1 2)
A.sup.2--X.sup.2--O--X.sup.6--(CH.sub.2).sub.sCH.sub.2CH.dbd.CH.sub.2
(3)
A.sup.1--X.sup.2--O--X.sup.6--(CH.sub.2).sub.tCH.sub.2CH.dbd.CH.sub.2
(14)
A.sup.2--X.sup.6--(CH.sub.2).sub.rCH.sub.2CH.dbd.CH.sub.2 (1 5)
[0062] In the formulae (12) to (15), each of r, s and t represents
an integer of 0 or at least 1, preferably 0, 1 or 2, particularly
preferably 0. A.sup.1, A.sup.2 and x.sup.2 are as defined above.
X.sup.6 represents a single bond or a bivalent hydrocarbon group.
5
[0063] In the formula (16), R.sup.1, R.sup.2 and X are as defined
above.
[0064] Specific examples of the fluorine-containing unsaturated
compound represented by the above formula (12) may be
C.sub.4F.sub.9CH.sub.2CH.dbd- .CH.sub.2,
C.sub.8F.sub.17CH.sub.2CH.dbd.CH.sub.2, C.sub.8F.sub.17(CH.sub.-
2).sub.2CH.dbd.CH.sub.2 and
C.sub.10F.sub.21CH.sub.2CH.dbd.CH.sub.2.
[0065] Specific examples of the fluorine-containing unsaturated
compound represented by the above formula (13) may be
F[CF(CF.sub.3)CF.sub.2O]CF(C-
F.sub.3)--CH.sub.2--O--CH.sub.2CH.dbd.CH.sub.2, and
F[CF(CF.sub.3)CF.sub.2O].sub.2CF(CF.sub.3)--CH.sub.2--O--CH.sub.2CH.dbd.C-
H.sub.2.
[0066] Specific examples of the fluorine-containing unsaturated
compound represented by the above formula (14) may be
C.sub.8F.sub.17(CH.sub.2).su- b.2--O--CH.sub.2CH.dbd.CH.sub.2 and
C.sub.8F.sub.17(CH.sub.2).sub.3--O--CH- .sub.2CH.dbd.CH.sub.2.
[0067] A specific example of the fluorine-containing unsaturated
compound represented by the above formula (15) may be
F{CF(CF.sub.3)CF.sub.2O}CF(C-
F.sub.3)--CF.sub.2--O--CF.sub.2CF.sub.2CH.sub.2CH.dbd.CH.sub.2.
[0068] In the hydrosililation, the amount of the
fluorine-containing unsaturated compound represented by the above
formulae (12) to (15) is preferably at least one equivalent, more
preferably from 1.1 to 2 equivalents, per equivalent of hydrogen
atoms bonded to the silicon atom in the compound represented by the
above formula (16).
[0069] The hydrosililation is carried out preferably in the
presence of a catalyst. As the catalyst, a catalyst containing a
transition metal is preferred, and a catalyst containing at least
one selected from platinum, rhodium and cobalt, is particularly
preferred. The amount of the catalyst is usually from about 1 to 10
ppm in the reaction system. However, in the present invention, it
is preferably from about 0.01 to 10 ppm, since the reaction
proceeds in a short time even when the amount of the catalyst is
small in the present invention.
[0070] The hydrosililation may be carried out in the presence of a
solvent, or substantially in the absence of a solvent. It is
preferably carried out in the absence of a solvent. In the absence
of a solvent, the amount of a solvent contained in the reaction
system is most preferably 0 (not contained at all). However, a
solvent may be present in such an amount to be used for the
preparation of a reagent to be used for the reaction.
[0071] For example, a small amount of a solvent used for dissolving
the catalyst may be present. The amount of a solvent in the
reaction system is preferably at most 1 mass %, more preferably
from 0 to 0.1 mass %. When the reaction is carried out
substantially in the absence of a solvent, there is a merit in that
no solvent will remain in the formed fluorine-containing organic
silicon compound represented by the above formula (1), and a
product of high quality can be obtained. Further, post treatment
after the reaction can easily be carried out.
[0072] The reaction temperature is preferably from about 70 to
100.degree. C. in a usual case.
[0073] The reaction time may be suitably changed depending upon the
compound to be used. It is usually from about 0.5 to 10 hours.
However, in the case of the present invention, it is preferably
from 0.5 to 5 hours, particularly preferably from 3 to 5 hours,
since the reaction proceeds even in a short period of time.
[0074] The fluorine-containing organic silicon compound of the
present invention is preferably produced by a method of hydrolyzing
the fluorine-containing organic silicon compound represented by the
above formula (10) while neutralizing hydrogen halide formed during
the hydrolysis, with a base.
[0075] As the base to be used for the production of the
fluorine-containing organic silicon compound of the present
invention, an inorganic base is preferred. Particularly preferred
is an inorganic weak base such as calcium carbonate, sodium
bicarbonate or magnesium carbonate. The amount of the base may be
at least equivalent to the acid to be formed. The amount of the
base is preferably from 1 to 1.5 equivalents, particularly
preferably from 1 to 1.05 equivalents, to the amount of the acid to
be formed.
[0076] Further, the amount of water to be used for the hydrolytic
reaction, may be at least equivalent to X (halogen atoms)
stoichiometrically. When an inorganic weak base is used as the
base, it is preferably used as dispersed or suspended in water. In
such a case, in order to have the inorganic weak base sufficiently
dispersed or suspended, the concentration of the base is preferably
from 1 to 30 mass %, particularly preferably from 5 to 15 mass %.
The inorganic base dispersed or suspended in water, is preferably
permitted to be present from the beginning of the reaction so that
the reaction system may not be acidic.
[0077] Further, at the time of carrying out the hydrolytic
reaction, a solvent of ether type may be employed. The reaction
temperature is preferably at most 10.degree. C.
[0078] If the above hydrolytic reaction is carried out without
using a base, a compound represented by the following formula (17)
which is a dehydrated condensate of a hydrolyzate (formula (1)) of
the fluorine-containing organic silicon compound, will be formed in
a large amount: 6
[0079] In the formula (17), R.sup.1, R.sup.2 and A.sup.f are as
defined above.
[0080] Whereas, when the production method of the present invention
is employed, the fluorine-containing organic silicon compound
represented by the above formula (1), of high quality, can be
produced without formation of the compound represented by the
formula (17). Further, in a case where the inorganic base is used
as dispersed or suspended in water, there is a merit that
separation of the organic layer and the aqueous layer after the
reaction can easily be carried out. If ammonia is used, the
resulting salt serves as a kind of an emulsifier to form a
suspension state, whereby separation tends to be difficult.
[0081] The fluorine-containing organic silicon compound of the
present invention is excellent in e.g. lubrication properties,
water and oil repellency, and oil and chemical resistance, and it
has a nature to lower the surface tension or refractive index and
is also excellent in e.g. electrical insulating properties, release
properties, defoaming properties and heat resistance.
[0082] The fluorine-containing organic silicon compound of the
present invention can be used as various functional materials
required to have the above properties. For example, when it is
applied as a surface treating agent for the treatment of a
substrate, it is capable of imparting properties such as
lubrication properties, water and oil repellency, and oil and
chemical resistance to the surface of the substrate. Further, by
its addition to a functional oil, a resin, rubber, etc., it is
possible to lower the surface tension or refractive index or to
impart e.g. electrical insulation properties, release properties,
water repellency, defoaming properties, oil resistance, solvent
resistance, lubrication properties or heat resistance. Particularly
when it is used as a surface treating agent, treatment by coating
is easy, and water attached to the surface can easily be
removed.
[0083] Further, the fluorine-containing organic silicon compound of
the present invention is a useful compound which can be used as an
intermediate for various fluorine-containing organic silicon
compounds.
[0084] The fluorine-containing organic silicon compound of the
present invention has a reactive hydroxyl group at its terminal,
whereby when it is used as a surface treating agent for the
treatment of the surface of a substrate, it is possible to impart
properties such as water and oil repellency, and oil and chemical
resistance to the surface of the substrate. Further, by its
addition to a resin, rubber, etc., it is possible to lower the
surface tension or refractive index or to impart properties such as
electrical insulating properties, release properties, water
repellency, defoaming properties, oil resistance, solvent
resistance, lubricating properties or heat resistance, to the
resin, rubber, etc. Especially when it is used as a surface
treating agent, it is possible to impart a property whereby water
attached to the surface can easily be removed.
[0085] Further, as shown in the following Reference Examples, it is
useful as a starting material for various industrial materials
which are required to have properties such as water and oil
repellency, stain-proofing properties and release properties.
EXAMPLES
[0086] The present invention will be described in detail with
reference to Examples. The present invention is by no means
restricted to such Examples.
Example 1
[0087] Into a glass container for reaction having a capacity of 0.5
l and equipped with a thermometer, a dropping funnel and a stirrer,
water (150 g) and CaCO.sub.3 (2.71 g) were put and stirred, and the
internal temperature was maintained to be from 0 to 50.degree. C.
Then, a solution having
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2Cl (30 g)
dissolved in diethyl ether (100 ml) was dropwise added from the
dropping funnel, and while maintaining the internal temperature of
the flask at a level of not higher than 5.degree. C., stirring was
continued for 30 minutes after completion of the dropwise
addition.
[0088] The reaction was terminated upon confirming the
disappearance of
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2Cl by gas
chromatography. After the termination of the reaction, double layer
separation was carried out, and the organic layer was dried by
adding magnesium sulfate. After removing magnesium sulfate by
filtration, diethyl ether was removed by an evaporator.
F(CF.sub.2).sub.8(CH.sub.2).s- ub.3Si(CH.sub.3).sub.2OH (28.4 g) as
a fluorine-containing organic silicon compound of the present
invention was obtained as a white solid.
[0089] The NMR spectrum and the IR spectrum of the above compound
are as follows.
[0090] .sup.1H--NMR .delta. (ppm): 0.18 (Si--CH.sub.3), 0.69
(Si--CH.sub.2), 1.56 (Si--OH), 1.70 (CH.sub.2--CH.sub.2--CH.sub.2),
2.11 (CF.sub.2--CH.sub.2)
[0091] .sup.19F--NMR .delta. (ppm): -81.7 (CF.sub.3), -115.1
(--CH.sub.2CF.sub.2--) -122.5.about.-124.1 (--CF.sub.2--), -126.9
(--CF.sub.2CF.sub.3)
[0092] IR (cm.sup.-1): 3680 (Si--OH), 1360.about.1300 (C--F.sub.3)
1250.about.1050 (C--F.sub.2), 1255 (Si--CH.sub.3), 1100 (Si--O)
Reference Example 1
[0093] Into a glass container for reaction having a capacity of 0.2
l and equipped with a thermometer and a stirrer,
[(CH.sub.3).sub.2SiO].sub.3 (13.8 g),
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2OH (10 )
obtained in Example 1, and tetrahydrofuran (hereinafter referred to
as THF, 60 ml) were put, and the internal temperature was
maintained to be 20.degree. C. Then, n-C.sub.4H.sub.9Li (a 15%
hexane solution, 45 .mu.l ) was put, followed by
polymerization.
[0094] After confirming disappearance of
[(CH.sub.3).sub.2SiO].sub.3 by gas chromatography,
(CH.sub.3).sub.2HSiCl (1.85 g) was put, followed by stirring for
one hour. After completion of the reaction, water (100 ml) was put,
followed by double layer separation, whereupon the organic layer
was washed with a 5% sodium hydrogen carbonate aqueous solution,
followed by double layer separation again, whereupon the organic
layer was dried by adding magnesium sulfate. After removing
magnesium sulfate by filtration, a volatile component was removed
under a condition of 100.degree. C./50 mmHg (=100.degree.
C./6.667.times.10.sup.4 Pa), the same applies hereinafter). A
transparent oil (23.7 g) represented by the following structural
formula, was obtained.
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2O[Si(CH.sub.3).sub.2O].-
sub.10Si(CH.sub.3).sub.2H
[0095] The NMR spectrum and the IR spectrum of the above compound
are as follows.
[0096] .sup.1H--NMR .delta. (ppm): 0.18 (Si--CH.sub.3), 0.69
(Si--CH.sub.2), 1.70 (CH.sub.2--CH.sub.2--CH.sub.2), 2.11
(CF.sub.2--CH.sub.2), 4.72 (Si--H)
[0097] .sup.19F--NMR .delta. (ppm): -81.7 (CF.sub.3), -115.1
(--CH.sub.2CF.sub.2--), -122.5.about.-124.1 (--CF.sub.2--), -126.9
(--CF.sub.2CF.sub.3)
[0098] IR (cm.sup.-1): 2150 (Si--H) 1360.about.1300 (C--F.sub.3),
1250.about.1050 (C--F.sub.2), 1255 (Si--CH.sub.3), 1100 (Si--O)
Reference Example 2
[0099] Into a glass container for reaction having a capacity of 0.2
l and equipped with a thermometer and a stirrer,
[F(CF.sub.2).sub.4(CH.sub.2).s- ub.2Si(CH.sub.3)O].sub.3 (57.0 g),
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.- sub.3).sub.2OH (10 g)
obtained in Example 1, and THF (60 ml) were put, and the internal
temperature was maintained to be 20.degree. C. Then,
n-C.sub.4H.sub.9Li (a 15% hexane solution, 45 .mu.l ) was put,
followed by polymerization.
[0100] After confirming disappearance of
[F(CF.sub.2).sub.4(CH.sub.2).sub.- 2Si(CH.sub.3)O].sub.3 by gas
chromatography, (CH.sub.3).sub.2HSiCl (1.85 g) was put, followed by
stirring for one hour. After completion of the reaction, water (100
ml) was put, followed by double layer separation. The organic layer
was washed with a 5% sodium hydrogen carbonate aqueous solution,
followed by double layer separation again, whereupon the organic
layer was dried by an addition of magnesium sulfate. After removing
magnesium sulfate by filtration, a volatile component was removed
under a condition of 100.degree. C./50 mmHg. A transparent oil
(64.7 g) represented by the following structural formula, was
obtained.
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2O[F(CF.sub.2).sub.4(CH.-
sub.2).sub.2Si(Ch.sub.3)O].sub.10Si(CH.sub.3).sub.2H
[0101] The NMR spectrum and the IR spectrum of the above compound
are as follows.
[0102] .sup.1H--NMR .delta. (ppm): 0.18 (Si--CH.sub.3), 0.69
(Si--CH.sub.2), 1.70 (CH.sub.2--CH.sub.2--CH.sub.2), 2.11
(CF.sub.2--CH.sub.2), 4.72 (Si--H)
[0103] .sup.19F--NMR .delta. (ppm): -81.7 (CF.sub.3) -115.1
(--CH.sub.2CF.sub.2--), -122.5.about.-124.1 (--CF.sub.2--), -126.9
(--CF.sub.2CF.sub.3)
[0104] IR (cm.sup.-1): 2150 (Si--H), 1360.about.1300 (C--F.sub.3),
1250.about.1050 (C--F.sub.2), 1255 (Si--CH.sub.3), 1100 (Si--O)
Reference Example 3
[0105] Into a glass container for reaction having a capacity of 0.1
l and equipped with a thermometer and a stirrer, the oil (27.4 g)
obtained in Reference Example 2, CH.sub.2.dbd.CHSi(OCH.sub.3).sub.3
(1.12 g) and a 10% isopropanol solution of chloroplatinic acid (0.1
g) were put, and then, the temperature was raised to 90.degree. C.,
followed by stirring for one hour.
[0106] The reaction was terminated upon confirming disappearance of
the peak of H--Si by IR. After termination of the reaction, a
volatile component was removed under a condition of 100.degree.
C./50 mmHg. A transparent oil (27.9 g) represented by the following
structural formula, was obtained.
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2O[F(CF.sub.2).sub.4(CH.-
sub.2).sub.2Si(CH.sub.3)O].sub.10Si
(CH.sub.3).sub.2((CH.sub.2).sub.2Si(OC- H.sub.3).sub.3)
[0107] The NMR spectrum and the IR spectrum of the above compound
are as follows.
[0108] .sup.1H--NMR .delta. (ppm): 0.18 (Si--CH.sub.3), 0.69
(Si--CH.sub.2), 1.70 (CH.sub.2--CH.sub.2--CH.sub.2), 2.11
(CF.sub.2--CH.sub.2), 3.68 (Si--OCH.sub.3)
[0109] .sup.19F--NMR .delta. (ppm): -81.7 (CF.sub.3), -115.1
(--CH.sub.2CF.sub.2--) -122.5.about.-124.1 (--CF.sub.2--), --126.9
(--CF.sub.2CF.sub.3)
[0110] IR (cm.sup.-1): 1360.about.1300 (C--F.sub.3),
1250.about.1050 (C--F.sub.2), 1255 (Si--CH.sub.3), 1100 (Si--O)
Reference Example 4
[0111] Into a glass container for reaction having a capacity of 0.2
l and equipped with a thermometer and a stirrer,
[(CH.sub.3).sub.2SiO].sub.3 (13.8 g),
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2OH (10 g)
obtained in Example 1, and tetrahydrofuran (THF, 60 ml) were put,
and the internal temperature was maintained to be 20.degree. C.
Then, n-C.sub.4H.sub.9Li (a 15% hexane solution, 34 .mu.l) was put,
followed by polymerization.
[0112] After confirming disappearance of
[(CH.sub.3).sub.2SiO].sub.3 by gas chromatography,
Si(OCH.sub.3).sub.4 (4.25 g) was put, followed by stirring for one
hour. After completion of the reaction, a volatile component was
removed under a condition of 100.degree. C./50 mmHg, and then,
pressure filtration was carried out. A transparent oil (24.8 g)
represented by the following structural formula, was obtained.
F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2O[Si(CH.sub.3).sub.2O].-
sub.10Si(OCH.sub.3).sub.3
[0113] The NMR spectrum and the IR spectrum of the above compound
are as follows.
[0114] .sup.1H--NMR .delta. (ppm): 0.18 (Si--CH.sub.3), 0.69
(Si--CH.sub.2), 1.70 (CH.sub.2--CH.sub.2--CH.sub.2), 2.11
(CF.sub.2--CH.sub.2), 3.80 (Si--OCH.sub.3)
[0115] .sup.19F--NMR .delta. (ppm): -81.7 (CF.sub.3), -115.1
(--CH.sub.2CF.sub.2--), -122.5.about.-124.1 (--CF.sub.2--), -126.9
(--CF.sub.2CF.sub.3)
[0116] IR (cm.sup.-1): 2150 (Si--H), 1360.about.1300 (C--F.sub.3),
1250.about.1050 (C--F.sub.2), 1255 (Si--CH.sub.3), 1100 (Si--O)
Example 2
[0117] Application of the Fluorine-Containing Organic Silicon
Compound of the Present Invention
[0118] F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2OH
obtained in Example 1, was dissolved at a concentration of 3 mass %
in an isopropanol solution. Glass was immersed in this solution for
30 seconds and then immersed in isopropanol, thereby to remove
excess F(CF.sub.2).sub.8(CH.su- b.2).sub.3Si(CH.sub.3).sub.2OH.
This glass was baked at 200.degree. C. for 3 minutes, whereupon the
contact angle was 110.degree., thus indicating that the glass
surface was provided with water repellency. Then, a water droplet
of 50 .mu.l was placed on this glass disposed horizontally, and the
glass was gradually inclined, whereby the water droplet moved at an
angle of 5.degree..
Comparative Example 1
[0119] A glass surface was treated in the same manner as in Example
2, by using F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(OCH.sub.3).sub.3
instead of F(CF.sub.2).sub.8(CH.sub.2).sub.3Si(CH.sub.3).sub.2OH.
The contact angle was 110.degree., thus indicating that the glass
surface was provided with water repellency. Then, a water droplet
of 50 .mu.l was placed on this glass disposed horizontally, and the
glass was gradually inclined, whereby the water droplet moved at an
angle of 30.degree..
[0120] The entire disclosure of Japanese Patent Application No.
2000-106835 filed on Apr. 7, 2000 including specification, claims,
drawings and summary are incorporated herein by reference in its
entirety.
* * * * *