HUPFIELD, Peter, Cheshire (Parc Y Gelli, Henfwlch Road Trevaughan, Carmarthen, SA336AA, GB)
OKAWA, Tadashi (2-2, Chigusakaigan, Ichihara-sh, Chiba 08, 2990108, JP)
IIMURA, Tomohiro (2-2, Chigusakaigan, Ichihara-sh, Chiba 08, 2990108, JP)
DOW CORNING CORPORATION (2200, West Salzburg Road Aubur, Michigan ., 48611, US)
HAYASHI, Masayuki (2-2, Chigusakaigan, Ichihara-sh, Chiba 08, 2990108, JP)
HUPFIELD, Peter, Cheshire (Parc Y Gelli, Henfwlch Road Trevaughan, Carmarthen, SA336AA, GB)
OKAWA, Tadashi (2-2, Chigusakaigan, Ichihara-sh, Chiba 08, 2990108, JP)
IIMURA, Tomohiro (2-2, Chigusakaigan, Ichihara-sh, Chiba 08, 2990108, JP)
CLAIMS
1. A fluorine-containing organopolysiloxane represented by the following general formula:
(where R 1 is the same as defined above, R 2 is an alkylene group, Q is a polystyrene- type residual radical, "a" is 0 or 1, and "b" is 0 or 1), a hydroxyl group, a hydrogen atom, or an alkoxy group, at least one Z being a group of general formula (I), and "m" being an integer equal to or greater than 1 } . 2. The fluorine-containing organopolysiloxane of Claim 1 , wherein the organic group that is designated by R 1 is a group that contains at least one group of formula: -CF 3 on a molecular terminal of the organic group, and either conatins or does not contain a group of formula: -CF 3 in a side chain of the organic group.
3. The fluorine-containing organopolysiloxane of Claim 1, wherein said organic group, which is designated by R 1 and contains a fluorine atom, is either an organic group that contains a fluorine atom and is represented by the following general formula:
- (CH 2 ) c - (O) d - R 3
(where "c" is an integer equal to or greater than 2; "d" is 0 or 1; R 3 is a fluorinated alkyl group that contains at least one group of formula: -CF 3 on its molecular terminal, and either contains or does not contain the group of formula: -CF 3 in a side chain of the fluorinated alkyl group) or an organic group that contains a fluorine atom which is represented by the following general formula: - (CH 2 ), - (O) d - (R 4 O) 6 - R 5 (where "c" is an integer equal to or greater than 2; "d" is 0 or 1 ; "e" is an integer equal to or greater than 1 ; R 4 is a fluorinated alkylene that contains or does not contain a group of formula: -CF 3 ; and R 5 is a fluorinated alkyl group that contains at least one group of formula: -CF 3 on a molecular terminal of the fluorinated alkyl group, and either contains or does not contain a group of formula: -CF 3 in a side chain of the fluorinated alkyl group).
4. The fluorine-containing organopolysiloxane of Claim 1, wherein said organic group, which is designated by R 1 and contains a fluorine atom, is a group selected from the groups of the following formulae: a fluorinated alkyl group that contains a fluorine atom and is represented by the following general formula:
~ (CH 2 ) C (CF 2 ) f F
(where "c" is an integer equal to or greater than 2; and "f" is an integer equal to or greater than 1); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) C CF (CF 3 ),
(where "c" is an integer equal to or greater than 2); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) c C (CF 3 ) 2 (CF 2 ) f CF 3 (where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) c CH (CF 3 ) (CH 2 ) f CF (CF 3 ) 2
(where "c" is an integer equal to or greater than 2; and "f" is an integer equal to or greater than 1); and an organic group that contains a fluorine atom and is represented by the following general formula:
- (CH 2 ) C O (CH 2 ) g CF (CF 3 ),
(where "c" is an integer equal to or greater than 2; and "g" is an integer equal to or greater than 2).
5. The fluorine-containing organopolysiloxane of Claim 1, wherein Q is a polystyrene-type residual radical that contains at least two repetitive units of the following general formula:
- C 2 H 2 (R 6 XC 6 H 5 ) - (where R 6 is a hydrogen atom or a methyl group) and wherein a molecular terminal is capped with a group originating from an anionic polymerization initiator.
6. A method of manufacturing a fluorine-containing organopolysiloxane of Claim 1 characterized by conducting a hydrosilylation reaction between (A) a fluorine- containing organopolysiloxane represented by the following general formula:
{where all R*'s are the same or different and designate organic groups that contain fluorine atoms or univalent hydrocarbon groups that do not contain fluorine atoms, at least one R 1 being an organic group that contains a fluorine atom; V is a group selected from the groups aforementioned R 1 , a hydrogen atom, or an alkoxy group; however, at least one V is a hydrogen atom; and "m" is an integer equal to or greater than 1 } and (B) a polystyrene-type compound represented by the following general formula:
R 7 - (SiR' 2 ) a - Q
(where R l 5 s may be the same or different; R 7 is an alkenyl group; Q is a polystyrene- type residual radical; and "a" is 0 or 1), said reaction being carried out in the presence of (C) a hydrosilylation catalyst.
7. The method of manufacturing a fluorine-containing organopolysiloxane according to Claim 6, wherein said organic group of component (A) that contains a fluorine atom is a group that contains at least one group represented by formula: -CF 3 on a molecular terminal of the organic group, and either contains or does not contain a group of formula: -CF 3 in a side chain of the organic group.
8. The method of manufacturing a fluorine-containing organopolysiloxane according to Claim 6, wherein said organic group that contains a fluorine atom and is designated by R 1 is either an organic group that contains a fluorine atom and is represented by the following general formula: - (CH 2 ) b - (O) c - R 3
(where "b" is an integer equal to or greater than 2; "c" is 0 or 1 ; R 3 is a fluorinated alkyl group that contains at least one group of formula: -CF 3 on a molecular terminal of the fluorinated alkyl group, and either contains or does not contain a group of formula: -CF 3 in a side chain of the fluorinated alkyl group) or an organic group that contains a fluorine atom which is represented by the following general formula:
- (CH 2 ) b - (O) c - (R 4 O) d - R 5
(where "b" is an integer equal to or greater than 2; "c" is 0 or 1 ; "d" is an integer equal to or greater than 1 ; R 4 is a fluorinated alkylene that contains or does not contain a group of formula: -CF 3 ; and R 5 is a fluorinated alkyl group that contains at least one group of formula: -CF 3 on a molecular terminal of the fluorinated alkyl group, and either contains or does not contain of a group of formula: -CF 3 in a side chain of the fluorinated alkyl group.
9. The method of manufacturing a fluorine-containing organopolysiloxane according to Claim 6, wherein said organic group, which is designated by R 1 and contains a fluorine atom, is a group selected from the groups of the following formulae: a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) c (CF 2 ) f F
(where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) C CF (CF 3 ),
(where "c" is an integer equal to or greater than 2); a fluorinated alkyl group represented by the following general formula: - (CH 2 ) C C (CF 3 ) 2 (CF 2 ) f CF 3
(where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) C CH (CF 3 ) (CH 2 ) f CF (CF 3 ) 2 (where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); or an organic group that contains a fluorine atom and is represented by the following general formula: - (CH 2 ) C O (CH 2 ) g CF (CF 3 ),
(where "c" is an integer equal to or greater than 2; and "g" is an integer equal to or greater than 2).
10. The method of manufacturing a fluorine-containing organopolysiloxane according to Claim 6, wherein Q is a polystyrene-type residual radical that contains at least two repetitive units of the following general formula:
- C 2 H 2 (R 6 XC 6 H 5 ) -
(where R is a hydrogen atom or a methyl group) and wherein a molecular terminal is capped with a group originating from an anionic polymerization initiator. 11. An organic polymer composition that contains a fluorine-containing organopolysiloxane according to any of Claims 1 to 5. |
DESCRIPTION
A FLUORINE-CONTAINING ORGANOPOLYSILOXANE, METHOD OF MANUFACTURING THEREOF, AND AN ORGANIC POLYMER COMPOSITION
Technical Field [0001] The present invention relates to a novel fluorine-containing organopolysiloxane, a method of manufacturing thereof, and an organic polymer composition containing the same.
Background Art
[0002] It is known that workability and mold-release properties of organic polymers, as well as lubricating properties of products molded from organic polymers, can be improved by adding fluorine-containing organopolysiloxanes. For example, Japanese Unexamined Patent Application Publication (hereinafter referred to as "Kokai") HOl- 282267 discloses an organopolysiloxane that contains polyfluoroalkyl groups with 3 to 20 carbon atoms. Kokai H07-233257 discloses an organopolysiloxane that contains perfluoroalkyl groups and linear-chain or branch-chain alkyl groups having three or more carbon atoms. Kokai 2001-172461 discloses an organopolysiloxane that contains perfluoroalkyl groups and polystyrene chains or polymethylstyrene chains. [0003] However, generally the fluorine-containing organopolysiloxanes have low surface tension and therefore cannot be uniformly admixed with organic polymers that are characterized by high surface tension. Because of poor compatibility with organic polymers, the aforementioned organopolysiloxanes cannot be uniformly dispersed in such polymers, and this creates a problem in manufacturing organic polymer compositions of high transparency. An attempt to improve compatibility with organic polymers by reducing concentration of fluorine in the aforementioned fluorine-containing organopolysiloxanes does not sufficiently improve the surface characteristics of organic polymers. In other words, with such measures it is difficult to improve oil-proof properties, lubricating properties, smoothness, resistance to wear, water-repellant oiling characteristics, waterproof properties, moisture-proof properties, anticorrosive properties, resistance to surface contamination, peeling properties, mold-release characteristics, etc. When in a liquid form, fluorine-containing organopolysiloxane decreases the strength of an organic polymer. Therefore, it is desirable to provide a fluorine-containing organopolysiloxane that
can be uniformly dispersed in organic polymers and that can sufficiently improve the surface characteristics of organic polymers.
[0004] It is an object of the present invention to provide a novel fluorine-containing organopolysiloxane that can be uniformly dispersed in an organic polymer and improve the surface characteristics thereof to a sufficient degree. It is another object to provide a method for manufacturing the aforementioned fluorine-containing organopolysiloxane. It is a further object to provide an organic polymer composition that contains the aforementioned fluorine-containing organopolysiloxane and is suitable for forming coating films that possess excellent transparency combined with good surface-lubricating properties.
Disclosure of Invention
[0005] The present invention provides a fluorine-containing organopolysiloxane represented by the following general formula:
(where R 1 is the same as defined above, R is an alkylene group, Q is a polystyrene-type residual radical, "a" is 0 or 1, and "b" is 0 or 1), a hydroxyl group, a hydrogen atom, or an alkoxy group, at leas one Z being a group of general formula (I), and "m" being an integer equal to or greater than 1 } . [0006] Furthermore, the method of the invention for manufacturing a fluorine- containing organopolysiloxane comprises conducting a hydrosilylation reaction between (A) a fluorine-containing organopolysiloxane represented by the following general formula:
{where all R''s may be the same or different and designate organic groups that contain fluorine atoms or univalent hydrocarbon groups that do not contain fluorine atoms, at least one R 1 being an organic group that contains a fluorine atom; V is a group selected from the groups corresponding to aforementioned R 1 , a hydrogen atom, or an alkoxy group; however, at least one V is a hydrogen atom; and "m" is an integer equal to or greater than 1 } and (B) a polystyrene-type compound represented by the following general formula:
R 7 - (SiR 1 ^ 3 - Q
(where R' 'S may be the same or different; R 7 is an alkenyl group; Q is a polystyrene-type residual radical; and "a" is 0 or 1), the aforementioned reaction being carried out in the presence of (C) a hydrosilylation catalyst.
[0007] The organic polymer composition of the present invention is the one that contains the aforementioned fluorine-containing organopolysiloxane.
Effects of Invention [0008] The fluorine-containing organopolysiloxane of the present invention is a novel compound that can be uniformly dispersed in organic polymers and can, to a sufficient degree, improve the surface characteristics of the organic polymer. The method of the present invention makes it possible to efficiently produce the aforementioned fluorine- containing organopolysiloxane. Since the organic polymer composition of the present invention contains the aforementioned fluorine-containing organopolysiloxane, it is suitable for forming coating films that possess excellent transparency combined with good surface-lubricating properties.
Detailed Description of the Invention
[0009] Let us first consider in more detail the fluorine-containing organopolysiloxane of the present invention. The aforementioned fluorine-containing organopolysiloxane of the invention is represented by the following general formula:
R 1 R 1 R 1 Z-SiO-(SiO)^Si-Z
I I l
R 1 R 1 R 1
[0010] In this formula, all R 1 's may be the same or different and may designate organic groups that contain fluorine atoms or univalent hydrocarbon groups that do not contain fluorine atoms. At least one R 1 is an organic group that contains a fluorine atom. Such organic group designated by R 1 that contains a fluorine atom may contain at least two groups represented by formula: -CF 3 . Furthermore, the organic group with a fluorine atom is a group that may contain at least one group of formula: -CF 3 on a molecular terminal of the organic group, and either contains or does not contain a group of formula: -CF 3 in a side chain of the organic group.
[0011] The aforementioned organic group that contains a fluorine atom is represented by the following general formula: - (CH 2 ) c - (O) d -R 3 or by the following general formula:
- (CH 2 ) C - (O) d - (R 4 O) 6 - R 5
In the above formula, R 3 is a fluorinated alkyl group that contains at least one group of formula: -CF 3 on a molecular terminal of the fluorinated alkyl group, and either contains or does not contain a group of formula: -CF 3 in a side chain of the fluorinated alkyl group; R 4 is a fluorinated alkylene that contains or does not contain a group of formula: -CF 3 ; and R 5 is a fluorinated alkyl group that contains at least one group of formula: -CF 3 on a molecular terminal of the fluorinated alkyl group, and either contains or does not contain a group of formula: -CF 3 in a side chain of the fluorinated alkyl group. In the above formula, "c" is an integer equal to or greater than 2; "d" is 0 or 1 ; and "e" is an integer equal to or greater than 1.
[0012] The preferable organic group that contains fluorine atoms is at least one group selected from the groups of the following formulae: a fluorinated alkyl group that contains a fluorine atom and is represented by the following general formula: - (CH 2 ) c (CF 2 ) f F
(where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); a fluorinated alkyl group represented by the following general formula:
(where "c" is an integer equal to or greater than 2); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) C C (CF 3 ) 2 (CF 2 ) f CF 3
(where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); a fluorinated alkyl group represented by the following general formula: - (CH 2 ) C CH (CF 3 ) (CH 2 ) f CF (CF 3 ) 2
(where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); and an organic group that contains a fluorine atom and is represented by the following general formula: - (CH 2 ) C O (CH 2 ) g CF (CF 3 ) 2
(where "c" is an integer equal to or greater than 2; and "g" is an integer equal to or greater than 2).
[0013] The aforementioned organic groups that contain fluorine atoms are exemplified by the following fluorinated alkyl groups: -CH 2 CH 2 CF 3
-CH 2 CH 2 CH 2 CF 3 -CH 2 CH 2 CH 2 CF(CF 3 ) 2 -CH 2 CH 2 CH 2 C(CF 3 ) 2 CF 2 CF 2 CF 3 -CH 2 CH 2 CH 2 CH(CF 3 )CH 2 CF(CF 3 ) 2 , or by the following fluorinated polyether groups:
-CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 CF(CF 3 ) 2 -(CH 2 ) 2 CF(CF 3 ) {OCF 2 CF(CF 3 )} 5 F -(CH 2 ) 2 CF 2 {OCF 2 CF(CF 3 )} 5 F -(CH 2 ) 3 OCH 2 CF(CF 3 ) {OCF 2 CF(CF 3 )} 5 F -(CH 2 ) 3 OCF 2 CF(CF 3 ) { OCF 2 CF(CF 3 ) } 5 F
[0014] The univalent hydrocarbon group, which is designated by R 1 and does not contain fluorine atoms, is exemplified by univalent hydrocarbon groups such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, dodecyl, octadecyl, or similar alkyl groups; vinyl, allyl, or similar alkenyl groups; phenyl, napththyl, or similar aryl groups. Most preferable of the above are methyl and phenyl groups.
[0015] In the above formula, Z designates a group selected from the same groups as those designated by R 1 , a group represented by the following general formula (I): - [R 2 - (SiR' 2 ) a ] b - Q,
a hydroxyl group, a hydrogen atom, or an alkoxy group. At least one Z is a group of general formula (I). In the above formula, R 1 S are the same or different organic groups that contain fluorine atoms or univalent hydrocarbon groups that do not contain fluorine atoms. Most preferable are univalent hydrocarbon groups that do not have unsaturated aliphatic bonds, in particular, groups such as methyl and phenyl groups. Furthermore, in the above formula, R 2 is an alkylene group that can be exemplified by ethylene, propylene, butylenes, pentylene, and hexylene. In the above formula, Q designates a polystyrene-type residual radical, which is a group that contains a polymer of styrene monomers. Such a radical can be specifically exemplified by a polystyrene-type residual radical that contains at least two repetitive units of the following general formula:
- C 2 H 2 (R 6 XC 6 H 5 ) - and wherein a molecular terminal is capped with a group originating from an anionic polymerization initiator. In this formula, R 6 is a hydrogen atom or a methyl group. The group originating from an anionic polymerization initiator may be exemplified by n-butyl, ethyl, n-amyl, triphenylmethyl, or similar substituted or non-substituted alkyl groups; isopropoxy, ethoxy, or similar alkoxy groups; - NH 2 , - NHC 6 H 5 , or similar amino groups; or hydroxyl groups. Most preferable are alkyl groups, especially butyl groups. Furthermore, in the above formula, "a" is 0 or 1 , and "b" is also 0 or 1. [0016] In the above formula, "m" is an integer equal to or greater than 0, and "n" is an integer equal to or greater than 1. Such a fluorine-containing organopolysiloxane of the invention can be exemplified by the compounds represented below by the following formulas, where "m" is an integer equal to or greater than 1 , "n" is an integer equal to or greater than 1, and "r" is an integer equal to or greater than 2.
[0017] The following is a detailed description of the method of the invention for manufacturing the above-described fluorine-containing organopolysiloxane. The manufacturing method of the invention is characterized by conducting a hydrosilylation reaction between (A) a fluorine-containing organopolysiloxane represented by the following general formula:
{where all R*'s may be the same or different and designate organic groups that contain fluorine atoms or univalent hydrocarbon groups that do not contain fluorine atoms, at least one R 1 being an organic group that contains a fluorine atom; V is a group selected from the groups corresponding to aforementioned R 1 , a hydrogen atom or an alkoxy group; however, at least one V is a hydrogen atom. Examples of alkoxy groups designated by V are methoxy, ethoxy, isopropoxy, and butoxy groups; "m" is 1 or an integer greater than 1 } and (B) a polystyrene-type compound which is represented by the following general formula: R 7 - (SiR' 2 ) a - Q
(where R''s are the same as defined above; R 7 is an alkenyl group; Q is a polystyrene-type residual radical; and "a" is 0 or 1), the reaction being carried out in the presence of (C) a hydrosilylation catalyst. [0018] The fluorine-containing organopolysiloxane of component (A), which is used in the above method, is represented by the following general formula:
[0019] In this formula, R 1 designates either the same or different organic groups which contain fluorine atoms or univalent hydrocarbon groups that do not contain fluorine atoms, but at least one R 1 should constitute an organic group that contains a fluorine atom. Such an organic group designated by R 1 that contains a fluorine atom may contain at least two groups represented by formula: -CF 3 . Furthermore, the organic group with a fluorine atom is a group that may contain at least one group of formula: -CF 3 on a molecular terminal of the organic group, and either contains or does not contain a group of formula: -CF 3 in a side chain of the organic group. The aforementioned organic group that contains a fluorine atom is represented by the following general formula:
- (CH 2 ) c - (O) d -R 3 or by the following general formula:
- (CH 2 )c - (O) d - (R 4 O) 6 - R 5
In the above formula, R 3 , R 4 , R 5 , "c", "d", and "e" are the same as defined above.
[0020] The preferable organic group that contains fluorine atoms is at least one group selected from the groups of the following formulae: a fluorinated alkyl group that contains a fluorine atom and is represented by the following general formula: - (CH 2 ) C (CF 2 ) f F
(where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) C CF (CF 3 ), (where "c" is an integer equal to or greater than 2); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) c C (CF 3 ) 2 (CF 2 ) f CF 3
(where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); a fluorinated alkyl group represented by the following general formula:
- (CH 2 ) C CH (CF 3 ) (CH 2 ) f CF (CF 3 ) 2
(where "c" is an integer equal to or greater than 2; and "f ' is an integer equal to or greater than 1); and an organic group that contains a fluorine atom and is represented by the following general formula:
- (CH 2 ) c O (CH 2 ) g CF (CF 3 ),
(where "c" is an integer equal to or greater than 2; and "g" is an integer equal to or greater than 2).
[0021] Examples of the aforementioned organic groups with fluorine atoms are the same fluorinated alkyl groups and fluorinated polyether groups that are listed above.
[0022] The univalent hydrocarbon groups that are designated by R 1 and do not contain fluorine atoms are exemplified by the same univalent hydrocarbon groups that are listed above. Most preferable of these groups are univalent hydrocarbon groups that do not contain fluorine atoms and do not have unsaturated aliphatic bonds. Examples of the most preferable groups of this type are methyl and phenyl groups.
[0023] In the above formula, V is a group selected from the groups corresponding to aforementioned R 1 , a hydrogen atom, or an alkoxy group; however, at least one V is a
hydrogen atom. Examples of alkoxy groups designated by V are methoxy, ethoxy, isopropoxy, and butoxy groups; and "m" is an integer equal to or greater than 1. [0024] The fluorine-containing organopolysiloxane that constitutes component (A) is exemplified by compounds represented by the formulae given below, where "m" and "n" are integers equal to or greater than 1.
CH 2 CH 2 CH 2 CH(CF 3 )CH 2 CF(CF 3 ) 2
CH 3 CH 3 CH 3
H-SiO-(SiO)-(SiO)F- -Si-H CH 3 CH 3 CH 3 CH 3
CH 2 CH 2 CH 2 OCH 2 CF(CF 3 )(OCF 2 CF(CF 3 )J 5 F
CH 3 CH 3 CH 3
H-SiO-(SiO)-(SiO)F" -Si-H CH 3 CH 3 CH 3 CH 3 [0025] The polystyrene-type compound of component (B) is represented by the following general formula:
R 7 - (SiR' 2 ) a - Q , where R 1 designates the same or different organic groups with fluorine atoms or univalent hydrocarbon groups that do not contain fluorine atoms. These groups are exemplified by those listed above. Most preferable of these groups are hydrocarbon groups that do not contain fluorine atoms. Even more preferable are univalent hydrocarbon groups that do not contain fluorine atoms and do not have unsaturated aliphatic bonds. Examples of such preferable groups are methyl and phenyl. Furthermore, in the above formula, R 7 designates an alkenyl group such as vinyl, allyl, butenyl, pentenyl, or hexenyl. Most preferable groups are vinyl, allyl, and hexenyl. Also, in the above formula, Q designates a styrene-type
residual radical. Such radical is contained in the polymers of the styrene monomers. More specifically, the aforementioned radical is exemplified by a polystyrene-type residual radical that is capped at a molecular terminal with a group originating from an anionic polymerization initiator and that contains at least two repetitive units of the following general formula:
- C 2 H 2 (R 6 )(C 6 H 5 ) -
[0026] In the above formula, R 6 is a hydrogen atom or a methyl group. Furthermore, the group originating from an anionic polymerization initiator is the same as defined above, preferably an alkyl group and most preferably a butyl group. In the above formula of the polystyrene-type compound of component (B), "a" is 0 or 1.
[0027] The aforementioned polystyrene-type compound of component (B) can be prepared by causing an anionic polymerization of styrene, α-methyl styrene, or a similar styrene-type monomer by using an anionic polymerization initiator such as n-butyl lithium, ethyl lithium, or a similar alkyl lithium; sodium n-amyl, sodium triphenylmethyl, or a similar sodium alkyl; or KNH 2 , or a similar metal amine; and then by causing a reaction with the product of polymerization and allyl chloride, hexenyl chloride, or a similar alkenyl -containing halide, or with dimethylvinylchlorosilane, allyldimethylchlorosilane, hexenyldimethylchlorosilane, or a similar alkenyl-containing chlorosilane. [0028] According to the manufacturing method of the invention, components (A) and (B) are subjected to a hydrosilylation reaction. There are no special restrictions with regard to the amounts in which component (B) can be added, but, in general, it is recommended to add this component in the amount of 0.01 to 10 moles per one mole of silicon-bonded hydrogen atoms of component (A). [0029] A hydrosilylation catalyst of component (C) which is used for acceleration of the hydrosilylation reaction between components (A) and (B) is exemplified by a platinum- type catalyst, a rhodium-type catalyst, or a palladium-type catalyst. The most preferable is the platinum-type catalyst, which is exemplified by a chloroplatinic acid, an alcohol- modified chloroplatinic acid, platinum black, a platinum-olefin complex, a platinum- alkenylsiloxane complex, or a platinum-carbonyl complex. In the aforementioned manufacturing method, there are no special restrictions regarding the amount in which component (C) is added, provided that the added amount accelerates the hydrosilylation between components (A) and (B). It is recommended, however, to add the catalyst in terms
of weight in the amount of 0.1 to 5000 ppm of the catalytic metal atoms of component (C) per total weight of components (A) and (B).
[0030] Also, there are no special restrictions regarding to the temperature and duration of the reaction in accordance with the manufacturing method of the invention. However, in order to accelerate the hydrosilylation reaction, the latter can be carried out with heating at a temperature in the range of 50 to 15O 0 C. If necessary, the process can be carried out with the use of an organic solvent. Such a solvent is represented by hexane, heptane, or a similar aliphatic hydrocarbon; toluene, xylene, hexafluorobenzene, 1,3- bis(trifluoromethyl)benzene, or a similar aromatic hydrocarbon; acetone, methylethylketone, or a similar ketone; as well as other solvents such as ethers, esters, etc. If necessary, the aforementioned organic solvents can be removed after completion of the hydrosilylation reaction to produce a fluorine-containing organopolysiloxane of the invention. Furthermore, the amount of residual silicon-bonded hydrogen atoms, which did not react and remained in the fluorine-containing organopolysiloxane obtained by the method of the invention, can be further reduced by subjecting olefins such as butene, pentene, hexene, heptene, etc., to a hydrosilylation reaction. [0031] The following is a more detailed description of the organic polymer composition of the invention. [0032] The organic polymer composition of the invention is characterized by including the aforementioned fluorine-containing organopolysiloxane. There are no special restrictions regarding the organic polymer that constitutes the main component of the aforementioned composition. For example, this may be polyethylene resin, polypropylene resin, ethylene-propylene-diene rubber, ethylene-propylene rubber, isoprene rubber, butyl rubber, styrene-butadiene rubber, polybutadiene rubber, NBR rubber, natural rubber, fluoro rubber propylene rubber, ABS resin, AS resin, SB resin, polyacetal resin, polystyrene resin, a vinylchloride- vinylacetate copolymer resin, polymethyl-methacrylate resin, saturated polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, esteracrylate resin, estermethacrylate resin, styrene resin, methylacrylate resin, methylmethacrylate or a similar ester methacrylate/styrene copolymer resin; siloxane cross-linked acrylic resin, organosilicone resin, polyester resin, polyurethane resin, polyarylate resin, polysulfine resin, amino resin, polycarbonate resin, cellulose resin, alkyd resin, and melamine resin. The above polymers can be used individually or in combinations.
[0033] If the aforementioned organic polymer composition of the invention contains an organic polymer with the aforementioned fluorine-containing organopolysiloxane, the latter is added in an amount that depends on factors such as the type of organic polymer, the purpose of improvement of the polymer, and compatibility between the resin and the added fluorine-containing organopolysiloxane. In general, however, it is recommended to add the fluorine-containing organopolysiloxane in the amount of 0.005 to 50 parts by weight, preferably 0.01 to 30 parts by weight per 100 parts by weight of the organic polymer. If the fluorine-containing organopolysiloxane is added in an amount smaller than the recommended lower limit, then the fluorine-containing organopolysiloxane will not produce the desired effect, and if the aforementioned component is added in an amount exceeding the recommended upper limit, this will either impair compatibility of the fluorine-containing organopolysiloxane with the organic polymer or will reduce the improvement-retaining properties, impair durability, and, in some cases, even reduce the strength of the molded products. [0034] There are no special limitations regarding the method suitable for the preparation of the organic polymer composition of the invention. For example, the composition can be easily prepared by mixing the aforementioned fluorine-containing organopolysiloxane and the organic polymer. The mixing process can be carried out by dispersing or dissolving a fluorine-containing organopolysiloxane in a solvent. There are no restrictions regarding the type of solvent, provided that it does not adversely affect the organic polymer. And then by removing the solvent after uniformly mixing the dispersion solution. Another method consists of direct addition of the fluorine-containing organopolysiloxane to the organic polymer with subsequent mixing and kneading. A third method consists of preliminarily preparing a master batch of the fluorine-containing organopolysiloxane in the organic polymer and then adding the master batch to the organic polymer and uniformly mixing the components. The equipment suitable for mixing the components and thus for preparing the organic polymer composition of the invention comprises the following devices: ultra-dispenser, nanomizer, microfluidizer, ultimizer, ultrasonic dispenser, Henschel mixer, kneader mixer, continuous-action kneader extruder, or the like.
[0035] When the composition is applied to the surface of a molded product, in order to facilitate the application operation, the composition is generally diluted prior to application with an appropriate organic solvent. Such solvent is exemplified by methyl cellosolve,
ethyl cellosolve, carbitol, or a similar glycol; benzene, toluene, xylene, chlorobenzene, or a similar aromatic hydrocarbon; acetone, methylethyl ketone, methylisobutyl ketone, or a similar ketone; ethyl acetate, butyl acetate, or a similar ester; 1,1,1-trifluorotrichloroethane, or a similar hydrocarbon that contains fluorine atoms. These solvents can be used in combinations of two or more.
[0036] The organic polymer composition of the invention may contain other additional components such as pigments, fillers, plasticizers, heat-resistant agents, thermal stabilizers, weatherproofing agents, mold-release agents, antioxidants, flame retardants, ultraviolet-ray absorbents, antistatic agents, vulcanization agents, vulcanization accelerators, etc. Examples
[0037] The fluorine-containing organopolysiloxane. method of manufacturing thereof, and the organic polymer composition of the invention will be further described in more detail with reference to application and comparative examples. In the following examples, the values of viscosities were measured at 25°C. [Application Example 1]
[0038] A flask was filled with 3.9 grams of an organopolysiloxane of the following average formula:
5 wt.% isopropyl alcohol solution of a chloroplatinic acid (the content of metallic platinum in terms of weight units was 20 ppm per total weight of the reaction raw material), 12 grams of a polystyrene-type compound represented by the following average formula:
C 4 H 9 (C 2 H 3 (C 6 H 5 )) , 4 ,-CH 2 CH = CH 2 , and 15.9 grams of toluene. The components were heated, and a reaction was carried out for 5 hours at 8O 0 C. Following this, 8.4 grams of 1-hexane were added, and the reaction was continued for another hour at 8O 0 C. On completion of the reaction, at a temperature of 110 0 C, the pressure was reduced to 1.3 kPa, whereby the organic solvent and the low- boiling-point components were removed by distillation. As a result, a white solid substance was obtained. 29 Si-Nuclear Magnetic Resonance analysis (hereinafter referred to as " 29 Si-
NMR"), 13 C-Nuclear Magnetic Resonance analysis (hereinafter referred to as " 13 C-NMR"), and Fourier transform infrared spectrophotometry (hereinafter referred to as "FT-IR") confirmed that the obtained white solid substance comprised a reaction mixture, the main components of which were a fluorine-containing organopolysiloxanes represented by the average formulae given below.
[Application Example 2]
[0039] A white solid substance was obtained by the same method as in Application Example 1, except that 12 g of a polystyrene compound of the following average formula:
CH 3
C 4 H 9 (C 2 H 3 (C 6 H 5 )J 141 -Si- (CH 2 J 4 CH=CH 2
CH 3 were used instead of 12 g of the polystyrene compound of the average formula:
C 4 H 9 (C 2 H 3 (C 6 H 5 )) , 41 -CH 2 CH = CH 2 were used in Application Example 1. 29 Si-NMR, 13 C-NMR, and FT-IR confirmed that the obtained white solid substance comprised a reaction mixture, the main components of which were fluorine-containing organopolysiloxanes represented by the average formulae given below.
[Application Example 3]
[0040] A white solid substance was obtained by the same method as in Application Example 1, except that 3.6 g of an organopolysiloxane of the following average formula:
[Application Example 4]
[0041] 8.3 parts by weight of a bisphenol Z-type polycarbonate resin (Z200, the product of Mitsubishi Gas Chemical Co., Ltd.) were dissolved in 100 parts by weight of monochlorobenzene. The solution was combined with 0.4 parts by weight of the fluorine- containing organopolysiloxane obtained in Application Example 1 , and the mixture was well shaken, whereby a uniform dispersion was obtained. The dispersion was applied onto a glass slide and dried in an oven. As a result, a coating film was formed. Contact angles of the coating film with water and with dimethylsilicone oil having a viscosity of 100 mm 2 /s were measured by means of a contact-angle measurement instrument of Kyowa Kaimen Kagaku Co., Ltd. The results of the measurements are shown in Table 1.
[Application Example 5]
[0042] A uniform dispersion was prepared in the same manner as in Application Example 4, except that 0.4 parts by weight of the fluorine-containing organopolysiloxane obtained in Application Example 2 were added. The dispersion was applied onto a glass slide and dried in an oven. As a result, a coating film was formed. Contact angles of the coating film with water and with dimethylsilicone oil having a viscosity of 100 mm 2 /s were measured by means of a contact-angle measurement instrument of Kyowa Kaimen Kagaku Co., Ltd. The results of the measurements are shown in Table 1. [Application Example 6]
[0043] A uniform dispersion was prepared in the same manner as in Application Example 4, except that 0.4 parts by weight of the fluorine-containing organopolysiloxane obtained in Application Example 3 were added, The dispersion was applied onto a glass slide and dried in an oven. As a result, a coating film was formed. Contact angles of the coating film with water and with dimethylsilicone oil having a viscosity of 100 mm 2 /s were measured by means of a contact-angle measurement instrument of Kyowa Kaimen Kagaku Co., Ltd. The results of the measurements are shown in Table 1.
[Comparative Example 1 ]
[0044] A uniform dispersion was prepared in the same manner as in Application
Example 4, except that 0.4 parts by weight of the fluorine-containing organopolysiloxane which was prepared by the same method as the one used in Application Example 2 and disclosed in Kokai 2001-172461 and which is represented by the following average formula.
[0045]
[Table 1]
Industrial Applicability
[0046] The fluorine-containing organopolysiloxane of the invention, when compounded with an organic polymer, makes it possible to form a coating film that, without reducing strength of the organic polymer, acquires characteristics such as uniform transparency, resistance to oil, surface lubrication, smoothness, reduced friction, water- repellency and oil-repellency, waterproof properties, moisture resistance, antiseptic properties, resistance to contamination, peeling ability, mold-release properties, etc. Therefore, the fluorine-containing organopolysiloxane can be used as a property-improving
agent for organic polymers. The fluorine-containing organopolysiloxane of the invention is suitable for use as the following: water-repellent oiling agent; lubricating agent; additive to a lubricating agent; rust-resistant agent; contamination-resistant agent; oil-resistant agent; waterproofing agent; peeling agent; mold-release agent; moisture-resisting agent; additive to paint and coatings; leveling agent for paint and coatings; gloss-imparting agent in combination with wax; surface-active agent; protective agent for various substrates such as fibers, metals, paper, wood, glass, ceramic, porcelain, magnets, minerals, or other inorganic substances; substrates coated by vapor-deposition methods with alloys having strong magnetic properties which contain iron, cobalt, and/or nickel as main components, in the presence of small amounts of aluminum, silicon, chromium, manganese, molybdenum, titanium, various heavy metals, rare earth metals, etc.; or iron, cobalt, chromium, or similar magnetic materials in the presence of minute quantities of oxygen; or protective films such as magnetic layers of magnetic disks or magnetic tapes formed by applying magnetic materials such as cobalt, chromium, etc., by means of a vapor- deposition method onto polyester or a similar plastic film. Furthermore, the fluorine- containing organopolysiloxane of the invention can also be used as an agent for treating magnetic recording media such as magnetic tapes, magnetic disks, optical magnetic disks, flexible disks, or similar magnetic recording media that require low-friction characteristics on the front and back surfaces.