JP2007177080A - Fluorine-containing organopolysiloxane, its manufacturing method and organic polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel fluorine-containing organopolysiloxane and its manufacturing method, and to provide an organic polymer composition that comprises the fluorine-containing organopolysiloxane and forms a film homogeneous, transparent and excellent in surface lubricating properties. <P>SOLUTION: The fluorine-containing organopolysiloxane is represented by general formula (1) äwherein R<SP>1</SP>is a fluorine atom-containing organic group or a monovalent hydrocarbon group bearing no fluorine atom, provided that at least one R<SP>1</SP>is a fluorine atom-containing organic group; Z is a group selected from the group consisting of R<SP>1</SP>above, a group represented by general formula (I): -[R<SP>2</SP>-(SiR<SP>1</SP><SB>2</SB>)<SB>a</SB>]<SB>b</SB>-Q (wherein R<SP>1</SP>is the same as above; R<SP>2</SP>is an alkylene group; Q is a polystyrene residue; a is 0 or 1; and b is 0 or 1), a hydroxy group, a hydrogen atom and an alkoxy group, provided that at least one Z is a group represented by general formula (I); and m in an integer of at least 1}. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel fluorine-containing organopolysiloxane, a method for producing the same, and an organic polymer composition containing the same.

  It is known to add a fluorine-containing organopolysiloxane in order to improve the molding processability and releasability of an organic polymer and improve the lubrication characteristics of a molded product. Examples of such fluorine-containing organopolysiloxane include: Patent Document 1 discloses an organopolysiloxane containing a polyfluoroalkyl group having 3 to 20 carbon atoms, and Patent Document 2 discloses a linear or branched alkyl group having 3 or more carbon atoms and a perfluoroalkyl group. An organopolysiloxane containing a fluoroalkyl group is disclosed, and Patent Document 3 discloses an organopolysiloxane containing a perfluoroalkyl group and a polystyrene chain or a polymethylstyrene chain.

However, in general, fluorine-containing organopolysiloxane has a low surface tension, and it is difficult to uniformly dissolve it in an organic polymer having a high surface tension, and the dispersion of the material is poor due to poor compatibility with the organic polymer. There is a problem that it is difficult to obtain an organic polymer composition that is insufficient and highly transparent. Moreover, if the compatibility with the organic polymer is increased by lowering the fluorine concentration in the fluorine-containing organopolysiloxane, the modification property of the organic polymer surface becomes insufficient, and the oil resistance, lubricity, smoothness, anti-friction property, Water and oil repellency, water resistance, moisture resistance, rust resistance, antifouling, releasability, releasability, etc. are difficult to develop, and when it is liquid, there is a problem that the strength of the organic polymer decreases. . Therefore, a fluorine-containing organopolysiloxane that can be uniformly dispersed in an organic polymer and can impart sufficient surface modification properties is desired.
JP-A-1-282267 JP-A-7-233257 JP 2001-172461 A

  An object of the present invention is to provide a novel fluorine-containing organopolysiloxane that can be uniformly dispersed in an organic polymer and impart sufficient surface modification properties, and a method for producing the same. The object of the present invention is to provide an organic polymer composition containing such a fluorine-containing organopolysiloxane, forming a film that is homogeneous, transparent, and excellent in surface lubricity.

｛式中、Ｒ¹は同じかまたは異なるフッ素原子含有有機基もしくはフッ素原子を有さない一価炭化水素基であり、但し、少なくとも１個のＲ¹はフッ素原子含有有機基であり、Ｚは、前記Ｒ¹、一般式(Ｉ)：
−[Ｒ²−(ＳiＲ¹ ₂)_a]_b−Ｑ
（式中、Ｒ¹は前記と同じであり、Ｒ²はアルキレン基であり、Ｑはポリスチレン系残基であり、ａは０または１であり、ｂは０または１である。）
で表される基、水酸基、水素原子、およびアルコキシ基からなる群より選択される基であり、但し、Ｚの少なくとも一つは前記一般式(Ｉ)で表される基であり、ｍは１以上の整数である。｝
で表される。 The fluorine-containing organopolysiloxane of the present invention has a general formula:

{Wherein R ¹ is the same or different fluorine atom-containing organic group or a monovalent hydrocarbon group having no fluorine atom, provided that at least one R ¹ is a fluorine atom-containing organic group, and Z is And R ¹ , the general formula (I):
− [R ² − (SiR ¹ ₂ ) _a ] _b −Q
(In the formula, R ¹ is the same as above, R ² is an alkylene group, Q is a polystyrene residue, a is 0 or 1, and b is 0 or 1.)
And a group selected from the group consisting of a hydroxyl group, a hydrogen atom, and an alkoxy group, provided that at least one of Z is a group represented by the general formula (I), and m is 1 It is an integer above. }
It is represented by

｛式中、Ｒ¹は同じかまたは異なるフッ素原子含有有機基もしくはフッ素原子を有さない一価炭化水素基であり、但し、少なくとも１個のＲ¹はフッ素原子含有有機基であり、Ｖは、前記Ｒ¹、水素原子、およびアルコキシ基からなる群より選択される基であり、但し、Ｖの少なくとも一つは水素原子であり、ｍは１以上の整数である。｝
で表される含フッ素オルガノポリシロキサンと(Ｂ)一般式：
Ｒ⁷−(ＳiＲ¹ ₂)_a−Ｑ
（式中、Ｒ¹は前記と同じであり、Ｒ⁷はアルケニル基であり、Ｑはポリスチレン系残基であり、ａは０または１である。）
で表されるポリスチレン系化合物を、(Ｃ)ヒドロシリル化反応用触媒の存在下、ヒドロシリル化反応することを特徴とする。 Further, the method for producing the fluorine-containing organopolysiloxane of the present invention comprises (A) a general formula:

{Wherein R ¹ is the same or different fluorine atom-containing organic group or a monovalent hydrocarbon group having no fluorine atom, provided that at least one R ¹ is a fluorine atom-containing organic group, and V is , R ¹ , a hydrogen atom and a group selected from the group consisting of alkoxy groups, provided that at least one of V is a hydrogen atom and m is an integer of 1 or more. }
And a fluorine-containing organopolysiloxane represented by formula (B):
_{^{R 7 - (SiR 1 2)}} a -Q
(In the formula, R ¹ is the same as above, R ⁷ is an alkenyl group, Q is a polystyrene residue, and a is 0 or 1.)
(C) Hydrosilylation reaction is carried out in the presence of a catalyst for hydrosilylation reaction.

  The organic polymer composition of the present invention is characterized by containing the above-mentioned fluorine-containing organopolysiloxane.

  The fluorine-containing organopolysiloxane of the present invention is a novel compound that can be uniformly dispersed in an organic polymer and can impart sufficient surface modification properties. The production method of the present invention comprises such a fluorine-containing organopolysiloxane. It can be manufactured efficiently. In addition, since the organic polymer composition of the present invention contains such a fluorine-containing organopolysiloxane, it is characterized in that it can form a film that is homogeneous and transparent and has excellent surface lubricity.

で表される。上式中、Ｒ¹は同じかまたは異なるフッ素原子含有有機基もしくはフッ素原子を有さない一価炭化水素基である。但し、少なくとも１個のＲ¹はフッ素原子含有有機基である。このＲ¹のフッ素原子含有有機基としては、式：−ＣＦ₃で表される基を少なくとも２個含有するフッ素原子含有有機基であることが好ましく、さらには、フッ素原子含有有機基の末端に、式：−ＣＦ₃で表される基を少なくとも１個含有し、該有機基の側鎖に、式：−ＣＦ₃で表される基を含有するか、または含有しないフッ素原子含有有機基であることが好ましい。このようなフッ素原子含有有機基として、具体的には、一般式：
−(ＣＨ₂)_c−(Ｏ)_d−Ｒ³
で表されるフッ素原子含有有機基、または一般式：
−(ＣＨ₂)_c−(Ｏ)_d−(Ｒ⁴Ｏ)_e−Ｒ⁵
で表されるフッ素原子含有有機基であることが好ましい。上式中、Ｒ³は、フッ化アルキル基の末端に、式：−ＣＦ₃で表される基を少なくとも１個含有し、該アルキル基の側鎖に、式：−ＣＦ₃で表される基を含有するか、または含有しないフッ化アルキル基である。また、上式中、Ｒ⁴は、式：−ＣＦ₃で表される基を含有するか、または含有しないフッ化アルキレン基である。また、上式中、Ｒ⁵は、フッ化アルキル基の末端に、式：−ＣＦ₃で表される基を少なくとも１個含有し、該アルキル基の側鎖に、式：−ＣＦ₃で表される基を含有するか、または含有しないフッ化アルキル基である。また、上式中、ｃは２以上の整数であり、ｄは０または１であり、また、ｅは１以上の整数である。 First, the fluorine-containing organopolysiloxane of the present invention will be described in detail.
The fluorine-containing organopolysiloxane of the present invention has a general formula:

It is represented by In the above formula, R ¹ is the same or different fluorine-containing organic group or a monovalent hydrocarbon group having no fluorine atom. However, at least one R ¹ is a fluorine atom-containing organic group. The fluorine atom-containing organic group represented by R ¹ is preferably a fluorine atom-containing organic group containing at least two groups represented by the formula: —CF ₃ , and further, at the end of the fluorine atom-containing organic group. , formula contains at least one group represented by -CF _3, in the side chain of the organic group of the formula: or containing a group represented by -CF _3, or does not contain a fluorine atom-containing organic group Preferably there is. As such a fluorine atom-containing organic group, specifically, a general formula:
_{- (CH 2) c - (} O) d -R 3
A fluorine atom-containing organic group represented by the general formula:
_{- (CH 2) c - (} O) d - (R 4 O) e -R 5
It is preferable that it is a fluorine atom containing organic group represented by these. In the above formula, R ³ is at the end of the fluoroalkyl group of the formula: a group represented by -CF ₃ least one contains, in a side chain of the alkyl group, the formula: represented by -CF ₃ It is a fluorinated alkyl group containing or not containing a group. In the above formula, R ⁴ is a fluorinated alkylene group containing or not containing a group represented by the formula: —CF ₃ . In the above formula, R ⁵ is the end of the fluoroalkyl group of the formula: a group represented by -CF ₃ least one contains, in a side chain of the alkyl group, the formula: Table with -CF ₃ A fluorinated alkyl group that contains or does not contain any of the groups described above. In the above formula, c is an integer of 2 or more, d is 0 or 1, and e is an integer of 1 or more.

Particularly preferred fluorine atom-containing organic groups have the general formula:
− (CH ₂ ) _c (CF ₂ ) _f F
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c CF (} CF 3) 2
(In the formula, c is an integer of 2 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c C (} CF 3) 2 (CF 2) f CF 3
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c CH (} CF 3) (CH 2) f CF (CF 3) 2
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c O (} CH 2) g CF (CF 3) 2
(In the formula, c is an integer of 2 or more, and g is an integer of 2 or more.)
Is at least one group selected from the group consisting of fluorine atom-containing organic groups.

As such a fluorine atom-containing organic group, for example,
-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
A fluorinated alkyl group such as
_{-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)} s F
-(CH ₂ ) ₂ CF ₂ {OCF ₂ CF (CF ₃ )} _s F
-(CH ₂ ) ₃ OCH ₂ CF (CF ₃ ) {OCF ₂ CF (CF ₃ )} _s F
_{- (CH 2) 3 OCF 2} CF (CF 3) {OCF 2 CF (CF 3)} s F
And fluorinated polyether groups such as

Examples of the monovalent hydrocarbon group having no fluorine atom for R ¹ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, dodecyl group, and octadecyl group; vinyl group Alkenyl groups such as allyl groups; monovalent hydrocarbon groups such as aryl groups such as phenyl groups and naphthyl groups, preferably methyl groups and phenyl groups.

In the above formula, Z represents R ¹ and the general formula (I):
− [R ² − (SiR ¹ ₂ ) _a ] _b −Q
And a group selected from the group consisting of a hydroxyl group, a hydrogen atom, and an alkoxy group, provided that at least one of Z is a group represented by the general formula (I). In the above formula, R ¹ is the same or different fluorine atom-containing organic group or monovalent hydrocarbon group having no fluorine atom, and examples thereof are the same groups as described above, preferably having an aliphatic unsaturated bond. A monovalent hydrocarbon group, particularly preferably a methyl group or a phenyl group. In the above formula, R ² is an alkylene group, and examples thereof include an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, preferably an ethylene group, a propylene group, and a hexylene group. In the above formula, Q is a polystyrene residue, which is a group containing a polymer of a styrene monomer. Specifically, the general formula:
−C ₂ H ₂ (R ⁶ ) (C ₆ H ₅ ) −
It is preferably a polystyrene-based residue having at least two repeating units represented by the formula and having the terminal blocked with a group derived from an anionic polymerization initiator. In the above formula, R ⁶ is a hydrogen atom or a methyl group. Examples of the group derived from the terminal anionic polymerization initiator include substituted or unsubstituted alkyl groups such as n-butyl group, ethyl group, n-amyl group and triphenylmethyl group; isopropoxy group and ethoxy group. An alkoxy group such as —NH ₂ , —NHC ₆ H ₅ or the like; or a hydroxyl group, preferably an alkyl group, and particularly preferably a butyl group. In the above formula, a is 0 or 1, and b is 0 or 1.

In the above formula, m is an integer of 0 or more, and n is an integer of 1 or more. Examples of the fluorine-containing organopolysiloxane of the present invention include the following compounds. In the formula, m is an integer of 1 or more, n is an integer of 1 or more, and r is an integer of 2 or more.

｛式中、Ｒ¹は同じかまたは異なるフッ素原子含有有機基もしくはフッ素原子を有さない一価炭化水素基であり、但し、少なくとも１個のＲ¹はフッ素原子含有有機基であり、Ｖは、前記Ｒ¹、水素原子、およびアルコキシ基からなる群より選択される基であり、但し、Ｖの少なくとも一つは水素原子であり、ｍは１以上の整数である。｝
で表される含フッ素オルガノポリシロキサンと(Ｂ)一般式：
Ｒ⁷−(ＳiＲ¹ ₂)_a−Ｑ
（式中、Ｒ¹は前記と同じであり、Ｒ⁷はアルケニル基であり、Ｑはポリスチレン系残基であり、ａは０または１である。）
で表されるポリスチレン系化合物を、(Ｃ)ヒドロシリル化反応用触媒の存在下、ヒドロシリル化反応することを特徴とする。 Next, the manufacturing method of the fluorine-containing organopolysiloxane of this invention is demonstrated in detail.
The production method of the present invention comprises (A) a general formula:

{Wherein R ¹ is the same or different fluorine atom-containing organic group or a monovalent hydrocarbon group having no fluorine atom, provided that at least one R ¹ is a fluorine atom-containing organic group, and V is , R ¹ , a hydrogen atom and a group selected from the group consisting of alkoxy groups, provided that at least one of V is a hydrogen atom and m is an integer of 1 or more. }
And a fluorine-containing organopolysiloxane represented by formula (B):
_{^{R 7 - (SiR 1 2)}} a -Q
(In the formula, R ¹ is the same as above, R ⁷ is an alkenyl group, Q is a polystyrene residue, and a is 0 or 1.)
(C) Hydrosilylation reaction is carried out in the presence of a catalyst for hydrosilylation reaction.

で表される。上式中、Ｒ¹は同じかまたは異なるフッ素原子含有有機基もしくはフッ素原子を有さない一価炭化水素基である。但し、少なくとも１個のＲ¹はフッ素原子含有有機基である。このＲ¹のフッ素原子含有有機基としては、式：−ＣＦ₃で表される基を少なくとも２個含有するフッ素原子含有有機基であることが好ましく、さらには、フッ素原子含有有機基の末端に、式：−ＣＦ₃で表される基を少なくとも１個含有し、該有機基の側鎖に、式：−ＣＦ₃で表される基を含有するか、または含有しないフッ素原子含有有機基であることが好ましい。このようなフッ素原子含有有機基として、具体的には、一般式：
−(ＣＨ₂)_c−(Ｏ)_d−Ｒ³
で表されるフッ素原子含有有機基、または一般式：
−(ＣＨ₂)_c−(Ｏ)_d−(Ｒ⁴Ｏ)_e−Ｒ⁵
で表されるフッ素原子含有有機基であることが好ましい。上式中、Ｒ³、Ｒ⁴、Ｒ⁵、ｃ、ｄ、およびｅは前記の通りである。 In the production method of the present invention, the fluorine-containing organopolysiloxane of component (A) has the general formula:

It is represented by In the above formula, R ¹ is the same or different fluorine-containing organic group or a monovalent hydrocarbon group having no fluorine atom. However, at least one R ¹ is a fluorine atom-containing organic group. The fluorine atom-containing organic group represented by R ¹ is preferably a fluorine atom-containing organic group containing at least two groups represented by the formula: —CF ₃ , and further, at the end of the fluorine atom-containing organic group. , formula contains at least one group represented by -CF _3, in the side chain of the organic group of the formula: or containing a group represented by -CF _3, or does not contain a fluorine atom-containing organic group Preferably there is. As such a fluorine atom-containing organic group, specifically, a general formula:
_{- (CH 2) c - (} O) d -R 3
A fluorine atom-containing organic group represented by the general formula:
_{- (CH 2) c - (} O) d - (R 4 O) e -R 5
It is preferable that it is a fluorine atom containing organic group represented by these. In the above formula, R ³ , R ⁴ , R ⁵ , c, d, and e are as described above.

Particularly preferred fluorine atom-containing organic groups have the general formula:
− (CH ₂ ) _c (CF ₂ ) _f F
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c CF (} CF 3) 2
(In the formula, c is an integer of 2 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c C (} CF 3) 2 (CF 2) f CF 3
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c CH (} CF 3) (CH 2) f CF (CF 3) 2
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c O (} CH 2) g CF (CF 3) 2
(In the formula, c is an integer of 2 or more, and g is an integer of 2 or more.)
Is at least one group selected from the group consisting of fluorine atom-containing organic groups. Examples of such fluorine atom-containing organic groups include the same fluorinated alkyl groups and fluorinated polyether groups as described above.

Examples of the monovalent hydrocarbon group having no fluorine atom for R ¹ include the same monovalent hydrocarbon groups as described above, preferably a monovalent hydrocarbon group having no fluorine atom and no aliphatic unsaturated bond. A hydrogen group, particularly preferably a methyl group or a phenyl group.

In the above formula, V is a group selected from the group consisting of R ¹ , a hydrogen atom, and an alkoxy group, provided that at least one of V is a hydrogen atom. Examples of the alkoxy group of V include a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group. In the above formula, m is an integer of 1 or more.

Examples of the fluorine-containing organopolysiloxane of the component (A) include the following compounds. In the formula, m is an integer of 1 or more, and n is an integer of 1 or more.

The polystyrene-based compound of component (B) has the general formula:
_{^{R 7 - (SiR 1 2)}} a -Q
It is represented by In the above formula, R ¹ is the same or different fluorine-containing organic group or a monovalent hydrocarbon group having no fluorine atom, and examples thereof are the same groups as described above. It is a monovalent hydrocarbon group, more preferably a monovalent hydrocarbon group having no fluorine atom and an aliphatic unsaturated bond, and particularly preferably a methyl group or a phenyl group. In the above formula, R ⁷ is an alkenyl group, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group, an allyl group, and a hexenyl group are preferable. In the formula, Q is a polystyrene-based residue, which is a group containing a polymer of a styrene monomer. Specifically, the general formula:
−C ₂ H ₂ (R ⁶ ) (C ₆ H ₅ ) −
It is preferably a polystyrene-based residue having at least two repeating units represented by the formula and having the terminal blocked with a group derived from an anionic polymerization initiator. In the above formula, R ⁶ is a hydrogen atom or a methyl group. Examples of the group derived from the terminal anionic polymerization initiator include the same groups as described above, preferably an alkyl group, and particularly preferably a butyl group. In the above formula, a is 0 or 1.

Such (B) component polystyrene compounds include styrene monomers such as styrene and α-methylstyrene, such as alkyllithiums such as n-butyllithium and ethyllithium; n-amyl sodium, triphenylmethylsodium and the like. Anion polymerization using an anionic polymerization initiator such as metal amines such as KNH ₂ , and alkenyl group-containing halides such as allyl chloride and hexenyl chloride, or dimethylvinylchlorosilane, allyldimethylchlorosilane, hexenyl. It can be prepared by reacting with an alkenyl group-containing chlorosilane such as dimethylchlorosilane.

  In the production method of the present invention, the component (A) and the component (B) are hydrosilylated. The amount of the component (B) added at that time is not particularly limited, but the silicon atom-bonded hydrogen atom in the component (A) is not limited. The amount of component (B) is preferably in the range of 0.01 to 10 moles relative to 1 mole.

  In the production method of the present invention, the catalyst for hydrosilylation reaction (C) for accelerating the hydrosilylation reaction of the components (A) and (B) includes a platinum catalyst, a rhodium catalyst, and a palladium catalyst. Exemplified, platinum catalyst is particularly preferable. Examples of the platinum catalyst of component (C) include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum black, platinum olefin complexes, platinum alkenylsiloxane complexes, and platinum carbonyl complexes. In the former production method, the amount of component (C) added is not particularly limited as long as it promotes the hydrosilylation reaction of components (A) and (B). The amount of the catalytic metal atom in the component (C) is in the range of 0.1 to 5,000 ppm with respect to the total weight of the component B).

  In the production method of the present invention, the reaction temperature, reaction time and the like are not particularly limited, but heating is preferably performed to promote the hydrosilylation reaction, and for example, heating to 50 to 150 ° C. is preferable. In the production method of the present invention, an organic solvent may be used. Usable organic solvents include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene, xylene, hexafluorobenzene, 1,3-bis (trifluoromethyl) benzene; ketones such as acetone and methyl ethyl ketone Other examples include ethers and esters. These organic solvents can be removed as necessary after the hydrosilylation reaction to obtain the fluorine-containing organopolysiloxane of the present invention. In the production method of the present invention, unreacted silicon-bonded hydrogen atoms remaining in the resulting fluorine-containing organopolysiloxane are reduced by hydrosilylation reaction of olefins such as butene, pentene, hexene, and heptene. Can do.

Next, the organic polymer composition of the present invention will be described in detail.
The organic polymer composition of the present invention is characterized by containing the above-mentioned fluorine-containing organopolysiloxane. The organic polymer that is the main component of the composition is not particularly limited. For example, 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 chloroprene rubber, ABS resin, AS resin, SB resin, polyacetal resin, polystyrene resin, vinyl chloride-vinyl acetate copolymer resin, polymethyl methacrylate resin, saturated polyester resin, polyamide resin, polyurethane resin, epoxy resin , Phenol resin, acrylic ester resin, methacrylic ester resin, styrene resin; (meth) acrylic ester such as methyl acrylate and methyl methacrylate and styrene copolymer resin; Examples include sun-crosslinked acrylic resins, organosilicon resins, polyester resins, polyurethane resins, polyarylate resins, polysulfone resins, amino resins, polycarbonate resins, polyfluorinated olefin resins, cellulose resins, alkyd resins, and melamine resins. Alternatively, a plurality of polymers may be mixed and used.

  In the organic polymer composition of the present invention, when the above-mentioned fluorine-containing organopolysiloxane is blended with the organic polymer, the amount of addition depends on the type of organic polymer, the purpose of modification, the resin and the fluorine-containing organo added to the resin. Although it depends on the compatibility with the polysiloxane, generally it is preferably within the range of 0.005 to 50 parts by weight, more preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the organic polymer. It is preferable to be within the range. This is because if the content of the fluorinated organopolysiloxane is less than the lower limit of the above range, the effect of adding the fluorinated organopolysiloxane cannot be exhibited, while if the content exceeds the upper limit of the above range, This is because the compatibility with the organic polymer may be reduced, the durability and durability of the modification function may be reduced, and the strength of the molded product may be reduced in some cases.

  The method for preparing the organic polymer composition of the present invention is not particularly limited. For example, the organic polymer composition can be easily produced by mixing the fluorine-containing organopolysiloxane and the organic polymer. As a mixing method, a fluorine-containing organopolysiloxane is dispersed or dissolved in a solvent (the solvent is not particularly limited as long as it does not adversely affect the organic polymer), and then added, and after uniform mixing, the solvent is removed directly. Examples thereof include a method of adding to a polymer and kneading, and a method of preparing a master batch with an organic polymer in advance, and then adding the master batch to the organic polymer and mixing uniformly. In addition, devices for mixing such components to produce the organic polymer composition of the present invention include ultradisperser, nanomizer, microfluidizer, optimizer, ultrasonic disperser, Hensel mixer, kneader mixer Examples thereof include a mixing device such as a continuous kneading extruder.

  On the other hand, when applying to the surface of a molded article, it is usually preferable to dilute in advance with an appropriate organic solvent in order to facilitate the application operation. Examples of the organic solvent include glycols such as methyl cellosolve, ethyl cellosolve, and carbitol; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate And esters such as butyl acetate; and fluorine-containing hydrocarbons such as 1,1,1-trifluorotrichloroethane. Two or more kinds of these organic solvents may be used in combination.

  In the organic polymer composition of the present invention, as other components, pigments, fillers, plasticizers, heat agents, heat stabilizers, weather resistance improvers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, You may contain an antistatic agent, a vulcanizing agent, a vulcanization accelerator, etc.

  The fluorine-containing organopolysiloxane, the production method thereof, and the organic polymer composition of the present invention will be described in detail with reference to Examples and Comparative Examples. In addition, the viscosity in an Example is the value measured at 25 degreeC.

で表されるオルガノポリシロキサン３.９ｇ、５重量％−塩化白金酸のイソプロピルアルコール溶液（反応原料の合計重量に対して、白金金属が重量単位で２０ｐｐｍとなる量）、平均式：
Ｃ₄Ｈ₉{Ｃ₂Ｈ₃(Ｃ₆Ｈ₅)}₁₄₁−ＣＨ₂ＣＨ＝ＣＨ₂
で表されるポリスチレン系化合物１２ｇ、トルエン１５.９ｇを加え、徐々に加熱し、８０℃で５時間反応した。次に、１−ヘキセン８.４ｇを加え、さらに８０℃で１時間反応を続けた。その後、１１０℃で１.３ｋＰａまで減圧して、有機溶媒や低沸点成分を除去することにより白色固体状物を得た。この白色固体状物を²⁹Ｓi−核磁気共鳴分析（以下、²⁹Ｓi−ＮＭＲ）、¹³Ｃ−核磁気共鳴分析（以下、¹³Ｃ−ＮＭＲ）、およびフーリエ積分赤外線分光分析（以下、ＦＴ−ＩＲ）により分析した結果、次の平均式で表される含フッ素オルガノポリシロキサンを主成分とする反応混合物であることが判明した。 [Example 1]
In flask, average formula:

3.9 g of an organopolysiloxane represented by the formula: 5% by weight-an isopropyl alcohol solution of chloroplatinic acid (amount in which platinum metal is 20 ppm by weight relative to the total weight of the reaction raw material), average formula:
C ₄ H ₉ {C ₂ H ₃ (C ₆ H ₅ )} ₁₄₁ —CH ₂ CH═CH ₂
Were added, and the mixture was gradually heated and reacted at 80 ° C. for 5 hours. Next, 8.4 g of 1-hexene was added, and the reaction was further continued at 80 ° C. for 1 hour. Thereafter, the pressure was reduced to 1.3 kPa at 110 ° C. to remove the organic solvent and low-boiling components, thereby obtaining a white solid. This white solid was analyzed by ²⁹ Si-nuclear magnetic resonance analysis (hereinafter ²⁹ Si-NMR), ¹³ C-nuclear magnetic resonance analysis (hereinafter ¹³ C-NMR), and Fourier integral infrared spectroscopy (hereinafter FT-IR). As a result, it was found that the reaction mixture was mainly composed of a fluorine-containing organopolysiloxane represented by the following average formula.

で表されるポリスチレン系化合物１２ｇを用いた以外は実施例１と同様にして、白色固体状物を得た。この白色固体状物を²⁹Ｓｉ−ＮＭＲ、¹³Ｃ−ＮＭＲ、およびＦＴ−ＩＲにより分析した結果、次の平均式で表される含フッ素オルガノポリシロキサンを主成分とする反応混合物であることが判明した。 [Example 2]
In Example 1, the average formula:
C ₄ H ₉ {C ₂ H ₃ (C ₆ H ₅ )} ₁₄₁ —CH ₂ CH═CH ₂
In place of 12 g of the polystyrene compound represented by the formula:

A white solid was obtained in the same manner as in Example 1 except that 12 g of the polystyrene compound represented by This white solid was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR. As a result, it was found to be a reaction mixture mainly composed of a fluorine-containing organopolysiloxane represented by the following average formula: did.

で表されるオルガノポリシロキサンの代わりに、平均式：

で表されるオルガノポリシロキサン３.６ｇを用いた以外は実施例１と同様にして、白色固体状物を得た。この白色固体状物を²⁹Ｓｉ−ＮＭＲ、¹³Ｃ−ＮＭＲ、およびＦＴ−ＩＲにより分析した結果、次の平均式で表される含フッ素オルガノポリシロキサンを主成分とする反応混合物であることが判明した。 [Example 3]
In Example 1, the average formula:

Instead of the organopolysiloxane represented by the average formula:

A white solid was obtained in the same manner as in Example 1 except that 3.6 g of the organopolysiloxane represented by formula (1) was used. This white solid was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR. As a result, it was found to be a reaction mixture mainly composed of a fluorine-containing organopolysiloxane represented by the following average formula: did.

[Example 4]
8.3 parts by weight of bisphenol Z-type polycarbonate resin (trade name Z200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dissolved in 100 parts by weight of monochlorobenzene. When 0.4 part by weight of the fluorinated organopolysiloxane obtained in Example 1 was added to this solution and well mixed, a uniform dispersion was obtained. This dispersion was applied to a slide glass and dried in an oven to form a film. The contact angle of the obtained film to water and dimethyl silicone oil having a viscosity of 100 mm ² / s was measured with a contact angle measuring device manufactured by Kyowa Interface Science. These measurement results are shown in Table 1.

[Example 5]
In Example 4, instead of the fluorine-containing organopolysiloxane obtained in Example 1, 0.4 parts by weight of the fluorine-containing organopolysiloxane obtained in Example 2 was added, and the same procedure as in Example 4 was performed. When a dispersion was prepared, a uniform dispersion was obtained. This dispersion was applied to a slide glass and dried in an oven to form a film. The contact angle of the obtained film to water and dimethyl silicone oil having a viscosity of 100 mm ² / s was measured with a contact angle measuring device manufactured by Kyowa Interface Science. These measurement results are shown in Table 1.

[Example 6]
In Example 4, instead of the fluorine-containing organopolysiloxane obtained in Example 1, 0.4 parts by weight of the fluorine-containing organopolysiloxane obtained in Example 3 was added, and the same procedure as in Example 4 was performed. When a dispersion was prepared, a uniform dispersion was obtained. This dispersion was applied to a slide glass and dried in an oven to form a film. The contact angle of the obtained film to water and dimethyl silicone oil having a viscosity of 100 mm ² / s was measured with a contact angle measuring device manufactured by Kyowa Interface Science. These measurement results are shown in Table 1.

で表される含フッ素オルガノポリシロキサンを０.４重量添加した以外は実施例４と同様にして分散液を調製したところ、均一な分散液が得られた。この分散液をスライドガラスへ塗布しオーブン中で乾燥させて皮膜を形成した。得られた皮膜の水および粘度１００ｍｍ²／ｓのジメチルシリコーンオイルに対する接触角を協和界面科学製の接触角測定装置により測定した。これらの測定結果を表１に示した。 [Comparative Example 1]
In Example 4, instead of the fluorine-containing organopolysiloxane obtained in Example 1, an average formula prepared according to the method described in Example 2 described in JP-A No. 2001-172461:

When a dispersion was prepared in the same manner as in Example 4 except that 0.4% by weight of the fluorine-containing organopolysiloxane represented by the formula (1) was added, a uniform dispersion was obtained. This dispersion was applied to a slide glass and dried in an oven to form a film. The contact angle of the obtained film to water and dimethyl silicone oil having a viscosity of 100 mm ² / s was measured with a contact angle measuring device manufactured by Kyowa Interface Science. These measurement results are shown in Table 1.

The fluorine-containing organopolysiloxane of the present invention, when blended with an organic polymer, does not reduce the strength of the organic polymer, has homogeneity and transparency, oil resistance, surface lubricity, smoothness, antifriction, It can be used as a modifier for organic polymers because it can form films with water and oil repellency, water resistance, moisture resistance, rust resistance, antifouling properties, releasability, releasability, etc. it can. The fluorine-containing organopolysiloxane of the present invention is, for example, a water / oil repellent, a lubricant, an additive for lubricant, a rust preventive, an antifouling agent, an oil resistant agent, a water resistant agent, a release agent, a release agent, Moisture-proofing agent, additive for paints / coating agents, leveling agent for paints / coating agents, polishing agent using wax, surfactant, various fibers, metal, paper, wood, glass, ceramic, ceramics, porcelain, Protective agents such as minerals such as ores, and ferromagnetic alloys deposited on substrates (mainly iron, cobalt and / or nickel, small amounts of aluminum, silicon, chromium, manganese, molybdenum, titanium, various heavy metals, rare earths) Magnetic tape or magnetic disk on which magnetic materials such as iron, cobalt, and chromium are vapor-deposited on plastic films such as polyester in the presence of trace amounts of oxygen) Or protective coating, is also suitable as surface and back surface treating agent for magnetic tapes, magnetic disks, magneto-optical disk, a magnetic recording medium such as a flexible disk antifriction properties are particularly required.

Claims (11)

General formula:

{Wherein R ¹ is the same or different fluorine atom-containing organic group or a monovalent hydrocarbon group having no fluorine atom, provided that at least one R ¹ is a fluorine atom-containing organic group, and Z is And R ¹ , the general formula (I):
− [R ² − (SiR ¹ ₂ ) _a ] _b −Q
(In the formula, R ¹ is the same as above, R ² is an alkylene group, Q is a polystyrene residue, a is 0 or 1, and b is 0 or 1.)
And a group selected from the group consisting of a hydroxyl group, a hydrogen atom, and an alkoxy group, provided that at least one of Z is a group represented by the general formula (I), and m is 1 It is an integer above. }
The fluorine-containing organopolysiloxane represented by these. Fluorine atom-containing organic group of R ¹ is, at the end of the organic group of the formula: a group represented by -CF ₃ least one contains, in the side chain of the organic group of the formula: represented by -CF ₃ The fluorine-containing organopolysiloxane according to claim 1, which contains or does not contain a group. The fluorine atom-containing organic group of R ¹ has the general formula:
_{- (CH 2) c - (} O) d -R 3
(In the formula, c is an integer of 2 or more, d is 0 or 1, R ³ contains at least one group represented by the formula: —CF ₃ at the terminal of the fluorinated alkyl group, (It is a fluorinated alkyl group containing or not containing a group represented by the formula: -CF ₃ in the side chain of the alkyl group.)
A fluorine atom-containing organic group represented by the general formula:
_{- (CH 2) c - (} O) d - (R 4 O) e -R 5
(Wherein c is an integer of 2 or more, d is 0 or 1, e is an integer of 1 or more, and R ⁴ contains a group represented by the formula: —CF ₃ , or A fluorinated alkylene group not containing, R ⁵ contains at least one group represented by the formula: —CF ₃ at the terminal of the fluorinated alkyl group, and the formula: —CF ₃ in the side chain of the alkyl group; Fluorinated alkyl group containing or not containing the group represented by ₃ )
The fluorine-containing organopolysiloxane according to claim 1, which is a fluorine atom-containing organic group represented by the formula: The fluorine atom-containing organic group of R ¹ has the general formula:
− (CH ₂ ) _c (CF ₂ ) _f F
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c CF (} CF 3) 2
(In the formula, c is an integer of 2 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c C (} CF 3) 2 (CF 2) f CF 3
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c CH (} CF 3) (CH 2) f CF (CF 3) 2
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c O (} CH 2) g CF (CF 3) 2
(In the formula, c is an integer of 2 or more, and g is an integer of 2 or more.)
2. The fluorine-containing organopolysiloxane according to claim 1, wherein the fluorine-containing organopolysiloxane is at least one group selected from the group consisting of fluorine atom-containing organic groups. Q is a general formula:
−C ₂ H ₂ (R ⁶ ) (C ₆ H ₅ ) −
(In the formula, R ⁶ is a hydrogen atom or a methyl group.)
The fluorine-containing organopolysiloxane according to claim 1, wherein the fluorine-containing organopolysiloxane is a polystyrene residue having at least two repeating units represented by formula (II) and having a terminal end blocked with a group derived from an anionic polymerization initiator. (A) General formula:

{Wherein R ¹ is the same or different fluorine atom-containing organic group or a monovalent hydrocarbon group having no fluorine atom, provided that at least one R ¹ is a fluorine atom-containing organic group, and V is , R ¹ , a hydrogen atom and a group selected from the group consisting of alkoxy groups, provided that at least one of V is a hydrogen atom and m is an integer of 1 or more. }
And a fluorine-containing organopolysiloxane represented by formula (B):
_{^{R 7 - (SiR 1 2)}} a -Q
(In the formula, R ¹ is the same as above, R ⁷ is an alkenyl group, Q is a polystyrene residue, and a is 0 or 1.)
The method for producing a fluorinated organopolysiloxane according to claim 1, wherein the polystyrene compound represented by the formula (C) is hydrosilylated in the presence of a catalyst for hydrosilylation reaction (C). In component (A), the fluorine atom-containing organic group represented by R ¹ contains at least one group represented by the formula: —CF ₃ at the end of the organic group, and the side chain of the organic group has the formula: or containing a group represented by -CF _3, or wherein the free method for producing a fluorine-containing organopolysiloxane according to claim 6. In component (A), the fluorine atom-containing organic group represented by R ¹ has the general formula:
_{- (CH 2) b - (} O) c -R 3
(In the formula, b is an integer of 2 or more, c is 0 or 1, R ³ contains at least one group represented by the formula: —CF ₃ at the terminal of the fluorinated alkyl group, (It is a fluorinated alkyl group containing or not containing a group represented by the formula: -CF ₃ in the side chain of the alkyl group.)
A fluorine atom-containing organic group represented by the general formula:
_{- (CH 2) b - (} O) c - (R 4 O) d -R 5
(In the formula, b is an integer of 2 or more, c is 0 or 1, d is an integer of 1 or more, and R ⁴ contains a group represented by the formula: —CF ₃ , or A fluorinated alkylene group not containing, R ⁵ contains at least one group represented by the formula: —CF ₃ at the terminal of the fluorinated alkyl group, and the formula: —CF ₃ in the side chain of the alkyl group; Fluorinated alkyl group containing or not containing the group represented by ₃ )
The method for producing a fluorine-containing organopolysiloxane according to claim 6, wherein the organic group is a fluorine atom-containing organic group represented by the formula: In component (A), the fluorine atom-containing organic group represented by R ¹ has the general formula:
− (CH ₂ ) _c (CF ₂ ) _f F
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c CF (} CF 3) 2
(In the formula, c is an integer of 2 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c C (} CF 3) 2 (CF 2) f CF 3
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c CH (} CF 3) (CH 2) f CF (CF 3) 2
(In the formula, c is an integer of 2 or more, and f is an integer of 1 or more.)
A fluorinated alkyl group represented by the general formula:
_{- (CH 2) c O (} CH 2) g CF (CF 3) 2
(In the formula, c is an integer of 2 or more, and g is an integer of 2 or more.)
7. The method for producing a fluorinated organopolysiloxane according to claim 6, wherein the fluorinated organopolysiloxane is at least one group selected from the group consisting of fluorine atom-containing organic groups. In the component (B), Q is a general formula:
−C ₂ H ₂ (R ⁶ ) (C ₆ H ₅ ) −
(In the formula, R ⁶ is a hydrogen atom or a methyl group.)
The production of a fluorinated organopolysiloxane according to claim 6, which is a polystyrene-based residue having at least two repeating units represented by formula (II) and having a terminal end blocked with a group derived from an anionic polymerization initiator. Method. An organic polymer composition comprising the fluorine-containing organopolysiloxane according to any one of claims 1 to 5.