JPH0782379A - Production of organosilicon polymer - Google Patents

Abstract

PURPOSE:To obtain an organosilicon polymer in a high yield without being accompanied by depolymn. by subjecting two specific diorganosiloxanes to addition polymn. in the presence of a hydrosilylation catalyst. CONSTITUTION:Two diorganosiloxanes of formulas I and II and if necessary a silane or siloxane of formula II are subjected to addition polymn. in the presence of a hydrosilylation catalyst to give an organosilicon polymer of formula IV. In those formulas, R<1> is a 1-10C monovalent hydrocarbon group contg. no aliph. unsatd. bond; m>=0; R<2> is 2-10C alkenyl; n>=0; R<3> is H or 2-10C alkenyl; p>=0; R<4> is H, a 1-10C monovalent hydrocarbon group contg. no aliph. unsatd. bond, or 2-10C alkenyl; q>=0; r>=0; and s>=1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organosilicon polymer, and more particularly to a method for producing an organosilicon polymer having a silalkylene siloxane unit in good yield without depolymerization.

[0002]

PRIOR ART General formula:

[Chemical 5] (In the formula, R is a monovalent hydrocarbon group, and a is a positive integer.) The organosilicon polymer having a silalkylene siloxane unit is more acidic than a general diorganopolysiloxane. Since it is difficult for the molecular chain to be cleaved by ionic substances such as alkali, its use in special fields is being investigated. Examples of the method for producing such an organosilicon polymer include a method of ring-opening polymerization of a cyclic silalkylene siloxane (Izvestiya Akademii).
Nauk SSSR, Seriya Khimicheskaya, No.4, 739-74
4, April, 1971, JP-A-4-65428 and JP-A-4-65429).

However, Izvestiya Akademii Nauk SSS
R, JP-A-4-65428 and JP-A-4-65442
In the method for producing an organosilicon polymer proposed in No. 9, 2,2,6,6-tetramethyl-1-oxa-2,6 is previously prepared.
-It was necessary to prepare a cyclic silalkylene siloxane such as disilacyclohexane, and there was a problem that it was difficult to prepare this cyclic silalkylene siloxane. Further, as reported in Izvestiya Akademii Nauk SSSR, in this ring-opening polymerization, there is a problem that a part of the obtained organosilicon polymer is depolymerized and the yield of the organosilicon polymer is reduced. It was

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.

That is, an object of the present invention is to provide a method for producing an organosilicon polymer having a silalkylene siloxane unit in good yield without depolymerization.

[0006]

Means for Solving the Problem and Its Action The present invention provides (A) general formula:

[Chemical 6] (In the formula, R ¹ has a carbon number of 1 to 1 having no aliphatic unsaturated bond.
It is 10 monovalent hydrocarbon groups, and m is a number of 0 or more. ) A diorganosiloxane represented by the formula (B):

[Chemical 7] (In the formula, R ¹ has a carbon number of 1 to 1 having no aliphatic unsaturated bond.
10 are monovalent hydrocarbon groups, R ² is an alkenyl group having 2 to 10 carbon atoms, and n is a number of 0 or more. ) A diorganosiloxane and optionally (C) a general formula:

[Chemical 8] (In the formula, R ¹ has a carbon number of 1 to 1 having no aliphatic unsaturated bond.
10 is a monovalent hydrocarbon group, R ³ is a hydrogen atom or an alkylene group having 2 to 10 carbon atoms, and p is a number of 0 or more. ) Is a silane or siloxane represented by (D)
A general formula characterized by addition polymerization in the presence of a catalyst for hydrosilylation reaction:

[Chemical 9] (In the formula, R ¹ has a carbon number of 1 to 1 having no aliphatic unsaturated bond.
10 monovalent hydrocarbon groups, R ⁴ is a hydrogen atom, a C 1-10 monovalent hydrocarbon group having no aliphatic unsaturated bond or a C 2-10 alkenyl group, and R ⁵ is It is an alkylene group having 2 to 10 carbon atoms, q is a number of 0 or more, r is a number of 0 or more, and s is a number of 1 or more. )
Relates to a method for producing an organosilicon polymer.

The manufacturing method of the present invention will be described in detail.

The component (A), a diorganosiloxane, has the general formula:

[Chemical 10] It is represented by. In the above formula, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond, and specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. Group, heptyl group, octyl group, nonyl group, alkyl group such as decyl group; phenyl group, tolyl group,
An aryl group such as a xylyl group; an aralkyl group such as a benzyl group and a phenethyl group are exemplified, and a methyl group and a phenyl group are preferable. In the above formula, m is a number of 0 or more.

Specific examples of the component (A) include the following diorganosiloxanes.

[0010]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17] (In the formula, x is a number of 1 or more and y is a number of 1 or more.)

The component (B), a diorganosiloxane, has the general formula:

[Chemical 18] It is represented by. In the above formula, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond, and specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. Group, heptyl group, octyl group, nonyl group, alkyl group such as decyl group; phenyl group, tolyl group,
An aryl group such as a xylyl group; an aralkyl group such as a benzyl group and a phenethyl group are exemplified, and a methyl group and a phenyl group are preferable. R ² is an alkenyl group having 2 to 10 carbon atoms, specifically, a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group,
Examples thereof include an octenyl group, a nonenyl group and a decenyl group, with a vinyl group and an allyl group being preferred. Also, in the above equation, n
Is a number of 0 or more.

Specific examples of such component (B) include the following diorganosiloxanes.

[0013]

[Chemical 19]

[Chemical 20]

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31] (In the formula, x is a number of 1 or more and y is a number of 1 or more.)

In the production method of the present invention, the amount of the component (B) added is not particularly limited. For example, the number of moles of the component (A) and (B)
The molar ratio of the components is preferably in the range of 0.5: 1.0 to 1.5: 1.0, and in order to prepare a relatively high molecular weight organosilicon polymer, (A) It is preferable that the component and the component (B) are equimolar.

In the production method of the present invention, the general formula:

[Chemical 32] A silane or siloxane represented by can be blended. In the production method of the present invention, the silane or siloxane as the component (C) acts as an end-capping agent for the obtained organosilicon polymer, and can control the degree of polymerization of the obtained organosilicon polymer. In the above formula, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond, and specifically, a methyl group, an ethyl group, a propyl group,
Examples include alkyl groups such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; aryl groups such as phenyl, tolyl, xylyl; aralkyl groups such as benzyl and phenethyl. , And preferably a methyl group or a phenyl group. R ³ is a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms. Specific examples of the alkenyl group for R ³ include a vinyl group, an allyl group,
Examples thereof include butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group and decenyl group, with vinyl group and allyl group being preferred. Further, in the above formula, p is a number of 0 or more, when p is 0, the component (C) is silane, and when p is a number of 1 or more, the component (C) is Is siloxane.

Examples of the silane or siloxane as the component (C) include silanes such as trimethylvinylsilane, triethylvinylsilane, trimethylallylsilane, triethylallylsilane, and triphenylvinylsilane; vinylpentamethyldisiloxane, allylpentamethyldisiloxane, one of A dimethylpolysiloxane in which the molecular chain end is blocked with a trimethylsiloxy group and the other molecular chain end is blocked with a dimethylvinylsiloxy group, one molecular chain end is blocked with a trimethylsiloxy group, and the other molecular chain end is Is a methylphenylpolysiloxane, and one of the molecular chain ends has a trimethylsiloxy group blocked and the other has a dimethylvinylsiloxy group blocked dimethylsiloxane / methylphenylsiloxane copolymer siloxa There are exemplified.

In the production method of the present invention, the addition amount of the component (C) is not particularly limited, and in order to adjust the organosilicon polymer having a relatively high molecular weight, the component (A) or the component (B) is added. It is preferable to use a very small amount.

The catalyst for hydrosilylation reaction (D) is an organosilicon polymer having a silalkylene siloxane unit, which promotes an addition reaction between a silicon atom-bonded hydrogen atom in component (A) and an alkenyl group in component (B). It is a catalyst for promoting the addition polymerization to the coalescence. The component (D) is not particularly limited, and examples thereof include platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, and organic peroxides, which are platinum-based catalysts because they significantly accelerate addition polymerization. Is preferred.
Specific examples of the platinum-based catalyst include platinum black, platinum-supported silica, platinum-supported activated carbon, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-vinylsiloxane complex, and platinum-olefin complex. In addition, in the production method of the present invention, the addition amount of the component (D) is a catalytic amount and is not particularly limited, but preferably the total amount of the components (A) and (B) is 1
It is in the range of 0.1 to 500 parts by weight with respect to, 000,000 parts by weight.

The production method of the present invention is characterized in that the component (A), the component (B) and, if necessary, the component (C) are subjected to addition polymerization in the presence of the component (D). In the manufacturing method of the present invention,
The order of adding the components (A) to (D) is arbitrary, and for example,
To the system of (B) component and (C) component, while stirring this system from room temperature under heating conditions, a method of adding the (A) component, the (A) component and
A method of adding the component (C) to the system of the component (B) while stirring the system under heating conditions from room temperature can be mentioned.

In the production method of the present invention, an organic solvent can be used as long as the object of the present invention is not impaired. In the production method of the present invention, a high molecular weight organosilicon polymer can be obtained by using an organic solvent. Specific examples of such organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; hexane,
Aliphatic hydrocarbon solvents such as heptane and octane; Alicyclic hydrocarbon solvents such as cyclohexane and cycloheptane;
Examples thereof include fluorine-containing aromatic hydrocarbon solvents such as trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene, and methylpentafluorobenzene.

The production conditions of the present invention are not particularly limited, and when the addition polymerization is carried out at normal pressure, the reaction temperature is from room temperature to the boiling point of the component (A) or the component (B) or the boiling point of the organic solvent used. And also (A) component, (B) component, (C)
When the reaction is carried out at a temperature not lower than the boiling points of the components and the organic solvent used, it is necessary to carry out addition polymerization under pressure. Further, the reaction time is not particularly limited, and varies depending on the reaction temperature.

The organosilicon polymer thus obtained has the general formula:

[Chemical 33] It is represented by. In the above formula, R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond, and specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. Group, heptyl group, octyl group, nonyl group, alkyl group such as decyl group; phenyl group, tolyl group,
An aryl group such as a xylyl group; an aralkyl group such as a benzyl group and a phenethyl group are exemplified, and a methyl group and a phenyl group are preferable. In addition, in the above formula, R ⁴ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond, or an alkenyl group having 2 to 10 carbon atoms. Specific examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms which does not have an aliphatic unsaturated bond for R ⁴ include the same groups as those for R ¹ . Specific examples of the alkenyl group for R ⁴ include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group and a decenyl group, preferably a vinyl group and an allyl group. Is. Further, in the above formula, R ⁵ is an alkylene group having 2 to 10 carbon atoms, specifically, ethylene group, propylene group,
Examples are methylethylene group, pentylene group, hexenylene group, heptenylene group, octenylene group, nonenylene group and decenylene group, and ethylene group and propylene group are preferable. In the above formula, q is a number of 0 or more and r is 0.
The above is a number, and s is a number of 1 or more. In the production method of the present invention, when the component (A) is added in excess with respect to the component (B), the molecular chain terminal of the obtained organosilicon polymer becomes a silicon atom-bonded hydrogen atom, and (B) When the component is excessively added to the component (A), the molecular chain terminal of the obtained organosilicon polymer becomes an alkenyl group having 2 to 10 carbon atoms. Furthermore, in the production method of the present invention, when the component (C) is added, the molecular chain terminal of the obtained organosilicon polymer has a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond. Becomes

Such an organosilicon polymer is a viscous liquid at room temperature, has a low surface tension, and is unlikely to undergo molecular chain scission by an ionic substance such as acid or alkali. Therefore, it is used as an oil. Besides, it can be used as a main material of an organic peroxide-curable silicone rubber composition, an addition reaction-curable silicone rubber composition, or a condensation reaction-curable silicone rubber composition. In addition, an organosilicon polymer having a silicon atom-bonded hydrogen atom at the molecular chain end prepares an organosilicon polymer having an organic functional group at the molecular chain end by addition reaction with an alkene having an organic functional group. The organic silicon polymer having an alkenyl group at the end of the molecular chain can be used as a raw material for the addition of an organosilicon polymer having an organic functional group at the end of the molecular chain by addition reaction with hydrogen silane having an organic functional group. It can be used as a raw material for preparing a coalescence.

[0024]

EXAMPLES The method for producing the organosilicon polymer of the present invention will be described in detail with reference to Examples. In the examples, the viscosity value is a value measured at 25 ° C.

[Example 1] 13.0 g in a reaction vessel
(0.097 mol) 1,1,3,3-tetramethyldisiloxane, 18.0 g (0.097 mol) 1,3-
Divinyl-1,1,3,3-tetramethyldisiloxane and 50 g of 1,3-bis (trifluoromethyl) benzene were added, and this was heated to 40 ° C. with uniform stirring. Then, with stirring, a 10% isochloropropanol solution of chloroplatinic acid was added dropwise to this system so that the content of platinum metal itself in the system was 40 ppm. It was observed that with the addition of chloroplatinic acid, the system generated heat up to 100 ° C. and the system thickened. Then, 1,3-bis (trifluoromethyl) benzene was distilled off to obtain a viscous liquid of 2,800 centipoise. The viscous liquid was analyzed by ¹ H-nuclear magnetic resonance spectral analysis (hereinafter, NMR) and infrared spectroscopic analysis (hereinafter, IR), and was confirmed to be polysilethylenesiloxane represented by the following average formula. It was In addition, gel permeation chromatography (hereinafter referred to as GP
When analyzed by C), the weight average molecular weight of this polysilethylene siloxane was 32,000 in terms of polydimethylsiloxane, and it was confirmed that the yield of polysilethylene siloxane determined from the peak area was 95%. Was done.

[0026]

[Chemical 34] (In the formula, z is a number of 1 or more.)

Example 2 13.0 g in a reaction vessel
(0.097 mol) of 1,1,3,3-tetramethyldisiloxane, 21.0 g (0.098 mol) of 1,3-
Diallyl-1,1,3,3-tetramethyldisiloxane and 60 g of toluene were added, and this was heated to 40 ° C. with uniform stirring. Then, with stirring, a 10% isochloropropanol solution of chloroplatinic acid was added dropwise to this system so that the content of platinum metal itself in the system was 40 ppm.
It was observed that with the addition of chloroplatinic acid, the system generated heat up to 100 ° C. and the system thickened. afterwards,
Toluene was distilled off to obtain a viscous liquid. ¹ this viscous liquid
When analyzed by 1 H-NMR and IR, it was confirmed to be a polysilpropylenesiloxane represented by the following average formula. Further, when the polysilpropylene siloxane was analyzed by GPC, the weight average molecular weight of the polysilpropylene siloxane was 6,000 in terms of polydimethylsiloxane, and the yield of the polysilpropylene siloxane obtained from the peak area was calculated. Is 91%
Was confirmed.

[0028]

[Chemical 35] (In the formula, z is a number of 1 or more.)

[Example 3] 13.0 g in a reaction vessel
(0.097 mol) of 1,1,3,3-tetramethyldisiloxane, 23.0 g (0.077 mol) of 1,3-
Bis (5-hexenyl) -1,1,3,3-tetramethyldisiloxane and 60 g of toluene were added, and this was heated to 40 ° C. while being uniformly stirred. Then, with stirring, a 10% isochloropropanol solution of chloroplatinic acid was added dropwise to this system so that the content of platinum metal itself in the system was 40 ppm. With the addition of chloroplatinic acid, this system
It was confirmed that the system generated heat up to 0 ° C. and the viscosity of this system increased. Then, toluene was distilled off to obtain a viscous liquid. When this viscous liquid was analyzed by ¹ H-NMR and IR, it was confirmed to be polysilhexenylene siloxane represented by the following average formula. Moreover, when this polysilhexenylene siloxane was analyzed by GPC,
The weight average molecular weight of this polysilhexenylene siloxane is 5,000 in terms of polydimethylsiloxane,
It was confirmed that the yield of polysilhexenylene siloxane obtained from the peak area was 95%.

[0030]

[Chemical 36] (In the formula, z is a number of 1 or more.)

Example 4 37.2 g in a reaction vessel
(0.2 mol) of 1,3-divinyl-1,1,3,3-
Tetramethyldisiloxane, 50 g toluene and 1
0.5 g of platinum-supporting carbon powder was added, and the mixture was heated to 50 ° C. with uniform stirring. Then, with stirring, 32.7 g (0.2 mol) of the average formula:

[Chemical 37] A mixture of the diorganopolysiloxane mixture represented by and 40 g of toluene was slowly added dropwise in the temperature range of 50 to 90 ° C. The system was heated to reflux at 112 ° C for 3 hours. Then, it cooled, the platinum carrying | support carbon powder was removed by decantation, and toluene was distilled off, and the viscous liquid was obtained. When this viscous liquid was analyzed by ¹ H-NMR and IR, it was confirmed to be a mixture of silethylenesiloxane / dimethylsiloxane copolymer represented by the following average formula. When this silethylene siloxane / dimethyl siloxane copolymer mixture was analyzed by GPC, the weight average molecular weight was 22,000 in terms of polydimethyl siloxane, and the sil ethylene siloxane / dimethyl siloxane was determined from the peak area. It was confirmed that the yield of the copolymer mixture was 96%.

[0032]

[Chemical 38] (In the formula, z is a number of 1 or more.)

Example 5 73.7 g of the average formula in a reaction vessel:

[Chemical Formula 39] The diorganosiloxane mixture represented by the formula, 70 g of toluene and 1 g of 0.5% by weight of platinum-supporting carbon powder were added, and the mixture was heated to 50 ° C. while being uniformly stirred. Then, with stirring, 13.4 g (0.1 mol) of 1,1,3,3-tetramethyldisiloxane and 1
A mixture with 5 g of toluene was slowly added dropwise in the temperature range of 50 to 90 ° C. The system was heated to reflux at 112 ° C for 3 hours. Then, it is cooled, the platinum-carrying carbon powder is removed by decantation, the toluene is distilled off,
A viscous liquid was obtained. This viscous liquid was analyzed by ¹ H-NMR and I
When analyzed by R, it was confirmed to be a mixture of silethylenesiloxane / dimethylsiloxane copolymer represented by the following average formula. In addition, this silethylene siloxane / dimethyl siloxane copolymer mixture was added to GPC.
The weight average molecular weight was 100,000 in terms of polydimethylsiloxane, and the yield of the silethylenesiloxane / dimethylsiloxane copolymer mixture determined from the peak area was 94%. Was done.

[0034]

[Chemical 40] (In the formula, z is an integer of 1 or more.)

Example 6 37.2 g in a reaction vessel
(0.2 mol) of 1,3-divinyl-1,1,3,3-
Tetramethyldisiloxane, 1.74 g (0.01 mol) of vinyl pentamethyldisiloxane, 26.8 g
(0.2 mol) of 1,1,3,3-tetramethyldisiloxane and 70 g of toluene were added, and this was heated to 55 ° C. with uniform stirring. Subsequently, 1 g of 0.5% platinum-supported carbon powder was added to this system, and this was heated in a temperature range of 50 to 90 ° C. while being uniformly stirred. The system was then heated to reflux at 112 ° C for 3 hours.
Then, it cooled, the platinum carrying | support carbon powder was removed by decantation, and toluene was distilled off, and the viscous liquid was obtained. When this viscous liquid was analyzed by ¹ H-NMR and IR, it was confirmed to be a mixture of silethylenesiloxane / dimethylsiloxane copolymer represented by the following average formula. In addition, this silethylene siloxane
When the dimethylsiloxane copolymer mixture was analyzed by GPC, the weight average molecular weight was 9,000 in terms of polydimethylsiloxane, and the yield of the silethylenesiloxane / dimethylsiloxane copolymer mixture was calculated from the peak area. Was confirmed to be 95%.

[0036]

[Chemical 41] (In the formula, z is a number of 1 or more.)

[0037]

The production method of the present invention is characterized in that an organosilicon polymer having a silalkylene siloxane unit can be produced in good yield without depolymerization.

Claims (1)

[Claims] 1. (A) General formula: (In the formula, R ¹ has a carbon number of 1 to 1 having no aliphatic unsaturated bond.
It is 10 monovalent hydrocarbon groups, and m is a number of 0 or more. ) A diorganosiloxane represented by the formula (B), a general formula: (In the formula, R ¹ has a carbon number of 1 to 1 having no aliphatic unsaturated bond.
10 are monovalent hydrocarbon groups, R ² is an alkenyl group having 2 to 10 carbon atoms, and n is a number of 0 or more. ), And optionally (C) a general formula: (In the formula, R ¹ has a carbon number of 1 to 1 having no aliphatic unsaturated bond.
10 is a monovalent hydrocarbon group, R ³ is a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, and p is a number of 0 or more. ) Is a silane or siloxane represented by (D)
A compound represented by the general formula: embedded image which is characterized by carrying out addition polymerization in the presence of a catalyst for a hydrosilylation reaction. (In the formula, R ¹ has a carbon number of 1 to 1 having no aliphatic unsaturated bond.
10 monovalent hydrocarbon groups, R ⁴ is a hydrogen atom, a C 1-10 monovalent hydrocarbon group having no aliphatic unsaturated bond or a C 2-10 alkenyl group, and R ⁵ is It is an alkylene group having 2 to 10 carbon atoms, q is a number of 0 or more, r is a number of 0 or more, and s is a number of 1 or more. )
A method for producing an organosilicon polymer represented by: