JP2000154252A - Novel silsequioxane-containing polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel silsesquioxane-containing polymer being solvent- soluble and having a high melting point, high heat resistance and high flame retardany, which polymer has a pentacyclo [9. 5. 1. 13.9. 15.15. 17.13] octasiloxane (PCOSI) skeleton. SOLUTION: Provided is silsesquioxane-containing polymer of formula I (wherein R and R' are each an alkyl optionally having a substituent, or an aryl optionally having substituents; q and q' are each 0 or a positive integer; m is 2-4; m' is 2 or 4; m" is 2-4; and n, n', and n" are each 0 or a positive integer, provided that at least one them is an integer of 2 or greater). The polymer is obtained by the hydrosilylation polymerization of a vinylsiloxane of formula II with PCOSI in the presence of a platinum-containing catalyst. The reaction can be performed at a temperature from 0 deg.C to the boiling point of the solvent used, and can be practiced at room temperature. In the reaction, the ratio of PCOSI to the vinyl vinylsiloxane is 2:1 to 1:4 by mole.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a heat-resistant silicon-containing polymer, in which most of the bonds involving silicon
The present invention relates to a silicone-type silsesquioxane polymer serving as a silicon-containing resin of a silicone type having an —O bond and a method for producing the same. A typical example of the heat-resistant silicone-type silicon-containing resin is a silicone resin, which is used for various film-forming materials, binders for various powders, sealing materials, electric insulating materials, and the like.

[0002]

2. Description of the Related Art Silicone resin is obtained by hydrolysis of trifunctional trichlorosilane and tetrafunctional tetrachlorosilane, and becomes insoluble with the progress of the reaction. .

On the other hand, a ladder silicone consisting of only a trifunctional monomer is soluble in various solvents and
Heat resistance, mechanical strength, etc. are extremely high and attract attention.
However, it can only change the last substituent remaining on the silicon, and no further improvement in structure can be expected.

On the other hand, trifunctional monomers form cubic octamers under certain conditions. If the remaining substituents on the silicon of this octakis (silsesquioxane) are functionalized hydride groups, further reaction is possible. A cubic octamer having a hydroxy anion can also be obtained from a tetrafunctional monomer or silicic acid. This can be reacted with chlorosilane or converted into a hydrosiloxy group for further reaction. Conventionally, polymers linked by hydrosilylation polymerization with a diene or the like or polycondensation with a bifunctional silane such as dichlorosilane have been reported, but all are insoluble and infusible polymers.

Further, a diol of silsesquioxane having a shape in which a cube is broken due to incomplete condensation is known, and a soluble polymer has been synthesized by condensation with dichlorosilane. However, this type of silsesquioxane is only a special example in which the substituents on silicon are limited to those of cyclohexyl group and cyclopentyl group, and are disadvantageous in terms of heat resistance.

The present inventors have already disclosed Japanese Patent Application Laid-Open No. 9-2960.
43, and 296044, with substituted diynes or terminal monoynes, and octakis (hydridosilsesquioxane), ie, pentacyclo [9.5.1.1 ^3,9 . 1
^5,15 . 1 ^7,13 ] octasiloxane (hereinafter simply referred to as PCOS
(Abbreviated as I) have been disclosed to provide silsesquioxane-containing polymers with very high thermal stability. However, none of these polymers showed a melting point, and it was difficult to process and mold by heat.

[0007]

DISCLOSURE OF THE INVENTION The present invention has an octakis (silsesquioxane) skeleton and is insoluble and infusible like the above-mentioned silicone resin and conventionally known silsesquioxane polymer. An object of the present invention is to provide a polymer that is soluble in a solvent, has a melting point, and has high heat resistance and flame retardancy.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they have obtained a silsesquioxane structure by hydrosilylation polymerization of PCOSI and divinylsiloxanes. It has been found that a silicon-containing polymer that is soluble in a solvent, has a melting point, and high heat resistance can be obtained. Based on this fact, the present invention has been completed.

That is, according to the present invention, the following general formula (1)

Embedded image (Wherein, R and R ′ represent an alkyl group which may have a substituent or an aryl group which may have a substituent, q and q ′ each represent 0 or a positive integer, and m represents 2,
Represents 3 or 4, m ′ represents 2 or 4, m ″ represents 2, 3 or 4, n, n ′ and n ″ are 0 or positive integers, and at least one of them Represents a positive number of 2 or more), and a silsesquioxane-containing polymer having a PCOSI skeleton is provided. Further, according to the present invention, in order to produce the silsesquiosan-containing polymer of the general formula (1),

Embedded image (Wherein, R and R ′ represent an alkyl group which may have a substituent or an aryl group which may have a substituent, and q and q ′ each represent 0 or a positive integer). Provided by subjecting the divinylsiloxanes to be subjected to hydrosilylation polymerization to PCOSl octasiloxane in the presence of a platinum-containing catalyst.

The portion represented by the following formula (3) in the general formula (1) indicates that the vinyl group of divinylsiloxane is additionally bonded to a hydrosilyl group in a different PCOSI.

Embedded image In addition, the portion represented by the following formula (4) in the general formula (1) indicates that the two states represented by the following formula (5) are included.

Embedded image

Embedded image

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R and R ′ represent an alkyl group which may have a substituent or an aryl group which may have a substituent. The alkyl group has 1 to 20, preferably 1 to 6 carbon atoms. The aryl group has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples of the alkyl group include
Methyl group, ethyl group, isopropyl group, tertiary butyl group,
A hexyl group and the like can be mentioned, and specific examples of the aryl group include a phenyl group, an anisyl group, a naphthyl group and the like.

The divinylsiloxane used as a reaction raw material in the present invention is represented by the general formula (2):

Embedded image (In the formula, R and R ′ represent an alkyl group which may have a substituent or an aryl group which may have a substituent, and q and q ′ represent 0 or a positive integer.) It is a compound represented by these. Examples of these divinylsiloxanes include 1,3-divinyltetramethyldisiloxane,
1,5-divinylhexamethyltrisiloxane, 1,7
-Divinyloctamethyltetrasiloxane, α, ω-divinylpoly (dimethylsiloxane), 1,3-divinyltetraphenyldisiloxane, 1,5-divinylhexaphenyltrisiloxane, 1,7-divinyloctaphenyltetrasiloxane, α, ω -Divinyl poly (diphenylsiloxane), vinyl-terminated diphenylsiloxane-
A dimethylsiloxane copolymer and the like can be mentioned.

In the present invention, these divinylsiloxanes are subjected to a hydrosilylation reaction with PCOSI,
A silsesquioxane-containing polymer having a PCOSI skeleton is synthesized.

[0014] A platinum-containing catalyst is used in the hydrosilylation reaction. As the platinum-containing catalyst, those conventionally used for hydrosilylation reactions can be used. To illustrate this, platinum divinyltetramethyldisiloxane,
Platinum cyclic vinylmethylsiloxane, tris (dibenzylideneacetone) diplatinum, chloroplatinic acid, bis (ethylene)
Examples thereof include tetrachlorodiplatinum, cyclooctadienedichloroplatinum, bis (cyclooctadiene) platinum, bis (dimethylphenylphosphine) dichloroplatinum, tetrakis (triphenylphosphine) platinum, and platinum carbon.

In the hydrosilylation reaction, various solvents commonly used in this reaction can be used. For example, toluene, benzene, hexane, ether and the like can be mentioned. This reaction can be carried out at various temperatures from 0 ° C. to the boiling point of the solvent, but can be carried out at room temperature without particular heating or cooling. The ratio of PCOSI to divinylsiloxanes in this reaction is from 2: 1 to 2 in terms of molar ratio from the viewpoint of yield and solubility.
A range of 1: 4 is desirable. After the reaction, a cast film or the like can be prepared as a polymer solution as it is,
It can also be used after fractionation using a reprecipitation, gel filtration column, GPC column or the like.

[0016]

The following examples are provided to clarify aspects of the present invention. However, the present invention is not limited to the following examples.

Example 1 Pentacyclo [9.5.1.1 ^3,9 . ^15.15 . 1 ^7,13 ]
Octasiloxane 212 mg (0.50 mmol),
93 mg of 1,3-divinyltetramethyldisiloxane
(0.50 mmol) was dissolved in 50 ml of toluene, 10 μl of a xylene solution of platinum divinyltetramethyldisiloxane (Huls PC072) was added, and the mixture was stirred at room temperature for 3 days. When the solution was fractionated on a GPC column, M _w
= 4,300 (M _n = 2,900) [formula (1), R = methyl, q = q ′ = 0] is 101.6 mg.
(33.3%).

¹ H NMR (C ₆ D ₆ ): -0.2 to 0.
5 (m), 0.5 to 1.0 (m), 1.0 to 1.5
(M), 4.2 to 4.7 (m) ppm. ^When calculated from ¹ H NMR, pentacyclo [9.5.
1.1 ^3,9 . ^15.15 . 1 ^{7, 13} ] octasiloxane: 1,
3-bis (phenylethynyl) benzene = 1: 1.62
Met. _{^{29 Si NMR (C 6 D 6}} ) -84.5~-83 (m),
-65.5 to -64 (m), 7 to 8 (m), 8 to 10
(M) ppm. mp 85-90 ° C

The TGA of this product was measured. The residual amount when heated to 984 ° C. at 10 ° C./min in a nitrogen atmosphere was 89.3%, and T _d5 was 595 ° C. When heated similarly in an air atmosphere, the temperature is 9
2.4% remained and T _d5 reached 569 ° C.

[0020]

According to the present invention, there is provided a novel silsesquioxane-containing polymer which is soluble in ordinary organic solvents, has a melting point, and has high heat resistance and flame retardancy.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masato Tanaka 1-1-1 Higashi, Tsukuba, Ibaraki Pref.

Claims (2)

[Claims] [Claim 1] The following general formula (1) (Wherein, R and R ′ represent an alkyl group which may have a substituent or an aryl group which may have a substituent, q and q ′ each represent 0 or a positive integer, and m represents 2,
Represents 3 or 4, m ′ represents 2 or 4, m ″ represents 2, 3 or 4, n, n ′ and n ″ are 0 or positive integers, and at least one of them Represents a positive number of 2 or more. ), Pentacyclo [9.5.
1.1 ^3,9 . ^15.15 . [ ^17,13 ] Silsesquioxane-containing polymers having an octasiloxane skeleton. 2. A compound of the general formula (2) (Wherein, R and R ′ represent an alkyl group which may have a substituent or an aryl group which may have a substituent, and q and q ′ each represent 0 or a positive integer). Divinylsiloxanes, and pentacyclo [9.5.1.
^13-9 . 1 ^{5,1 5.} [ ^7,13 ] octasiloxane is subjected to hydrosilylation polymerization in the presence of a platinum-containing catalyst, and is represented by the following general formula (1): (Wherein, R and R ′ represent an alkyl group which may have a substituent or an aryl group which may have a substituent, q and q ′ each represent 0 or a positive integer, and m represents 2,
Represents 3 or 4, m ′ represents 2 or 4, m ″ represents 2, 3 or 4, n, n ′ and n ″ are 0 or positive integers, and at least one of them Represents a positive number of 2 or more), pentacyclo [9.5.1.
^13-9 . ^15.15 . [ ^17,13 ] A method for producing a silsesquioxane-containing polymer having an octasiloxane skeleton.