JPH0649218A - Cross-linkable polysilane composition and its cured product - Google Patents

Abstract

PURPOSE:To obtain a polysilane composition, comprising both terminal- alkenylpolysilanes, an alkenyl group-containing compound and a hydrosilylating catalyst and capable of forming solvent-insoluble tough cross-linked films after cross-linking and curing. CONSTITUTION:The cross-linkable polysilane composition comprises (A) both terminal-alkenylpolysilanes, (B) a compound containing >=3 alkenyl groups in one molecule and (C) a hydrosilylating catalyst. The component (A) is a expressed by the formula (R<1> to R<4> are l-12C alkyl or aryl; n, m and p are 0<=n<=10; 0<=m<=10; n+m>=10 and p >=1). A rhodium metallic complex is used as the component (C). Symbol p in the formula is preferably >=10. The component (B) is preferably a hydrogenpolysiloxane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable polysilane composition and a cured product thereof which can obtain a strong solvent-insoluble polysilane crosslinked film after crosslinking and curing.

[0002]

2. Description of the Related Art Siloxane compositions having a mechanism of curing by a hydrosilylation reaction are characterized in that they do not form by-products and cure rapidly to a deep portion. For example, it is used in a wide range of fields such as molded rubber, adhesives, potting materials for electric / electronic parts, and release coating materials such as paper and films.

On the other hand, in a curable composition using polysilanes, an example reported by hydrosilylation reaction is:
There is one in which polysilanes having hydrogen as a side chain substituent and trivinylphenylsilane are cured using a chloroplatinic acid catalyst (Robert West, Journal of Organometallic Chemistry, vol. 300, 327-).
However, in this method, there are problems that the reactivity of the side chain substituent is low and that the polysilane chain is cleaved by the chloroplatinic acid catalyst and is further oxidized.

Further, a polysilane curing method using a photocrosslinking reaction of a polysilane having an alkenyl group in its side chain alone, or a curing method by a photocrosslinking reaction of a polysilane and a polyfunctional unsaturated compound has been reported (Robert. Waist,
Journal of Organometallic Chemistry, 300, 327-346, 1986).

However, this method has a problem that the property of polysilane cannot be imparted to the crosslinked film as it is because the method uses the cleavage of polysilane chain.

Further, soluble polysilane is soluble in various general organic solvents, and it is possible to form a film by using it. However, since the solubility is limited, the solution viscosity is increased to form a thick film. It was difficult and limited for applications where thick films had to be formed.

The present invention has been made in view of the above circumstances, and does not break the polysilane chain during the crosslinking reaction.
The property of polysilane can be added to the cured product as it is.
An object of the present invention is to provide a crosslinkable polysilane composition capable of forming a thick film and a cured product thereof.

[0008]

Means and Actions for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that alkenylpolysilanes having both terminals and a compound having at least three hydrosilyl groups in one molecule are selected. It is effective to carry out the hydrosilylation reaction in the presence of a hydrosilylation catalyst to achieve the above-mentioned object, and in this case, particularly by using a rhodium metal complex as the hydrosilylation catalyst, it is possible to more reliably prevent the polysilane chain from being cleaved. I found that I can do it.

Further, polysilane having alkenyl groups at both terminals has high reactivity with a compound having a hydrosilyl group (≡SiH), and easily crosslinks and cures without breaking the polysilane chain by heating or the like and is insoluble in a solvent. A polysilane cross-linked film is obtained, it is solvent-insoluble and can be overcoated, and a thick film can be formed.In addition, the end-crosslinked type polysilane cross-linked film is interestingly very tough and wear-resistant. The inventors of the present invention have found that they can also be applied to materials that require durability such as strength, and have completed the present invention.

Therefore, the present invention comprises (A) alkenylpolysilanes having both terminals, (B) a compound having at least three alkenyl groups in one molecule, and (C) a hydrosilylation catalyst. Provided is a polysilane composition and a cured product obtained by curing the composition.

The present invention will be described in more detail below. The crosslinkable polysilane composition of the present invention contains, as described above, alkenylpolysilanes having both ends as essential components. In this case, the polysilanes may be any polysilanes having alkenyl groups at both ends, and in particular, those represented by the following general formula (1) can be used.

[0012]

Embedded image A [(R ¹ R ² Si) _n (R ³ R ⁴ Si) _m ] _p A (1)

In the formula, A is an alkenyl group having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl group,
Examples thereof include an allyl group and a propenyl group. Also, R ¹ ,
R < ² >, R < ³ >, and R < ⁴ > are the same or different and each are a substituted or unsubstituted C1-12, preferably C1-10 alkyl or aryl group. Examples of the alkyl group include a methyl group, ethyl group and propyl group, and examples of the aryl group include a phenyl group and a tolyl group. n, m, and p are 0 ≦ n ≦ 10 and 0 ≦ m ≦, respectively.
10 is an integer satisfying n + m ≧ 10 and p ≧ 1, and p is 5 or more to show the properties of polysilane such as photoconductivity.
It is particularly preferably 10 or more.

The both-end alkenyl group represented by the above formula (1) can be synthesized by a general coupling reaction of polysilane using chlorosilane having the alkenyl group.

The compound having at least 3 hydrosilyl groups in one molecule of the component (B), which is an essential component of the crosslinkable polysilane composition of the present invention, is a compound of the siloxypolysilanes having alkenyl groups at both terminals of the component (A). A compound for adding to an alkenyl group by a hydrosilylation reaction, and a hydrosilyl group (≡SiH) for making it insoluble in a solvent.
Is required in three or more in one molecule.

Examples of the compound having at least three alkenyl groups in one molecule include organohydrogensiloxane and organohydrogensilane. Specifically, hydrogen polysiloxane represented by the following formula (4) can be preferably used.

[0017]

[Chemical 3] (In the formula, R is a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, R'is a substituted or unsubstituted alkyl group or aryl group, k is 3 or more, and j is an integer satisfying 0 or more.)

Not only such linear polysiloxanes but also the following cyclic polysiloxanes can be used.

[0019]

Embedded image (MeHSiO) _a a = 3
4, 5 or 6

Further, polyorganosilane represented by the following formula can also be preferably used.

[0021]

Embedded image (MePhSi) _b (MeHSi) _c (MePhHSi) ₃ SiPh PhSiH ₃ H ₂ PhSiSiPhH ₂

In the above formula, Me is a methyl group,
Ph is a phenyl group.

The compounding amount of these at least three hydrosilyl groups is 0.5 to 5 moles of hydrosilyl groups, especially 1 to 5 moles of alkenyl groups in the polysilanes having alkenyl groups at both ends of the component (A). It is preferable to mix them in a ratio of 1 to 3 mol.

The component (C) of the composition of the present invention is a hydrosilylation catalyst, which is a catalyst for reacting the alkenyl group in the component (A) with the hydrosilyl group of the component (B).

As the hydrosilylation catalyst, a metal complex of Group 8 of the periodic table can be preferably used, and Fe, Ni,
As a complex of Co, Pt, Rh, and Ir, specifically, Rh complex, tris (triphenylphosphine) rhodium chloride, carbonium tris (triphenylphosphine) rhodium (I) hydride, chlorobis (cyclooctene) rhodium (I) ) Dimer, rhodium (I) dicarbonylacetylacetonate, etc., Pt complexes include platinum vinyl siloxane, chloroplatinic acid, etc., but in the present invention, rhodium metal complex is preferably used from the viewpoint of preventing silicon-silicon bond cleavage. To be

It is preferable that these compounds are usually used in a state of being dissolved in a solvent such as toluene, xylene, benzene, tetrahydrofuran, butanol. Further, the amount of the hydrosilylation catalyst used is preferably in the range of 0.0001 to 1% by weight based on the polysilane of the component (A) as a metal.

The crosslinkable polysilane composition of the present invention optionally contains, in addition to the above-mentioned essential components, additives such as a reaction inhibitor, an inorganic filler, a heat resistance improver, a colorant and an adhesion improver. can do.

The composition of the present invention is obtained by mixing the above-mentioned components according to a usual method, is formed into a film by a film forming method such as a bar coater, and is heated at a temperature of 70 to 200 ° C. for 0.5 to 3 hours. Thus, cross-linking can be performed to obtain a solvent-insoluble cross-linked polysilane.

[0029]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples.

Example 1 Methylphenyl polysilane having vinyl groups at both ends represented by the following formula (number average molecular weight: 520)
0) 0.26 g, 0.005 g of 1,3,5,7-tetramethylcyclotetrasiloxane are dissolved in 0.74 g of toluene, and a 1% solution of tris (triphenylphosphine) rhodium chloride (catalyst A) in tetrahydrofuran 0.26 g was added and a film was formed using a bar coater.
After forming the film, the film was left under a temperature condition of 100 ° C. for 3 hours to obtain a crosslinked polysilane film.

[0031]

[Chemical 6]

When the solubility of the obtained crosslinked polysilane film in toluene was examined, it was found to be completely insoluble. The result of the pencil hardness test was H.

Examples 2 to 4 Carbonium tris (triphenylphosphine) rhodium (I) hydride (catalyst B) and chlorobis (cyclooctene) as catalysts
An experiment was conducted in the same manner as in Example 1 except that rhodium (I) dimer (catalyst C) and rhodium (I) dicarbonylacetylacetonate (catalyst D) were used. As a reference, the same experiment was conducted on the polysilane film before crosslinking.

As a result, the polysilane film before cross-linking was soluble in toluene, which was 2B in the pencil hardness test, whereas all the cross-linked polysilane films of the examples were insoluble in toluene and in the pencil hardness test. Was H.

[Examples 5 to 8] Tris (methylphenylsilyl) phenylsilane was used as the organohydrogensilane, and the above catalyst A (Example 5), catalyst B (Example 6) and catalyst C (Example 7) were used. An experiment was conducted in the same manner as in Example 1 using Catalyst D (Example 8).

As a result, all of the crosslinked polysilane films were insoluble in toluene and had H in the pencil hardness test.

[Examples 9 and 10] Platinum vinyl siloxane toluene solution (platinum 1.0% by weight) as a catalyst (Example 9), butanol chloroplatinate solution (platinum 1.0% by weight)
An experiment was conducted in the same manner as in Example 1 except that (Example 10) was used.

As a result, all of the crosslinked polysilane films were insoluble in toluene, and were H in the pencil hardness test. In addition, IR analysis confirmed the generation of new siloxane.

[0039]

EFFECTS OF THE INVENTION The crosslinkable polysilane composition of the present invention enables a crosslinking reaction without breaking the polysilane chain,
It provides a solvent-insoluble and tough cured film that retains the properties of polysilane as it is, and is effectively applied to materials that require durability such as abrasion resistance and strength.

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[Procedure amendment]

[Submission date] November 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

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[Claims]

Embedded image A [(R ¹ R ² Si) _n (R ³ R ⁴ Si) _m ]
_p A ... (1) (wherein A is an alkenyl group having 1 to 12 carbon atoms,
R ¹ , R ² , R ³ and R ⁴ are the same or different and are each a substituted or unsubstituted C 1-12 alkyl group or aryl group, and n, m and p are 0 ≦ n ≦ 10 and 0 ≦, respectively. m ≦
It is an integer satisfying 10, n + m ≧ 10 and p ≧ 1. )
The composition according to claim 1 or 2, which is represented by

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

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Accordingly, the present invention, (A) at both ends alkenyl polysilane compound, (B) at least three heat in a molecule
A crosslinkable polysilane composition comprising a compound having a dolosilyl group and a (C) hydrosilylation catalyst, and a cured product obtained by curing the composition.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

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At least 3 residues are contained in one molecule.
Examples of the compound having a dolosilyl group include organohydrogensiloxane and organohydrogensilane. Specifically, hydrogen polysiloxane represented by the following formula (4) can be preferably used.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Hisashi Umehara 3-2-1 Sakado, Takatsu-ku, Kawasaki City, Kanagawa Prefecture Corporate Research Center, Shin-Etsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. (A) Alkenyl polysilanes having both terminals,
A crosslinkable polysilane composition comprising (B) a compound having at least three alkenyl groups in one molecule and (C) a hydrosilylation catalyst. 2. A composition according to claim 1, wherein the hydrosilylation catalyst is a rhodium metal complex. 3. An alkenyl polysilane having both terminals is represented by the following general formula (1): A [(R ¹ R ² Si) _n (R ³ R ⁴ Si) _m ] _p A ... (1) ( However, in the formula, A is an alkenyl group having 1 to 12 carbon atoms,
R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted or unsubstituted alkyl or aryl groups having 1 to 12 carbon atoms, and n, m and p are 0 ≦ n ≦ 10 and 0 ≦, respectively. m ≦ 1
It is an integer that satisfies 0, n + m ≧ 10, and p ≧ 1. 3. The composition according to claim 1 or 2, which is represented by 4. A cured product obtained by curing the crosslinkable polysilane composition according to claim 1, 2.