JP2600111B2 - Method for producing silicon-containing polymer compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for producing a silicon-containing polymer compound. More specifically, the present invention is useful as a photoresist material or a pre-ceramic material, or as a material for a conductive material, wherein the main chain constituent element is composed of a silicon atom or a silicon atom and a carbon atom, and The present invention relates to a method for efficiently and industrially producing a silicon-containing polymer compound having a Si—Si bond therein.

[0002]

2. Description of the Related Art Recently, silicon-containing polymer compounds in which a main chain constituent element is a silicon atom or a silicon atom and a carbon atom have attracted attention as a photoresist material, a preceramic material and the like. In addition, a polymer compound having a main chain composed of only silicon atoms or a carbon π-electron system (eg, C = C bond) and silicon atoms is added with a Lewis acid such as iodine, antimony pentafluoride, or iron trichloride. Doped is known as a conductive material.

Heretofore, the main-chain constituent elements consist of silicon atoms or silicon atoms and carbon atoms, and Si-
It is known that a silicon-containing polymer compound having a Si bond can be obtained by a method based on a wurtz-type coupling reaction of an α, ω-bis (halosilyl) compound. However, in this method, it is necessary to perform dehalogenation using an alkali metal such as metal sodium, and as a result, an alkali metal halide is produced as a by-product, and the obtained polymer has a polydisperse molecular weight distribution. However, this is not an industrially advantageous method.

[0004] In addition, a method is known in which a ring compound having a ring structure having a Si-Si bond is subjected to ring-opening polymerization in the presence of an anionic initiator such as alkyllithium, silylpotassium, and ammonium fluoride. Journal of the American Chemical Society (J.
Am. Chem. Soc. ) "Vol. 111, No. 7641
(1989), Vol. 113, p. 1046 (1991), “MacroMolecules (Macro)
Vol. 27, p. 2360 (1994)]. However, in this method, in order to obtain a polymer having a high molecular weight, the reaction temperature must be-
It is necessary to maintain the temperature at a low temperature of 50 ° C. or less, which is not an industrially advantageous method.

Further, as a method for producing a silicon-containing polymer compound by reacting a cyclic compound having an Si—Si bond in a ring structure in the presence of a transition metal complex, a catalytic amount of tris (dibenzylidene) is dissolved in acetonitrile. Acetone) A method of reacting 1,1,2,2-tetramethyl-1,2-disilacyclopentane in the presence of palladium and triphenylphosphine [“Polymer Preprint Japan”
s, Japan), Vol. 40, p. 355 (199
1 year) or 1,2-difluoro- in the presence of a catalytic amount of tetrakis (triphenylphosphine) palladium.
1,2-dimethyl-1,2-disilacyclopentane
A method of reacting at 00 ° C. [“Journal of Organometallic Chemistry (J. Organome)
t. Chem. ) "Vol. 114, C19 (1976)
Years)], but cannot be practically used because of many by-products or the indeterminate structure and molecular weight of the polymer obtained.

[0006]

The present invention overcomes the drawbacks of the prior art by utilizing a novel reaction, wherein the main chain constituent element comprises a silicon atom or a silicon atom and a carbon atom, and An object of the present invention is to provide a method for efficiently and industrially producing a silicon-containing polymer compound having a Si-Si bond in a chain.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a method for producing a polymer compound containing silicon in the main chain, and as a result, have found that a Si-Si bond is formed in a ring structure. It has been found that the object can be achieved by reacting at least one cyclic compound having a specific structure in the presence of a specific ratio of a specific chain disilane and a specific metal complex, and performing ring-opening polymerization, Based on this finding, the present invention has been completed.

That is, the present invention provides (A) a four-membered or five-membered ring compound in which the ring-constituting element comprises a silicon atom or a silicon atom and a carbon atom and has at least one Si—Si bond in the ring structure. In the presence of (B) a chain disilane having at least one ethynyl group bonded to a silicon atom and (C) a palladium complex or a platinum complex in an amount of 0.5 mol or less per 1 mol of the cyclic compound. Characterized in that the main chain constituent element is composed of a silicon atom or a silicon atom and a carbon atom, and Si-S is contained in the main chain.
It is intended to provide a method for producing a silicon-containing polymer compound having an i-bond.

In the method of the present invention, the cyclic compound (A) used as a main raw material has a ring-constituting element comprising a silicon atom or a silicon atom and a carbon atom, and has at least one Si-Si bond in the ring structure. And a four-membered or five-membered ring compound.

As such a cyclic compound, for example, a compound represented by the general formula

Embedded image [X in the formula is -CR ⁵ R ⁶ -or -SiR ⁵ R ^6- (where R ⁵ and R ⁶ are a hydrogen atom or a hydrocarbon group, and are bonded to the respective carbon atoms or silicon atoms. Each R ⁵ and R ⁶ may be the same or different, and two of them may be connected to form a cyclic structure together with the carbon atom or silicon atom to which they are bonded. Wherein two or three Xs may be the same or different, R ¹ , R ² , R ³ and R ⁴ are hydrocarbon radicals and n is an integer of 2 or 3] The compounds represented can be mentioned. Specific examples of such compounds include, for example, 1,1,2,2-tetramethyl-1,2-
Disilacyclobutane, 1,1,2,2,3,3,4,4
-Octamethyl-1,2-disilacyclobutane, 1,
1,2,2-tetramethyl-3,4-diisopropylidene-1,2-disilacyclobutane, 1,2-diphenyl-1,2-dimethyl-1,2-disilacyclobutane,
1,1,2,2-tetramethyl-1,2-disilacyclopentane, 1,2-diphenyl-1,2-dimethyl-
1,2-disilacyclopentane, 1-phenyl-1,
2,2-trimethyl-1,2-disilacyclopentane,
1,1,2,2-tetramethyl-3,4-benzo-1,
2-disilacyclobutene, 1,2-diphenyl-1,2
-Dimethyl-3,4-benzo-1,2-disilacyclobutene, 1,2-diethyl-1,2-dimethyl-3,4-
Benzo-1,2-disilacyclobutene, 1,1,2,2
-Tetraethyl-3,4-benzo-1,2-disilacyclobutene, 1,2,3,4-tetramethyl-1,2,2
3,4-tetraphenylcyclotetrasilane, 1,1,
There are 2,2,3,3,4,4-octaethylcyclotetrasilane, 1,2,2,3,3,4,4,5,5-nonamethyl-1-phenylcyclopentasilane and the like.

On the other hand, in the method of the present invention, the chain disilane of component (B) used in combination with component (A) has at least one ethynyl group on a silicon atom. An appropriate substituent may be introduced. Examples of the substituent include an alkyl group, an aryl group, a trialkylsilyl group, and an alkoxy group.

Examples of such chain disilanes include, for example, those represented by the general formula

Embedded image Wherein at least one of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is —C 12C—R (where R is a hydrogen atom, a hydrocarbon group, a trialkylsilyl group, Alkoxy group)
And the other is a hydrogen atom or a hydrocarbon group]. Specific examples of such compounds include, for example, 1-ethynyl-1,1,2,2
2,2-pentamethyldisilane, 1-phenylethynyl-1,1,2,2,2-pentamethyldisilane, 1-
(1-propynyl) -1,1,2,2,2-pentamethyldisilane, 1-trimethylsilylethynyl-1,1,
2,2,2-pentamethyldisilane, 1,2-bis (phenylethynyl) -1,1,2,2-tetramethyldisilane, 1,1-bis (phenylethynyl) -1,2,2
2,2-tetramethyldisilane, 1,1,2-tris (phenylethynyl) -1,2,2-trimethyldisilane, 1,1,2,2-tetrakis (phenylethynyl)
-1,2-dimethyldisilane, 1,1,1,2,2-pentakis (phenylethynyl) -2-methyldisilane,
Hexakis (phenylethynyl) disilane, 1-phenylethynyl-2-phenyl-1,1,2,2-tetramethyldisilane, 1,2-bis (phenylethynyl)-
1,2-diphenyl-1,2-dimethyldisilane, 1,
1,1-tris (phenylethynyl) -2,2,2-triphenyldisilane, 1-phenylethynyl-1,1,1
2,2,2-pentaethyldisilane, 1,2-bis (phenylethynyl) -1,2-dipropyl-1,2-dimethyldisilane, 1,2-bis (phenylethynyl)-
There are 1,2-dibenzyl-1,2-dimethyldisilane and the like.

In the present invention, the chain disilanes of the component (B) must be used in a proportion of 0.5 mol or less based on 1 mol of the cyclic compound of the component (A).
Usually, 0.001 to 0.5 with respect to 1 mol of the cyclic compound.
Mole, preferably 0.01 to 0.2 mole.

In the present invention, if the component (B) is not present, the initial reaction does not proceed, and the desired high molecular weight polymer cannot be obtained.

In the present invention, (C) a palladium complex or a platinum complex is used as a catalyst. As these complexes, conventionally known ones can be used, but it is preferable to use a compound at least partially soluble in the reaction system in terms of the reaction rate. It is particularly preferred that these complexes contain an organic ligand, such as phosphine, phosphinite, phosphonite, phosphite, olefin, β-diketonato ligand, conjugated ketone, nitrile, amine Carboxylate ligand, carbon monoxide and the like.

The organic ligand includes, for example, trimethylphosphine, tributylphosphine, triethylphosphine, tricyclohexylphosphine, triphenylphosphine, tri (p-tolyl) phosphine, tri (p
Chain phosphines such as -anisyl) phosphine, diphenylmethylphosphine, phenyldimethylphosphine, P-methylphospholene, P-methylphosphol, 9
Phosphines such as 1-methyl-9-phosphabicyclo [4.2.1] nonane, 1,2-bis (dimethylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,3-bis (Diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane,
1,1′-bis (dimethylphosphino) ferrocene,
1,1'-bis (diphenylphosphino) ferrocene,
bisphosphines such as α, α′-bis (dimethylphosphino) -o-xylene and 1,2-bis (dimethylphosphino) benzene, methyl dimethylphosphinite,
Phosphinites such as phenyl diphenylphosphinite, phosphonites such as dimethyl methylphosphonite and dimethylphenylphosphonite, triethyl phosphite, triphenyl phosphite, and 1-phospha-
2,6,7-trioxa-4-ethylbicyclo [2.
2.2] phosphites such as octane, ethylene, propylene, cyclooctene, maleic anhydride, 1,5-hexadiene, 1,5-cyclooctadiene, 1,3-cyclopentadiene, 2,5-norbornadiene, 1,3,3
Olefins such as 5,7-cyclooctatetraene, dienes, β-diketonato ligands such as acetylacetonate, conjugated ketones such as dibenzylideneacetone, nitriles such as acetonitrile and benzonitrile, ethylenediamine, 2,2'-bipyridyl And carboxylato ligands such as acetonate.

In the present invention, specific examples of the palladium complex and platinum complex used as a catalyst include tetrakis (triphenylphosphine) palladium, tetrakis (diphenylmethylphosphine) palladium, dichlorobis (trimethylphosphine) palladium, and dichlorobis (triethylphosphine). Palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (phenyldimethylphosphine) palladium, dichloro [1,2-bis (dimethylphosphino) ethane] palladium, dichloro [1,3-bis (diphenylphosphino) propane] palladium, Dichloro [1,4-bis (diphenylphosphino) butane] palladium, dichloro [1,2-bis (diethylphosphino) ethane] palladium, dichloro [1 1'-bis (diphenylphosphino) ferrocene] palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichloro (η-1,5-cyclooctadiene) palladium, bis (η-allyl) Palladium, (η-ethylene) bis (triphenylphosphine)
Palladium, dichlorobis (benzonitrile) palladium, dichloroethylenediaminepalladium, palladium acetate, (η-ethylene) bis (triphenylphosphine) platinum, tetrakis (triphenylphosphine) platinum, tetrakis (diphenylmethylphosphine) platinum,
Tetrakis (triethylphosphine) platinum, dichlorobis (triphenylphosphine) platinum, dibromobis (triethylphosphite) platinum, bis (η-1,5-cyclooctadiene) platinum, dichloro (η-1,5-cyclooctadiene) platinum , Dicarbonylbis (tributylphosphine) platinum, carbonatobis (tricyclohexylphosphine) platinum, bis (dibenzylideneacetone) bis (triphenylphosphine) platinum, tris (dibenzylideneacetone) diplatinum, dichlorobis (benzonitrile) platinum, dichlorobis ( (Acetonitrile) platinum and the like.

In the present invention, these complexes may be used alone or in combination of two or more, and together with these complexes, the same or different distributions as those contained in the complexes may be used. One or more ligands may be added to the reaction system. The amount of these complexes used may be a so-called catalytic amount, and is usually 0.1 to 1 mol of the cyclic compound (A).
It is selected in the range of 00001 to 0.5 mol. When a ligand is added together with the complex, the amount is preferably selected so that the molar ratio to the palladium or platinum atom in the complex is in the range of 1 to 20.

In the present invention, the reaction can be easily carried out without using a solvent, but the reaction may be carried out in a solvent if necessary. As the solvent, in consideration of the reactivity of the cyclic compound to be reacted and the chain disilanes, for example, solvents such as aromatic hydrocarbons, saturated aliphatic or saturated alicyclic hydrocarbons, and alkyl ethers are used. It is advantageous to choose from.

In the present invention, the reaction proceeds even at 0 ° C. or lower, but it can be heated to a temperature of about 250 ° C. to increase the reaction rate. From the viewpoints of reaction rate and suppression of side reactions, the preferred reaction temperature is generally in the range of 0 to 200 ° C, and particularly preferably in the range of 50 to 150 ° C, though it depends on the type of raw materials used. .

The separation of the product after the completion of the reaction can be carried out by a commonly used known means, for example, a method such as distillation, recrystallization or chromatography.

In this way, a silicon-containing polymer compound in which the main chain constituent elements are composed of silicon atoms or silicon atoms and carbon atoms and have a Si--Si bond in the main chain can be efficiently obtained. As the silicon-containing polymer obtained by the method of the present invention, for example, a general formula

Embedded image Wherein X, R ¹ , R ² , R ³ , R ⁴ and n have the same meaning as described above, and have a weight average molecular weight of 6 × 10 ² to 1 × 10 ⁶ . Range.

[0023]

According to the present invention, the main chain constituent element is composed of silicon atom or silicon and carbon atom, and S in the main chain.
A silicon-containing polymer compound having an i-Si bond can be produced efficiently and industrially advantageously. The silicon-containing polymer compound obtained by the method of the present invention is useful as a photoresist material or a preceramic material, or as a material for a conductive material.

[0024]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 0.5 mmol of 1,1,2,2-tetramethyl-1,2-disilacyclopentane, 1,2-bis (phenylethynyl) -1,1,2,2-tetramethyldisilane
0.05 mmol and dichloro [1,4-bis (diphenylphosphino) butane] palladium 0.005 mm
ol mixture was charged into a glass sealed tube under nitrogen.
Heated to 0 ° C. for 15 hours. After opening, the reaction mixture was analyzed by gas chromatography and found to be 1,1,
It was confirmed that 2,2-tetramethyl-1,2-disilacyclopentane was consumed by 56%. The palladium complex was removed by florisil column chromatography using benzene as the eluent, and the volatile components were further removed under reduced pressure, whereby colorless gel-like poly (tetramethyldisilylene-trimethylene) was consumed. ,
It was isolated in a yield of 61% based on 1,2,2-tetramethyl-1,2-disilacyclopentane. The obtained poly (tetramethyldisilylene-trimethylene) has the following circulating units, and its analytical data is shown below.

[0026]

Embedded image

¹ H-NMR (CDCl ₃ ) (ppm); δ
1.42-1.27 (m, 2H), 0.7-0.6
(M, 4H), 0.02 ( s, 12H) 13 C-NMR (CDCl 3) (ppm); δ 20.2
(2C), 19.9, -3.8 (4C) ²⁹ Si-NMR (CDCl ₃ ) (ppm); δ −1
8.6 IR (liquid film) (cm ^-1 ); 1245 GPC analysis (based on polystyrene); weight average molecular weight
1.2 × 10 ³ , dispersity 1.4

Comparative Example 1 In Example 1, 1,2-bis (phenylethynyl)
The reaction was carried out in the same manner as in Example 1 except that -1,1,2,2-tetramethyldisilane was not used. After opening, the reaction mixture was analyzed by gas chromatography. 44% of 2-tetramethyl-1,2-disilacyclopentane is consumed, and the consumed raw material 1,
1,1, which is a cyclic dimer with a yield of 89% based on 1,2,2-tetramethyl-1,2-disilacyclopentane
2,2,6,6,7,7-octamethyl-1,2,6
It was confirmed that 7-tetrasiladecane was produced. GPC analysis of this reaction mixture (based on polystyrene) confirmed that only a small amount (5% or less) of poly (tetramethyldisilylene-trimethylene) was formed.

Example 2 In Example 1, 1,1,2,2-tetramethyl-
1,2,3 instead of 1,2-disilacyclopentane
Use 4-tetramethyl-1,2,3,4-tetraphenylcyclotetrasilane and use toluene as the solvent
The reaction was carried out in the same manner as in Example 1 except that 0.1 ml was used, and the reaction mixture was analyzed by ²⁹ Si-NMR.
6% of raw material 1,2,3,4-tetramethyl-1,2,2
It was confirmed that 3,4-tetraphenylcyclotetrasilane was consumed. This reaction mixture was treated in the same manner as in Example 1. As a result, the starting material 1,2,3,4-tetramethyl-1,2,3,4-tetraethyl which consumed poly (methylphenylsilylene) represented by the following formula was obtained. Obtained in a yield of 28% based on phenylcyclotetrasilane. The various data of poly (methylphenylsilylene) are as follows and were consistent with the values described in the literature.

[0030]

Embedded image

GPC analysis (based on polystyrene); weight average molecular weight 1.5 × 10 ³ , dispersity 2.0

Claims (4)

(57) [Claims] (A) The ring-constituting element is composed of a silicon atom or a silicon atom and a carbon atom, and Si—S is contained in the ring structure.
(B) a chain having at least one ethynyl group bonded to a silicon atom in an amount of 0.5 mol or less based on 1 mol of the cyclic compound; Characterized in that the reaction is carried out in the presence of disilanes and (C) a palladium complex or a platinum complex, wherein the main chain constituent element comprises a silicon atom or a silicon atom and a carbon atom, and a Si-Si bond is formed in the main chain. A method for producing a high molecular weight silicon-containing polymer compound. 2. The chain disilane as the component (B) is converted into the component (A)
2. The method according to claim 1, wherein the compound is used in an amount of 0.001 to 0.5 mol per 1 mol of the cyclic compound. 3. The palladium complex or platinum complex of the component (C) is added in an amount of 0.000 to 1 mol of the cyclic compound of the component (A).
3. The method according to claim 1, wherein the compound is used in an amount of from 0.01 to 0.5 mol. 4. The method according to claim 1, wherein the reaction temperature is 0 to 200 ° C.