JPH02166124A - Production of polysilane - Google Patents

Abstract

PURPOSE:To obtain an Si-H bond-containing high-MW polysilane in high yields within a short time by polymerizing a trihydrosilane or a mixture thereof with a dihydrosilane through dehydrogenation in the presence of a specified catalyst. CONSTITUTION:A trihydrosilane (e.g. phenylsilane) or a mixture thereof with a dihydrosilane (e.g. methylphenylsilane) is polymerized desirably in a molar ratio of 0.25 or larger through dehydrogenation in the presence of a complex catalyst prepared by coordinating at least one ligand selected from among an organophosphorus, compound, an organoarsenic compound and an organoantimony compound with at least one member selected from among Rh, Pt and compounds thereof [e.g. hydridocarbonyltris(triphenylphosphine) rhodium: HRh(CO)(PPh3)3].

Description

[Detailed description of the invention]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing polysilane, and more particularly, the present invention relates to a method for producing polysilane, and more particularly, trihydrosilanes or a mixture of trihydrosilanes and dihydrosilanes are dehydrogenated in the presence of a specific catalyst to form silicon-hydrogen bonds. The present invention relates to a method for producing a polysilane having the following properties. Technical background of the invention and its problems Polysilane is a useful compound used in photoresists, semiconductors, electronic materials such as conductors, ceramic precursors, photopolymerization initiators, and the like. Therefore, there is a strong desire to develop an inexpensive and efficient manufacturing method for polysilane as described above. Heretofore, the following methods have been disclosed as methods for producing polysilanes having silicon-hydrogen bonds. (a) A method for producing polysilane by dehydrogenating trihydrosilanes in the presence of a titanocene or zircocene catalyst (Journal of Organometallic Chemistry (J, Organometal, C.
hes+,), vol. 279, 1985, C-11~C
-18 pages and Journal of American Chemical Society (-(J, As+, Chem, Soc,
),. Volume 108, No. 14, 1988, 4059-406
(page 6). Cp TIR'2 or Cp2 ZrR" 2nR
3illa 1----→ →si juice--+ II (n
= ~1 0) + n 2 (b) Method for producing polysilane by dehydrogenating dihydrosilanes in the presence of a diphenyltitanocene catalyst (Proceedings of the 57th Autumn Annual Meeting of the Chemical Society of Japan IA)
417, 1988). R″ (n −2 to 9) (c) A method for producing disilane by reacting phenylmethylsilane in the presence of a bis(triphenylphosphine)ethylene platinum catalyst (Organometallics
ometal, ), Volume 8, 1987, 1590-
1591 pages). (Ph3P)21't(i12C-CI+.)Ph2S
Il! 2 11PhMesI-8IPhMeH (27%) (d) A method for producing disilane by reacting diphenylsilane in the presence of a chlorotris(triphenylphosphine)rhodium catalyst (Journal of Organometallic Chemistry (J, Organomota!, Ches.
), vol. 55, 1973, pp. 07-C8). (Ph3P)3RhCI Ph2Sil! 2 1(P h S i −S t P !12 t((
38%) (e) A method for producing disilane and trisilane by reacting dihydrosilaanthracene in the presence of a chlorotris(triphenylphosphine)rhodium catalyst (Organometal, Vol. 6, 1987, 1595- 1596 pages). 7u −(ES I −('s t −n + ++
-(s + - is also Si % I -II, etc.) However, the production method disclosed above has the following problems. Namely, due to dehydrogenation polymerization of trihydrosilanes or dihydrosilanes, Methods for producing dimer- or trimer-or-more polysilanes have been limited to production methods that use titanocene or zircocene as catalysts.Furthermore, even with production methods that use titanocene or zircocene as catalysts, the degree of polymerization of the resulting polysilanes is low. 10 at most
The average molecular weight is about 900 to 1,400, and there are problems in that polysilane with a high degree of polymerization cannot be obtained and the reaction rate is slow. As described above, a method for producing high molecular weight polysilane by dehydrogenation polymerization of trihydrosilanes or dihydrosilanes has not been known. OBJECT OF THE INVENTION The present invention aims to solve the problems associated with the prior art, in which polysilane with a high molecular weight cannot be obtained and the reaction rate is slow when producing polysilane by dehydrogenation polymerization of hydrosilanes. The purpose is to provide an inexpensive and efficient method for producing high molecular weight polysilane. Summary of the Invention While investigating various methods for producing polysilane, the present inventors have discovered that hydrosilanes are combined with (i) at least one metal or compound selected from rhodium and platinum, and (i) an organic phosphorus compound, an organic arsenic. When the reaction is carried out in the presence of a complex catalyst composed of at least one type of ligand selected from organic antimony compounds and organic antimony compounds, high molecular weight polysilane can be produced in high yield and in a short time. This discovery led to the completion of the present invention. That is, in the method for producing polysilane according to the present invention, when producing a polysilane having a silicon-hydrogen bond by dehydrogenating hydrosilanes, trihydrosilanes,
or a mixture of trihydrosilanes and dihydrosilanes; (i) at least one member selected from rhodium and platinum;
Dehydrogenation polymerization as described above in the presence of a complex catalyst comprising a seed metal or compound coordinated with (i) at least one ligand selected from an organic phosphorus compound, an organic arsenic compound, and an organic antimony compound. It is characterized by a reaction. DETAILED DESCRIPTION OF THE INVENTION The method for producing polysilane according to the present invention will be specifically described below. Hydrosilanes In the present invention, as raw materials for producing polysilanes,
Trihydrosilanes represented by the following formula [11] are used alone, or trihydrosilanes and the following formula [1]
A mixture with dihydrosilanes shown in [1] is used. R' 81 H 3...[1] RIR2Si H 2...[11] [In the formula, R and R2 may be the same or different, and are an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, group or triorganosilyl group. ] As the trihydrosilanes represented by the above formula [1],
Specifically, methylsilane, ethylsilane, propylsilane, butylsilane, hexylsilane, phenylsilane, naphthylsilane, P-phenyl-phenylsilane, tolylsilane, benzylsilane, phenethylsilane, cyclohexylsilane, (triphenylsilyl)silane, (
Examples include trimethylsilyl)silane. Further, the dihydrosilanes represented by the above formula [1] include dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, dihexylsilane,
Diphenylsilane, dinaphthylsilane, di(P-phenyl-phenyl)silane, ditolylsilane, dibenzylsilane, diethylsilane, dicyclohexylsilane, di(
triphenylsilyl)silane, methylphenylsilane,
Methylnaphthylsilane, methyltolylsilane, methylbenzylsilane, (triphenylsilyl)methylsilane,
Examples include (trimethylsilyl)methylsilane. In the present invention, when using a mixture of trihydrosilanes and dihydrosilanes, the order of trihydrosilanes/
It is preferable to use a mixture in which the molar ratio of dihydrosilanes is 0.25 or more. Complex Catalyst In the present invention, when dehydrogenating the hydrosilanes as described above, (i) at least one metal or compound selected from rhodium and platinum is added to (i) an organic phosphorus compound, an organic arsenic compound, and an organic antimony compound. A complex catalyst formed by coordinating at least 18i ligands selected from compounds is used. Rhodium metal or rhodium compound The rhodium metal or rhodium compound used in the present invention includes rhodium metal supported on activated carbon, silica, etc., rhodium black, zero-valent complex of rhodium, monovalent, divalent, trivalent, and pentavalent rhodium. Examples include valent compounds or complexes. Specifically, such rhodium compounds or complexes include Rh (CO)8, Rh, (CO)1□,
Rh (CO), Rh (GO) (norbornadiene), [Rh (u-OMe) (i,5-
cyclooctadiene)]2, [Rh(μm0g)(i,
5-cyclooctadiene)]2,[Rh(μmCI)
(CIl□-CIl□)2]2, [Rh (μmCD
)(CO) 2] 2, [Rh(μm0Ac)(i,5
-cyclooctadiene)]2, [Rh (μm0Ph)
(i,5-cyclooctadiene)]2, RhB(i,5
-cyclooctadiene)6 (Co3)3, -[Rh(OAc) ], [RhCN, ][R
h (μmCjri(π-allyl)], RhC1
13, RhBr, Rh1a, etc. Platinum metal or platinum compound The platinum metal or platinum compound used in the present invention includes platinum metal supported on activated carbon, silica, etc., platinum black, a zero-valent complex of platinum, a divalent or tetravalent compound or complex of platinum, etc. It is. Specifically, such platinum compounds or complexes include Pt(II2NCII.C■■2N!12)2, C
113C113 Pt(Nil) CI 5Pt(CIl
CN) 2 (J6. to 2PtCN 4, Pt(II□N
C112C1l□Nl[2) Cll2, II PtC
l, PtCl2 (i,5-cyclooctadiene), Pt (acetylacetonate), PtC
Examples include N2, PtCfI, and the like. Ligand The ligand used in the present invention has the following formula [■] or [I
V] and the like. R3 3...[■] R-E-CHR-CHR-ER...[IV] [In the formula,
E is phosphorus, arsenic or antimony, R3 may be the same or different and is an alkyl group, aryl group, cycloalkyl group or aralkyl group, R
4 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, or an aralkyl group. ] The above formula

As a ligand represented by [■] or [■E,
Specifically, P M 8 ,, P E t 1P
Bu a', PPh, P(Cll Ph)
, PPh Me, ^5ee3. AsEt, A
s13u3, AsPh3, As (Cll2 Ph)
3. AsPhMe, SbMe, 5bEt
, 5bBu, 5bPh3. Sb (Cll
Ph), 5bPh2 rib, Ph2P-Cll2-
CH! 2-PPh2, Ph As-C112-Cl
12-^5Phz, Ph Sb-Cll2- C11
2-5bPh2 and the like. As the complex catalyst used in the present invention, a complex catalyst in which the above-mentioned ligand is coordinated to the above-mentioned rhodium and/or platinum metal or its compound may be used, or the above-mentioned rhodium and/or Platinum metal or its compound and the above-mentioned ligand may be mixed I7 in the reaction system and used while producing a complex catalyst in the reaction system. When producing a complex catalyst in a reaction system, it is preferable to mix the ligand and rhodium and/or platinum metal or a compound thereof in a molar ratio of 1 to 20. Specifically, the above-mentioned complex catalyst used in the present invention includes IIRh(CO)(PPh3't 3, II
Rh(CO)(AsPh), IIRh(CO)
(SbPh3) 3, PhCfl(PPh)
, RhCl3(AsPha)s, RhOff
(SbPh) , IRh(PPh3) , [
PPh Rh(OAc)], RhC13(PHt
3) 3. PtCN 2(Co) PPh8, Pt(P
Et3) 2CIl II, PtC1(PPh)
, ptcΩ2 (AsPhs) 2. PtCN7
(SbPh), PtBr2(PEt3)
2. [Pt(PBu)(J], Pt02
(r'Pb3) 2. PL(PPh), Pt
(Ph2PC112CI12PPh2>C12, etc.) In the complex catalyst used in the present invention, rhodium and/or platinum metal oxidatively adds silicon-hydrogen bonds to form silicon-silicon bonds as shown in the following formula. It is also presumed that the ligand contributes to the stabilization of the rhodium and/or platinum complex and plays a role in sustaining the dehydrogenation polymerization reaction. The rhodium and/or platinum complex catalyst used in the invention can also be used as an olefin hydrosilylation catalyst, so if an olefin compound such as cyclohexene is present in the reaction system, cyclohexyl groups will be added to the side chains of the resulting polysilane. Organic groups such as It is preferable to carry out the reaction in the absence of oxygen and/or water in the reaction system as a hydrogen gas atmosphere.If oxygen and/or water is present in the reaction system, silicon-hydrogen bonds are oxidized and silanol groups and siloxane It becomes easier to form bonds.The polymerization reaction may be carried out under normal pressure, or may be carried out under reduced pressure or increased pressure.The reaction temperature is 0 to 2
It is desirable that the temperature is 00°C, preferably 15 to 150°C. The rhodium and/or platinum complex catalyst in the reaction system is preferably used in an amount of about 10-6 to 10 mol, preferably about 10 to 10-z mol, per mol of the hydrosilane. The reaction may be carried out in the presence or absence of a solvent. When using a solvent, toluene,
Hydrocarbon solvents such as xylene, heptane, dodecane, ditolylbutane, and cumene are preferably used. Further, when an olefin compound such as cyclohexene is used as the hydrocarbon solvent, it is hydrogenated to form cyclohexane, and as described above, it is possible to produce a polysilane having a cyclohexyl group in the side chain. The reaction time varies depending on the reaction temperature, but is usually 2~
24 hours is sufficient. Effects of the Invention According to the method for producing polysilane according to the present invention, polysilane having a higher molecular weight than conventionally known polysilanes can be obtained in a short time and in a high yield. Furthermore, by using the method of the present invention, dihydrosilanes, whose polymerization ability was not known in the past, can be incorporated into the polysilane main chain to form -12Slh units by mixing them with trihydrosilanes. becomes. Furthermore, the polysilane obtained in the present invention has silicon in the side chain.
Since it has hydrogen bonds, various chemical modifications are possible by performing a hydrosilylation reaction with an olefin compound. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 Capacity 50ml with reflux condenser, stirrer and thermometer
After purging the inside of the glass flask with argon gas, 10 mmol of phenylsilane (PhSIll3) and hydridocarbonyltris(triphenylphosphine)rhodium (llRh (CO) (PPh) were added as a catalyst.
3) 0.2 mmol of 3) was introduced and stirred at 25°C for 1 hour. Then, the mixture was stirred in an oil bath.
The temperature was maintained at 110°C and the reaction was carried out for a total of 12 hours. After the reaction was completed, the resulting reaction mixture was diluted with 30 ml of dry toluene, and then a polysilane fraction was fractionated using column chromatography packed with silica gel. When toluene was removed by evaporation from this fraction, polysilane was obtained in a yield of 80% (based on PhS1113). GPC analysis revealed that the obtained polysilane had a number average molecular weight (KYn) of 1970 and a weight average molecular weight (Mw) of 38.
It was found to have a value of 00. In addition, it was found by infrared absorption spectrum and NMR analysis that the basic fJ-Raku of the main chain of the obtained polysilane was +Ph5JII)-. Example 2 As a catalyst, cis-bis(triphenylphosphine)dicoo platinum (cls-PtCl22(PPh3)2
) Polysilane was produced in the same manner as in Example 1, except that 0.2 mmol was used. As a result, the yield of polysilane was 85% (PhSI113
standard), Mn is 3210, and Fay is 3
300, and the basic skeleton of the main chain is the same as in Example 1 (P
It was hSII. Comparative Example 1 As a catalyst, dimethyl titanocene (Cp2Tl(C1(
3) 2) Production of polysilane was attempted in the same manner as in Example 1, except that 0.2 mmol was used. As a result, the basic skeleton of the main chain of the polysilane obtained is −
(-PhSIll), but both Mn and Mv are 1
It was found that the value was less than 00.0. Comparative Example 2 As a catalyst, diμmchlorotetratonyl dirhodium ([I?h(μmCI!')(CO)2]2)0.
An attempt was made to produce polysilane in the same manner as in Example 1 except that 1 mmol was used, but polysilane could not be obtained. Comparative Example 3 Chloroplatinic acid (HPtC11-6r120'
) Polysilane was attempted to be produced in the same manner as in Example 1 except that 12 mmol of B 2 O was used, but polysilane was not obtained. Examples 3 to 9 Rhodium or platinum compound as catalyst and ligand as shown in Table 1
Polysilane was produced in the same manner as in Example 1, except that the mixture was used in the proportions shown in . The results are shown in Table 1. Yield 11 of polysilane in the table, Ph
5II! It is a standard. Moreover, the basic bone Bc of the main chain was +Ph5II+. Examples 10 to 13 The type of trihydrosilane as a raw material was changed as shown in Table 2, and cis-bis(triphenylphosphine)dichloroplatinum (cps-PtC1(PPh3)) was used as a catalyst.
2) 0. Polysilane was produced in the same manner as in Example 1 except that 2 mmol was used. The results are shown in Table 2. The yield of polysilane in the table is based on the trihydrosilane used. Examples 14-15 Polysilane was produced in the same manner as in Example 1, except that a total of 10 mmol of the mixture of trihydrosilane and dihydrosilane shown in Table 3 was used as the raw material, and the catalyst shown in Table 3 was used. . The results are shown in Table 3. The basic skeletons of the main chains of the obtained polysilanes are +Ph5111+ and +PhMoSIMeP, respectively.
h) (Example 14) or -(PhS11) and +PhC
11281CII. It was a mixture of Ph+- (Example 15) units. Example 16 Except that 30 ml of dry toluene was used as the reaction solvent,
Polysilane was produced in the same manner as in Example 1. As a result, the yield of polysilane was 72% (P IIS I
IIs standard), Mn was 1800, Mw was 3500, and the basic skeleton of the main chain was the same as in Example 1 (PhS11). Example 17 15 ml of dry toluene instead of 30 ml of dry toluene
Polysilane was produced in the same manner as in Example 16, except that a mixture of 15 ml of cyclohexene and 15 ml of cyclohexene was used. As a result, the conversion rate of Ph5II 3 was 98%, the Mn of the obtained polysilane was 1600, and the Mv was 3000. Structural solution of polysilane h

Claims (1)

[Claims] 1. When producing a polysilane having a silicon-hydrogen bond by dehydrogenating hydrosilanes, trihydrosilanes or a mixture of trihydrosilanes and dihydrosilanes are combined with (i) rhodium; , at least one metal or compound selected from platinum, and (ii) at least one selected from organic phosphorus compounds, organic arsenic compounds, and organic antimony compounds.
1. A method for producing polysilane, which comprises carrying out the dehydrogenation polymerization reaction in the presence of a complex catalyst in which a species of ligand is coordinated.