JPH02184691A - Preparation of silane oligomer - Google Patents

Abstract

PURPOSE:To inexpensively and efficiently provide the subject compound by subjecting a trihydrosilane, dihydrosilane or monohydrosilane to a dehydrative condensation reaction in the presence of a specific complex catalyst. CONSTITUTION:For example, a trihydrosilane of a formula: R<1>SiH3 (R<1> is alkyl, triorganosilyl, etc.) (e.g. methylsilane) is subjected to a dehydrative condensation reaction in the presence of a complex catalyst [e.g. RuCl2(PPh3)3] (Ph is phenyl) in the atmosphere of an inert gas such as helium at 0-200 deg.C for 2-24hr to provide the objective compound, the complex catalyst being prepared by allowing ruthenium metal or a compound thereof (e.g. RuO2) to form a complex with an ligand comprising an organic phosphorus compound, organic arsenic compound or organic antimony compound [e.g. a ligand of a formula: ER4 (E is P, As or Sb; R<4> is alkyl, aryl, etc.)] in a mol ratio of 1-20:1. The ruthenium complex catalyst is preferably used in an amount of 10<-6>-10<-2>mol per mol of the hydrosilane and, when a solvent is used, toluene, etc., are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing silane oligomers, and more particularly, the present invention relates to a method for producing silane oligomers, and more specifically, a method for producing silane oligomers, in which trihydrosilanes, dihydrosilanes, or monohydrosilanes are dehydrogenated and condensed in the presence of a specific catalyst. The present invention relates to a method for producing a silane oligomer.

Technical Background of the Invention Silane oligomers are useful compounds used in photoresists, semiconductors, electronic materials such as conductors, ceramic precursors, photopolymerization initiators, ultraviolet absorbers, oxygen absorbers, silylation agents, etc. .

Therefore, there is a strong demand for the development of a dehydrogenation condensation method for hydrosilanes that can produce silane oligomers inexpensively and efficiently.

Heretofore, the following methods have been disclosed as methods for producing silane oligomers by dehydrogenation condensation reaction of trihydrosilanes or dihydrosilanes.

(a) A method for obtaining silane oligomers by dehydrogenation condensation of trihydrosilanes in the presence of a titanocene or zirconocene catalyst (Journal of Organometallic
Chemistry (J.

Organos+eta1. Chew,),, Part
Volume 279, 1985, pages C-11-C-13 and Journal of the American Chemical Society (J, Ag, Chθ■.

Soc, ), Volume 108, No. 14, 1986, 4
059-408B).

CpTIR'2 or CI)2 ZrR" 2nR3I
IIs (b) Method for obtaining silane oligomers by dehydrogenation condensation of dihydrosilanes in the presence of a diphenyltitanocene catalyst (Proceedings of the 57th Autumn Annual Meeting of the Chemical Society of Japan IA417.1
988).

R' (n -2 to 9) (c) Phenylmethylsilane was added to bis(triphenylphosphine)ethylene in the presence of a platinum catalyst in the presence of 1. Method for obtaining disilane by dehydrogenation condensation (Organometallics (Org)
anoIletal, ), Volume 8, 1987, 15
90-1591).

(Ph P) Pt(II C-C112) Ph
MeSltlz 1IPhMesi-3I
Method for obtaining disilane by dehydrogenation condensation of PhMell (27%) (diphenylsilane) in the presence of chlorotris(triphenylphosphine)rhodium catalyst (Journal of Organometallic Chemistry (J, Or
ganometal, Chem,), Volume 55, 19
1978, pp. 07-C8).

(Ph3P)3RhCF Ph2Sll+2 HPh Sl-5iPh2I+ (38%) A method for obtaining disilane and trisilane by dehydrogenating (e) dihydrosilaanthracene in the presence of a chlorotris(triphenylphosphine)rhodium catalyst (Organometal, ), Volume 6, 198
7, pp. 1595-1596).

(PPh3) 3RhCj) 〆1-1? ,,5i112 On the other hand, as conventional dehydrogenation condensation methods for producing disilane using monohydrosilanes, the following methods have been disclosed.

(a) A method of dehydrogenating dimethylphenylsilane in the presence of a bis(trimethylphosphine)dichloroplatinum catalyst to obtain disilane in a yield of 7% (Applied Organometallic Chemistry (Appl, Organo
Metal, Ches, ), Volume 2, 1988, pp. 91-92 and Proceedings of the 57th Autumn Annual Meeting of the Chemical Society of Japan I IVB15.1988).

PtCI (PMea) 2 2 M +3 2 S i P h IIMe P
hPh51-8IPh 2+ll2 (7,0%) In addition, the above literature states that when the above reaction is carried out using a ruthenium and iridium complex catalyst, disilane cannot be obtained, and dimethyl used as a raw material It is stated that only methyldiphenylsilane, a disproportionation reaction product of phenylsilane, was obtained.

By the way, the method for producing a silane oligomer by the dehydrogenation synthesis reaction of hydrosilanes disclosed above had the following problems. That is, the method of obtaining dimer-trimer or more silane oligomers by dehydrogenation condensation of trihydrosilanes or dihydrosilanes is limited to methods using titanocene or zirconocene as a catalyst, and the problem is that the reaction rate is slow. was there. On the other hand, methods for obtaining disilane by dehydrogenation condensation of monohydrosilanes are limited to methods using platinum complexes as catalysts, and have the problem of extremely low yields.

Purpose of the Invention The present invention is directed to a conventional method for producing silane oligomers by dehydrogenation condensation reaction of hydrosilanes, which has problems such as limited usable catalysts, slow reaction rate, and low yield. In view of this, the purpose of the present invention is to solve these problems, and to provide a method for producing silane oligomers that can be produced inexpensively and efficiently by dehydrogenation condensation reaction of hydrosilanes. There is.

Summary of the Invention The present inventors have investigated various methods for producing silane oligomers by dehydrogenation condensation reaction of hydrosilanes, and found that (i)
) Dehydrogenation condensation of hydrosilanes in the presence of a complex catalyst consisting of a ruthenium metal or compound coordinated with (ii) at least one type of ligand selected from an organic phosphorus compound, an organic arsenic compound, and an organic antimony compound. The inventors have discovered that silane oligomers can be produced in high yield and in a short time by doing so, and have completed the present invention.

That is, in the method for producing a silane oligomer according to the present invention, (i) a ruthenium metal or compound is coordinated with (ii) at least one ligand selected from an organic phosphorus compound, an organic arsenic compound, and an organic antimony compound. The method is characterized in that trihydrosilanes, dihydrosilanes, or monohydrosilanes are subjected to dehydrogenation condensation in the presence of a complex catalyst to produce a silane oligomer.

DETAILED DESCRIPTION OF THE INVENTION The method for dehydrogenation condensation of hydrosilanes according to the present invention will be specifically described below.

Silane oligomer In this specification, the silane oligomer refers to dimers to about 100j units, which are dehydrogenation condensation products of hydrosilanes used as raw materials.

In the present invention, when trihydrosilanes or dihydrosilanes are used as raw materials, a 3-100 mer silane oligomer as shown in the following formula is obtained.

A dimeric disilane is obtained.

t 12 nR81■3+mRRII2 That is, as shown in the above formula, when trihydrosilanes are used as a raw material, a silane oligomer having a silicon-hydrogen bond in the side chain is obtained, and when dihydrosilanes are used as a raw material, In this case, the basic skeleton of the main chain is -fR
'R2Sf+-, and a silane oligomer having a silicon-hydrogen bond at the terminal is obtained. When a mixture of trihydrosilanes and dihydrosilanes is used, a silane oligomer is obtained in which the basic skeleton of the main chain is a mixture of +RSil++ units and 1+R'R2Si+- units.

On the other hand, in the present invention, when monohydrosilanes are used as raw materials, trihydrosilanes represented by the following formula [■] or trihydrosilanes represented by the following formula [ Dihydrosilanes represented by 11 or monohydrosilanes represented by the following formula [ml] are used.

R' SI H 3... [I] R' R2Si H 2... [11 R' R2R8Si H... [■] [In the above formula, RR and R3 may be the same or different, and group, aryl group, cycloalkyl group, aralkyl group or triorganosilyl group. ] As the trihydrosilanes represented by the above formula [I],
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 [n] 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 addition, specific examples of the monohydrosilanes represented by the above formula [m] include triethylsilane, tripropylsilane, tributylsilane, trihexylsilane, triphenylsilane, tribenzylsilane, tricyclohexylsilane, and triphenethylsilane. , phenyldimethylsilane, (trimethylsilyl)dimethylsilane, (triethylsilyl)diethylsilane, (triphenylsilyl)
Examples include dimethylsilane, (trimethylsilyl)diphenylsilane, and diphenylmethylsilane.

In the present invention, these hydrosilanes may be used alone or in combination of two or more.

Complex Catalyst In the present invention, when dehydrogenating the above hydrosilanes, (i) ruthenium metal or compound (ii)
) A complex catalyst is used in which at least one type of ligand selected from an organic phosphorus compound, an organic arsenic compound, and an organic antimony compound is coordinated.

Ruthenium metal or ruthenium compound The ruthenium metal or ruthenium compound used in the present invention includes ruthenium metal supported on activated carbon, silica, etc., ruthenium black, a zero-valent complex of ruthenium, a monovalent ~
These include octavalent compounds or complexes.

Specifically, such ruthenium compounds or complexes include RuO5RuO, I? uCg2, RuCgS
RuCgSRuBr, RuF1RuF4.
[RuP], RuF 5RuF,
K2RuCN6.54 5 B Ru(CO), Ru(011)Cl2 5Ru(O
COCII3) 3, Ru(OCOCP), R
Examples include u (1,5-cyclooctadiene)C,92.

Ligand The ligand used in the present invention has the following formula [IVl or [
These include compounds represented by Vl.

ER'...[IVlR'
E-CHR5-CHR-ER... [V] [wherein,
E is phosphorus, arsenic or antimony, each R4 may be the same or different and is an alkyl group, aryl group, cycloalkyl group or aralkyl group, R
5 is hydrogen, an alkyl group, an aryl group, a cycloalkyl group, or an aralkyl group. ] Specifically, the ligand represented by the above formula [IVl or [Vl] includes PMa 1PEta, P 13 u
3, PPh, P(Cll Ph), PPh
MeSAsMe3. AsEt5AsBu3,A
sPh3, AS(C112Ph)3, AsPh Me
SSbMea, 5bEta, 5bBua, 5bP
ha, Sb (C1l Ph), SbPh2M
e-Ph2P-Cl12- C112-PPh2, Ph
As-C112-Cl12-As Ph2,P
hSb-(, 11-C112-5bPh2, etc.).

As the complex catalyst used in the present invention, a complex catalyst in which the above-mentioned ligand is coordinated to the above-mentioned ruthenium metal or its compound may be used, or a complex catalyst in which the above-mentioned ruthenium metal or its compound and the above-mentioned A complex catalyst may be used while being mixed with a ligand in the reaction system and generating a complex catalyst in the reaction system. When producing a complex catalyst in a reaction system, it is preferable to mix the ligand and ruthenium metal or its compound in a molar ratio of 1 to 20.

Specifically, the above-mentioned complex catalyst used in the present invention includes RuCfI(PPhs) 3. RuC,l
? (AsPh), RuC1'2
(SbPl+s) a, Ru(PPh) (
OCOCII ), Ru(AsPh3) 3 (
OCOC1l), Ru(SbPh)
(OCOCII), Ru(PPha2
33 32a) 3
(OCOCF), Ru (AsPh)
(OCOCFs)2, Ru (5bPh)
(OCOCP), Ru (Phz PCI
I2 ClI2 PPh ) Cjl' S
Ru (Ph ASC112ClI2 AsPh
) Off, Ru (Ph 5bCI12
C112SbPh2) 2Cll, Ru(Co)
(PPh), RuCN2(Co)2
(PPh), Ru(CO)(PPh)
CD 5RuC, Q a (PPh), R
u1lC! I(CO)(PPh), Ruff
Examples include (PPha)4.

In the complex catalyst used in the present invention, when ruthenium metal is desorbed from the metal by oxidatively adding a silicon-hydrogen bond as shown in the following formula, A silicon-silicon bond is formed, and the ligand contributes to stabilizing the ruthenium complex,
It is presumed that it plays a role in sustaining the dehydrogenation condensation reaction.

-"II R'5t-3IR' If +lI
+Meta1 Furthermore, the ruthenium complex catalyst used in the present invention can also be used as an olefin hydrosilylation catalyst. Therefore, when trihydrosilanes are used as raw materials, the side chain of the silane oligomer, which is the dehydrogenation condensation product, has a silicon-hydrogen bond, so if an olefin compound such as cyclohexene is present in the reaction system, An organic group such as a cyclohexyl group is introduced into the side chain of the obtained silane oligomer.

Dehydrogenation condensation conditions The dehydrogenation condensation reaction of the present invention is carried out in an inert gas atmosphere such as nitrogen, helium, or argon, or the system is evacuated before the reaction and the reaction product, hydrogen gas atmosphere, is added to the reaction system. It is preferable to carry out the reaction in the absence of oxygen or water. If oxygen or water is present in the reaction system, silicon-
Hydrogen bonds are oxidized, making it easier to generate silanol groups and siloxane bonds.

The dehydrogenation condensation reaction as described above may be carried out under normal pressure, or may be carried out under reduced pressure or increased pressure. Further, it is desirable that the reaction temperature is 0 to 200°C, preferably 15 to 150°C.

The ruthenium complex catalyst in the reaction system is desirably used in an amount of about 10 to 10-1 mol, preferably about 10 to 10-2 mol, per 1 mol of the hydrosilane.

Further, the dehydrogenation condensation reaction as described above may be carried out in the presence or absence of a solvent. When a solvent is used, hydrocarbon solvents such as toluene, xylene, heptane, dodecane, ditolylbutane, and cumene are preferred.

In addition, when trihydrosilanes are used as raw materials and an olefin compound such as cyclohexene is used as a hydrocarbon solvent, it is hydrogenated to form cyclohexane, and as mentioned above, a silane oligomer having a cyclohexyl group in the side chain is formed. can be manufactured.

The reaction time varies depending on the reaction temperature, but is usually 2 to 2
4 hours is sufficient.

Effects of the Invention According to the present invention, when trihydrosilanes or dihydrosilanes are used as raw materials, a silane oligomer having a higher molecular weight than conventionally known silane oligomers can be obtained in a short time and in a high yield. Furthermore, when monohydrosilanes are used as raw materials, disilane can be obtained in a short time and in high yield.

Furthermore, according to the present invention, the silane oligomer obtained when trihydrosilanes are used as a raw material has a silicon-hydrogen bond in the side chain, so it can be subjected to various chemical modifications by performing a hydrosilylation reaction with an olefin compound. is possible.

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 50 m with reflux condenser, stirrer and thermometer
After replacing the inside of the glass flask with argon gas, 10 mmol of phenylsilane (PhSi[I3) and tris(triphenylphosphine)dichlororuthenium (RuCj!2 (PPh3)) as a complex catalyst were added.
8) 0.2 mmol was introduced and stirred at 25°C for 1 hour. Thereafter, the mixture was stirred in an oil bath for 110 min.
The reaction was carried out for a total of 12 hours while maintaining the temperature at .degree.

After the reaction was completed, 30 ml of dry toluene was added for dilution, and a silane oligomer fraction was collected using column chromatography packed with silica gel. When toluene was removed by evaporation from this fraction, a silane oligomer was obtained in a yield of 74% (based on PhS1118).

GPC analysis revealed that the obtained silane oligomer had a number average molecular weight (Mn) of 1,200 and a weight average molecular weight (My) of 2.800. Also,
Infrared absorption spectrum and NMR analysis revealed that the basic skeleton of the main chain of the obtained silane oligomer was +phsut←.

Example 2 Diphenylsilane (Ph 5i112') as raw material
10 mmol and dihydridotetrakis(triphenylphosphine)ruthenium (RLI2(
PPh3) 4) Diphenylsilane was subjected to a comprehensive dehydrogenation reaction in the same manner as in Example 1, except that 0.2 mmol was used.

As a result, the yield of silane oligomer was 60% (Ph
5ill 2 standard), Mn is 720, My is 1,
200, and the basic skeleton of the main chain is -Hphstph÷
It was found that it consists of units and has a silicon-hydrogen bond at the end.

Comparative Example 1 As a catalyst, dimethyl titanocene (cp2Tl(C11
3) 2) A dehydrogenation condensation reaction was attempted in the same manner as in Example 1 except that 0.2 mmol was used.

As a result, it was found that the base skeleton of the main chain of the obtained silane oligomer consisted of -+phst+t÷, but both Mn and My were less than 1.000.

Comparative Example 2 Ruthenium trichloride (Rucls) 0.2 as a catalyst
A dehydrogenation condensation reaction was attempted in the same manner as in Example 1 except that millimole was used, but no silane oligomer was obtained.

Comparative Example 3 As a catalyst, (l,5-cyclooctadiene)dichlororuthenium (Ru(1,5-COD)CI2) 0.
A dehydrogenation condensation reaction was attempted in the same manner as in Example 2 except that 2 mmol was used, but no silane oligomer was obtained.

Example 3 Diphenylmethylsilane (Ph 2 MeS
ill) 10 mmol and tris(triphenylphosphine)di(trifluoroacetic acid)ruthenium (RLI(OCOCP3) 2(PPh8) 3) as complex catalyst
A dehydrogenation condensation reaction was carried out in the same manner as in Example 1 except that 0.2 mmol was used. Gas chromatographic analysis of the product revealed that dimer tetraphenyldimethyldisilane was produced in a yield of 28% (Ph2 MeSll (based on)).

Comparative Example 4 Ruthenium tribromide (RuBr 3) as a catalyst 0.
A dehydrogenation condensation reaction was attempted in the same manner as in Example 3 except that 2 mmol was used, but disilane was not obtained.

Examples 4 to 7 A dehydrogenation condensation reaction was carried out in the same manner as in Example 1, except that a ruthenium complex catalyst or a mixture of a ruthenium compound and a ligand was used as the catalyst in the amounts shown in Table 1.

The results are shown in Table 1, and the yield of the obtained silane oligomer was based on phsut 3, and the basic skeleton of its main chain was +Ph5l11+.

Examples 8 to 11 Except for using trihydrosilane or a mixture of li trihydrosilane and dihydrosilane shown in Table 2 as raw materials,
A dehydrogenation condensation reaction was carried out in the same manner as in Example 1. The results are shown in Table 2, and the yield of the obtained silane oligomer is based on the hydrosilane used.

Example 12 Except that 30 ml of dry toluene was used as the reaction solvent,
A dehydrogenation condensation reaction was carried out in the same manner as in Example 1.

As a result, the yield of silane oligomer was 70% (PhSI
113 standard), Mn is 900, Mw is 2.500
The basic skeleton of the main chain is +Ph5II as in Example 1.
It was ++-.

Example 13 A dehydrogenation condensation reaction was carried out in the same manner as in Example 1, except that a mixture of 15 ml of dry toluene and 15 ml of cyclohexene was used as the reaction solvent.

As a result, the conversion rate of Ph51113 was 72%, the Mn of the obtained silane oligomer was 1,200, and the Mw was 2.
．． It was 800. Structural analysis of the silane oligomer revealed that the basic skeleton of the main chain was +Ph5l11>- units.

Example 14 β-naphthyldimethylsilane ([[)ゝSI
A dehydrogenation condensation reaction was carried out in the same manner as in Example 1 except that 10 mmol of IIMe 2 ) was used. Gas chromatographic analysis of the product revealed that the dimer di(β-
Naphthyl)tetramethyldisilane with a yield of 25% (7Si
11Me2 standard).

1゜ 2゜ 3゜ 4゜ Display of incidents 1999 Special permission wish 3rd ° No. 907 name of invention Silane oligomer manufacturing method person who makes corrections Relationship to the incident Patent applicant Name Tonen Petrochemical Co., Ltd. teenager Reason Man (Postal code 141) 3rd floor, Araku Building, 2-19-2 Nishigotanda, Tokyo Parts Ward

Claims (1)

[Claims] (1) In the presence of a complex catalyst consisting of (i) ruthenium metal or a compound coordinated with (ii) at least one type of ligand selected from an organic phosphorus compound, an organic arsenic compound, and an organic antimony compound, trihydrosilane 1. A method for producing a silane oligomer, which comprises producing a silane oligomer by dehydrogenating and condensing dihydrosilanes, dihydrosilanes, or monohydrosilanes.