JPH05262880A - Production of polysilane - Google Patents

Abstract

PURPOSE:To effectively produce a polysilane compd. having a high degree of polymn. by reacting a hydrosilane compd. in the presence of a catalyst comprising a mixture of specific compds. CONSTITUTION:A polysilane compd. is produced by reacting a hydrosilane compd. in the presence of a catalyst comprising a mixture contg. a metallocene compd. of the formula: LL' MCl2 [wherein M is Ti, Zr, or Hf; and L and L' are each a cyclopentadienyl group (substd. by a 1-6C alkyl group), a cyclopentadienyl group substd. by an R<1>R<2>R<3>Si- group (wherein R<1>, R<2>, and R<3> are each H, 1-12C alkyl, aralkyl, or 6-12C aryl), an indenyl group (substd. by a 1-6C alkyl group), or an indenyl group substd. by an R<1>R<2>R<3>Si-group provided that L and L' may be cross-linked by a 1-4C alkylene or specific silylene group] and a silyl compd. of the formula: R<9>R<10>R<11>SiA [wherein R<9>, R<10>, and R<11> are each 1-12C alkyl, aralkyl, 6-12C aryl, or an R12R<13>R<14>Si- group (wherein R<12>, R<13>, and R<14> are each 1-8C alkyl or aryl); and A is Li, Na, or K].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polysilanes, and more specifically, using a mixture containing a specific metal complex and a specific silyl compound or a mixture containing a specific metal complex and a specific metal hydride as a catalyst. A method for producing polysilanes from a silane compound monomer using the same.

[0002]

2. Description of the Related Art Polysilanes are expected to be used as electronic materials such as semiconductors and electric conductors, nonlinear optical materials, photoreactive materials such as photoresists and photopolymerization initiators, or ceramic precursors, and have recently attracted attention. Taking a bath.

By the way, conventionally, polysilanes have generally been produced by a method represented by the following general formula (7).

[0004]

[Chemical 10]

(In the formula, R ¹⁵ and R ¹⁶ are hydrocarbon groups.) However, in the above-mentioned method for producing the polysilanes, twice the molar amount of metallic sodium is used with respect to the silane compound monomer, which is very costly. It is high. Moreover, sodium metal has a risk of ignition and is difficult to handle. Furthermore, since a large amount of sodium chloride is by-produced, a step of removing this sodium chloride from the polysilane is required.

Therefore, in recent years, as shown in the following general formula (8), research has been conducted to synthesize polysilanes by dehydrogenative condensation of hydrosilanes using a complex catalyst.

[0007]

[Chemical 11]

(In the formula, R ¹⁷ is an alkyl group, an alkyl group having a substituent, a phenyl group or a phenyl group having a substituent, and an RR 'having an alkyl group or a phenyl group as a substituent.
R ″ is a Si type silyl group, R ¹⁸ is hydrogen, an alkyl group,
It is an alkyl group having a substituent, a phenyl group or a phenyl group having a substituent, and an RR′R ″ Si type silyl group having an alkyl group or a phenyl group as a substituent.
R'and R "are hydrogen, an alkyl group having 1 to 12 carbon atoms,
Alternatively, it is selected from an aralkyl group or an aryl group having 6 to 12 carbon atoms, and these may be the same or different. ) So far, Cp ₂ TiMe ₂ [J.
Am. Chem. Soc., 108 , 4059 (198).
6)], Cp ₂ TiPh ₂ [Chem. Lett., 198].
9, 83], Cp ₂ ZrMe ₂ [Can.J.Chem.,
64 , 1677 (1986)], Ni (dppp) Me ₂
[JP-A-1-198631], RuCl ₂ (PPh ₃ ) ₃ ,
HRh (CO) (PPh ₃ ) ₃ , PtCl ₂ (PPh ₃ ) ₂ [Nikka 58th Annual Meeting, 1IIA31, 1989] and the like have been developed. However, only about 40-mer polymers have been obtained from trihydrosilanes, and 2-3-mer oligomers have been obtained from dihydrosilanes.

[0009]

DISCLOSURE OF THE INVENTION The present invention is directed to the production of polysilanes from hydrosilanes by using a catalyst system which is cheaper and more readily available than known catalysts and which has a higher degree of polymerization than known catalysts. An object of the present invention is to provide a method for producing polysilanes, which can efficiently produce

[0010]

Means for Solving the Problems As a result of intensive studies in view of the above situation, the present inventors have found that a mixture containing a specific metal complex and a specific silyl compound, or a specific metal complex and a specific metal. The present invention has been completed by finding that polysilanes can be more efficiently produced from hydrosilanes by using a mixture containing hydride as a catalyst.

That is, according to the first aspect of the present invention,
(A) The following general formula (1)

[0012]

LL'MCl ₂ (1) [In the formula, M represents Ti, Zr, or Hf. L and L ′ are unsubstituted cyclopentadienyl and have 1 to 6 carbon atoms.
Cyclopentadienyl substituted with an alkyl group of the following general formula (2)

[0013]

Embedded image R ¹ R ² R ³ Si— (2) (wherein R ¹ , R ² , and R ³ are hydrogen, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, or 6 to 1 carbon atoms).
Selected from two aryl groups, which may be the same or different. } Cyclopentadienyl substituted with a silyl group, unsubstituted indenyl, indenyl substituted with an alkyl group having 1 to 6 carbon atoms, or indenyl substituted with a silyl group represented by the general formula (2) above. And may be the same as or different from each other.
Further, between L and L'is an alkylene having 1 to 4 carbon atoms, or a general formula (3)

[0014]

[Chemical 14] {In the formula, R ⁷ and R ⁸ are selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, or an aryl group having 6 to 12 carbon atoms, and these may be the same or different. ] Which may be crosslinked with silylene]], and (B) the following general formula (4)

[0015]

Embedded image R ⁹ R ¹⁰ R ¹¹ SiA (4) [wherein R ⁹ , R ¹⁰ and R ¹¹ are each a carbon number of 1 to 12]
A linear or branched alkyl group or aralkyl group, an aryl group having 6 to 12 carbon atoms, or the following general formula (5)

[0016]

Embedded image R ¹² R ¹³ R ¹⁴ Si— (5) (wherein R ¹² , R ¹³ and R ¹⁴ are selected from an alkyl group or an aryl group having 1 to 8 carbon atoms and may be the same or different) Good. } And are the same or different.

A represents Li, Na, or K. ]
There is provided a method for producing polysilanes, which comprises reacting hydrosilanes to produce polysilanes using a mixture containing a silyl compound represented by

According to a second aspect of the present invention, (A)
The following general formula (1)

[0019]

LL'MCl ₂ (1) [In the formula, M represents Ti, Zr, or Hf. L and L ′ are unsubstituted cyclopentadienyl and have 1 to 6 carbon atoms.
Cyclopentadienyl substituted with an alkyl group of the following general formula (2)

[0020]

Embedded image R ¹ R ² R ³ Si— (2) (wherein R ¹ , R ² , and R ³ are hydrogen, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, or 6 to 1 carbon atoms).
Selected from two aryl groups, which may be the same or different. } Cyclopentadienyl substituted with a silyl group, unsubstituted indenyl, indenyl substituted with an alkyl group having 1 to 6 carbon atoms, or indenyl substituted with a silyl group represented by the general formula (2) above. They may be the same or different from each other.
Further, between L and L'is an alkylene having 1 to 4 carbon atoms, or a general formula (3)

[0021]

[Chemical 19] {In the formula, R ⁷ and R ⁸ are selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, or an aryl group having 6 to 12 carbon atoms, and these may be the same or different. ] Which may be crosslinked with silylene], and (B) ′ represented by the following general formula (6)

[0022]

A'Xn (6) (In the formula, A'is Li, Na, K, Ca, Al, R ⁴
_(3-n) Al, LiAl, LiAlR ⁵ _(4-n) , NaAlR ⁵
_(4-n) , B, R ⁴ _(3-n) B, LiB, LiBR ⁵ , NaB,
Represents KB or R ⁶ B, R ⁴ is an alkyl group having 1 to ⁵ carbon atoms, R ⁵ is an alkyl or alkoxyl group having 1 to 8 carbon atoms, and R ⁶ is a quaternary ammonium group having 1 to 4 carbon atoms; Show.

However, when a plurality of R ⁴ , R ⁵ and R ⁶ are present, they may be the same or different.

X is H or D, and n is 1 to 4
Is an integer. The method for producing polysilanes is characterized by producing a polysilane by reacting hydrosilanes with a mixture containing a metal hydride represented by the formula 1) as a catalyst.

The present invention will be described in more detail below.

In the first embodiment of the present invention, a mixture containing (A) a metallocene compound represented by the general formula (1) and (B) a silyl compound represented by the general formula (4) is used as a catalyst.

Examples of the metallocene compound represented by the general formula (1) include dichlorobis (η-cyclopentadiene).
Nyl) titanium , dichlorobis (η-methylcyclopenta
Dienyl) titanium , dichlorobis (η-dimethylcyclo
Pentadienyl) titanium , dichlorobis (η-trimethyl)
Rucyclopentadienyl ) titanium , dichlorobis (η-
Pentamethylcyclopentadienyl) titanium, dichlorobis (η-trifluoromethylcyclopentadienyl)
Titanium, dichlorobis (η-trimethylsilylcyclope
Ntajieniru) titanium, dichloro (.eta. pentamethylcyclopentadienyl) (.eta. cyclopentadienyl) titanium, dichloro (.eta. trifluoromethyl cyclopentadienyl) (.eta. cyclopentadienyl) titanium, dichloromethylene-bis (Η-Cyclopentadienyl) titanium, dichloroethylene bis (η-cyclopentadienyl) titanium, dichloropropylene bis (η-cyclopentadienyl) titanium, dichlorodimethylsilylene bis
(Η-Cyclopentadienyl) titanium , dichlorobis
(Η-Indenyl) titanium , dichlorobis (η-methylindenyl) titanium, dichlorobis (η-dimethylindenyl) titanium, dichlorobis (η-trimethylsilylindenyl) titanium, dichloromethylenebis (η-indenyl) titanium, dichloroethylenebis ( η-Indeni
) Titanium , dichloropropylene bis (η-indenyl) titanium, dichlorobis (η-cyclopentadienyl )
Ru) zirconium , dichlorobis (η-methylcyclope
N-dienyl) zirconium , dichlorobis (η-dimme
Cylcyclopentadienyl ) zirconium , dichlorobi
Sus (η-trimethylcyclopentadienyl) zirconium
Arm, dichlorobis (.eta. pentamethylcyclopentadienyl) zirconium, dichlorobis (.eta. trifluoromethyl cyclopentadienyl) zirconium, dichloro
Bis (η-trimethylsilylcyclopentadienyl) di
Ruconium , dichloro (η-pentamethylcyclopentadienyl) (η-cyclopentadienyl) zirconium, dichloro (η-trifluoromethylcyclopentadienyl) (η-cyclopentadienyl) zirconium,
Dichloromethylene bis (η-cyclopentadienyl) zirconium, dichloroethylene bis (η-cyclopentadienyl) zirconium, dichloropropylene bis (η
-Cyclopentadienyl ) zirconium, dichlorodim
Tillsilylene bis (η-cyclopentadienyl) zirco
Ni , dichlorobis (η-indenyl) zirconium
Arm, dichlorobis (.eta.-methylindenyl) zirconium, dichlorobis (.eta.-dimethyl indenyl) zirconium, dichlorobis (.eta. trimethylsilyl) zirconium, dichloromethylene-bis (.eta. indenyl) zirconium, dichloroethylene bis (.eta. Inn
Denyl) zirconium , dichloropropylene bis ( η-
Indenyl) zirconium, dichlorobis (η-cyclo
Pentadienyl) hafnium , dichlorobis (η-methyl)
(Lucyclopentadienyl) hafnium , dichlorobis
(Η-Dimethylcyclopentadienyl) hafnium , di
Chlorobis (η-trimethylcyclopentadienyl) ha
Funiumu, dichlorobis (.eta. pentamethylcyclopentadienyl) hafnium, dichlorobis (.eta. trifluoromethyl cyclopentadienyl) hafnium, dichloro
Lobis (η-trimethylsilylcyclopentadienyl)
Hafnium , dichloro (η-pentamethylcyclopentadienyl) (η-cyclopentadienyl) hafnium,
Dichloro (η-trifluoromethylcyclopentadienyl) (η-cyclopentadienyl) hafnium, dichloromethylenebis (η-cyclopentadienyl) hafnium, dichloroethylenebis (η-cyclopentadienyl) hafnium, dichloropropylenebis (Η-Cyclopentadienyl) hafnium, dichlorodimethylsilyle
Nbisu (.eta.-cyclopentadienyl) hafnium, Axis
Lolobis (η-indenyl) hafnium , dichlorobis (η-methylindenyl) hafnium, dichlorobis (η-dimethylindenyl) hafnium, dichlorobis (η-trimethylsilylindenyl) hafnium, dichloromethylenebis (η-indenyl) hafnium, dicu
Examples thereof include loroethylenebis (η-indenyl) hafnium and dichloropropylenebis (η-indenyl) hafnium. The metallocene compound may be used alone or in combination of two or more selected from the above.

Among the above, those with an underline are the most preferred metacerone compounds.

Examples of the silyl compound represented by the general formula (4) include phenyldimethylsilyllithium and diphene.
Nylmethylsilyllithium , t-butyldiphenylsilyllithium, triphenylsilyllithium , tris (to
Limethylsilyl) silyllithium , trimethylsilylna
Thorium , sodium triethylsilyl, sodium tri-n-propylsilyl, sodium tri-i-propylsilyl, sodium tri-n-butylsilyl, tri-
n-Hexylsilyl sodium, triphenylsilylna
Thorium , sodium ethyldimethylsilyl, n-propyldimethylsilylsodium, i-propyldimethylsilylsodium, n-butyldimethylsilylsodium, t-butyldimethylsilylsodium, n-hexyldimethylsilylsodium, cyclohexyldimethylsilylsodium, n-octyl Dimethylsilyl sodium, n-decyldimethylsilyl sodium, phenyl
Sodium dimethylsilyl, sodium benzyldimethylsilyl, sodium phenethyldimethylsilyl, di-
n-Butylmethylsilyl sodium, diphenylmethyl
Sodium silyl, sodium t-butyldiphenylsilyl, sodium tris (trimethylsilyl) silyl ,
Trimethylsilyl potassium , triethylsilyl potassium, tri-n-propylsilyl potassium, tri-i-propylsilyl potassium, tri-n-butylsilyl potassium, tri-n-hexylsilyl potassium, triphenyl
Silyl potassium , ethyl dimethyl silyl potassium, n-
Propyldimethylsilyl potassium, i-propyldimethylsilyl potassium, n-butyldimethylsilyl potassium, t-butyldimethylsilyl potassium, n-hexyldimethylsilyl potassium, cyclohexyldimethylsilyl potassium, n-octyldimethylsilyl potassium, n
-Decyldimethylsilyl potassium, phenyldimethyl
Lilpotassium , benzyldimethylsilylpotassium, phenethyldimethylsilylpotassium, di-n-butylmethylsilylpotassium, diphenylmethylsilylpotassium , t
-Butyldiphenylsilylpotassium , tris (trimethyl
And rusilyl) silyl potassium . The silyl compound may be used alone or in combination of two or more selected from the above.

Among the above, those with an underline are preferred silyl compounds. The use ratio of the metallocene compound and the silyl compound is 1
The metallocene compound is usually 0.01 to 0.00 mol.
10 mol, preferably 0.1 to 5 mol, silyl compound is usually 0.005 to 50 mol, preferably 0.05 to
It is 20 mol.

As additives to the catalyst, 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-12-crown-4, dibenzo-15-crown-5, dibenzo-18-crown are added. Crown ethers such as -6 and diamines such as tetramethylethylenediamine may be added. The use ratio of the additive is usually 0.005 to 50 per 100 mol of hydrosilanes.
mol, preferably 0.05 to 20 mol.

In the first embodiment of the present invention, hydrosilanes are reacted with a mixture containing the metallocene compound and the silyl compound as a catalyst to produce polysilanes.

The hydrosilanes are usually hydromonosilanes, hydrodisilanes, hydrotrisilanes, or a mixture of two or more of these.

Specific examples of hydromonosilanes include silane , methylsilane , ethylsilane , and n-.
Propylsilane , (3,3,3-trifluoropropyl)
Silane , n-butylsilane , t-butylsilane , (1-
Methylpropyl) silane , (2-methylpropyl) sila
Emissions, Amirushiran, n- hexyl silane, cyclohexyl
Rushiran, n- heptyl silane, n- octyl silane,
n-nonylsilane , n-decylsilane , n-dodecylsilane
Orchid , phenylsilane , p-tolylsilane , mesityl
Orchids, benzyl silane, Fenechirushiran, (trimethylene
Lusilylmethyl) silane , dimethylsilane , diethyl
Orchid , di-n-propylsilane , bis (3,3,3-trifluoropropyl) silane, di-n-butylsilane , di-t-butylsilane, di (1-methylpropyl) silane, di (2-methylpropyl) ) Silane, diamylsilane, di-n- hexylsilane, dicyclohexylsilane, di-n-heptylsilane , di-n-octylsila
Emissions, di -n- Nonirushiran, di -n- decylsilane, di -n- dodecyl, diphenylsilane, di -p- tolylsilane, Jimeshichirushiran, dibenzyl silane, di
Phenethylsilane , bis (trimethylsilylmethyl) silane, ethylmethylsilane, methyl-n-propylsilane, methyl (3,3,3-trifluoropropyl) silane, methyl-i-propylsilane, n-butylmethylsilane, t- Butylmethylsilane, methyl (1-methylpropyl) silane, methyl (2-methylpropyl) silane, amylmethylsilane, n-hexylmethylsilane,
Cyclohexylmethylsilane, n-heptylmethylsilane, methyl-n-octylsilane, methyl-n-nonylsilane, n-decylmethylsilane, n-dodecylmethylsilane, methylphenylsilane , p-tolylmethylsila
Emissions, methyl mesityl silane, benzyl methyl silane, main
Examples thereof include tylphenethylsilane , methyl (trimethylsilylmethyl) silane, (p-methylphenethyl) silane, ethylphenylsilane and t-butylphenylsilane.

Among the above, those with an underline are the preferred hydromonosilanes.

Specific examples of hydrodisilanes include disilane , methyldisilane , and ethyldisila.
N -propyldisilane , (3,3,3-trifluoro
Propyl) disilane , n-butyldisilane , t-butyl
Disilane , (1-methylpropyl) disilane , (2-me
Tylpropyl) disilane , amyldisilane , n-hexyl
Rudisilane , cyclohexyldisilane , n-heptyldi
Silane , n -octyldisilane , n-nonyldisilane ,
n-decyldisilane , n-dodecyldisilane , phenyl
Disilane, p- tolyl disilane, Meshichirujishiran, base
Benzyldisilane , phenethyldisilane , (trimethylsilane
Rylmethyl) disilane , 1,1-dimethyldisilane , 1,
1-diethyldisilane , 1,1-di-n-propyldisi
Run , 1,1-di-n-butyldisilane , 1,1-di-n
-Amyldisilane , 1,1-di-n-hexyldisila
Emissions, 1,1-dicyclohexyl disilane, 1,1-diphenyl
Nyldisilane , 1,1-dimesityldisilane , 1-ethyl-1-methyldisilane, 1-methyl-1-n-propyldisilane, 1-methyl-1-i-propyldisilane,
1-n-butyl-1-methyldisilane, 1-t-butyl-1-methyldisilane, 1-n-hexyl-1-methyldisilane, 1-cyclohexyl-1-methyldisilane,
1-n-heptyl-1-methyldisilane, 1-methyl-
1-n-octyldisilane, 1-n-decyl-1-methyldisilane, 1-methyl-1-phenyldisilane, 1-
(P-Methylphenethyl) -1-methyldisilane, 1-
Methyl-1- (β-phenethyl) disilane, 1-p-tolyl-1-methyldisilane, 1-phenyl-1-ethyldisilane, 1-t-butyl-1-phenyldisilane, 1
-(Phenyldimethylsilyl) -1-methyldisilane,
1- (trimethylsilyl) -1-methyldisilane, 1,
2-dimethyldisilane , 1,2-diethyldisilane , 1,
2-di-n-propyldisilane , 1,2-di-n-butyl
Ludisilane , 1,2-di-n-amyldisilane , 1,2-
Di-n-hexyldisilane , 1,2-dicyclohexyl
Disilane , 1,2-diphenyldisilane , 1,2-dimesy
Cyldisilane , 1-ethyl-2-methyldisilane, 1-
Methyl-2-n-propyldisilane, 1-methyl-2-
i-propyldisilane, 1-n-butyl-2-methyldisilane, 1-t-butyl-2-methyldisilane, 1-n
-Hexyl-2-methyldisilane, 1-cyclohexyl-2-methyldisilane, 1-n-heptyl-2-methyldisilane, 1-methyl-2-n-octyldisilane, 1
-N-decyl-2-methyldisilane, 1-methyl-2-
Phenyldisilane, 1- (p-methylphenethyl) -2
-Methyldisilane, 1-methyl-2- (β-phenethyl) disilane, 1-p-tolyl-2-methyldisilane,
1-phenyl-2-ethyldisilane, 1-t-butyl-
2-phenyldisilane, 1- (phenyldimethylsilyl) -2-methyldisilane, 1- (trimethylsilyl)
-2-methyldisilane, trimethylsilylsilane, triphenylsilylsilane, (t-butyldimethylsilyl)
Silane, 1,1,2-trimethyldisilane, 1,1,2-triethyldisilane, 1,1,2-tri-n-propyldisilane, 1,1,2-tri-n-butyldisilane, 1,1, Two
-Tri-n-amyldisilane, 1,1,2-tri-n-hexyldisilane, 1,1,2-tricyclohexyldisilane, 1,1,2-triphenyldisilane, 1,1,2-trimesityldisilane, 1,1-diethyl-2-methyldisilane, 1,1-dimethyl-2-n-propyldisilane,
1,1-dimethyl-2-i-propyldisilane, 1,1-
Di-n-butyl-2-methyldisilane, 1,1-di-t
-Butyl-2-methyldisilane, 1,1-di-n-hexyl-2-methyldisilane, 1,1-dicyclohexyl-2-methyldisilane, 1,1-di-n-heptyl-2
-Methyldisilane, 1,1-dimethyl-2-n-octyldisilane, 1,1-di-n-decyl-2-methyldisilane, 1,1-dimethyl-2-phenyldisilane, 1,1
-Di- (p-methylphenethyl) -2-methyldisilane, 1,1-dimethyl-2- (β-phenethyl) disilane, 1,1-di-p-tolyl-2-methyldisilane, 1,
1-diphenyl-2-ethyldisilane, 1,1-di-t
-Butyl-2-phenyldisilane, 1,1-di (phenyldimethylsilyl) -2-methyldisilane, 1,1-bis (trimethylsilyl) -2-methyldisilane, 1-ethyl-2,2-dimethyldisilane, 1 -Methyl-2,2-
Di-n-propyldisilane, 1-methyl-2,2-di-
i-propyldisilane, 1-n-butyl-2,2-dimethyldisilane, 1-t-butyl-2,2-dimethyldisilane, 1-n-hexyl-2,2-dimethyldisilane,
1-cyclohexyl-2,2-dimethyldisilane, 1-
n-heptyl-2,2-dimethyldisilane, 1-methyl-2,2-di-n-octyldisilane, 1-n-decyl-2,2-dimethyldisilane, 1-methyl-2,2-diphenyldisilane, 1- (p-methylphenethyl) -2,
2-dimethyldisilane, 1-methyl-2,2-di (β-
Phenethyl) disilane, 1-p-tolyl-2,2-dimethyldisilane, 1-phenyl-2,2-diethyldisilane, 1-t-butyl-2,2-diphenyldisilane, 1
-(Phenyldimethylsilyl) -2,2-dimethyldisilane, 1- (trimethylsilyl) -2,2-dimethyldisilane, 1,1,1,2-tetramethyldisilane, 1,1,
1,2-tetraethyldisilane, 1,1,1,2-tetra-
n-propyldisilane, 1,1,1,2-tetra-n-butyldisilane, 1,1,1,2-tetra-n-amyldisilane, 1,1,1,2-tetra-n-hexyldisilane,
1,1,1,2-tetracyclohexyldisilane, 1,1,
1,2-tetraphenyldisilane, 1,1,1,2-tetramesityldisilane, 1,1,2,2-tetramethyldisilane, 1,1,2,2-tetraethyldisilane, 1,1,2, Two
-Tetra-n-propyldisilane, 1,1,2,2-tetra-n-butyldisilane, 1,1,2,2-tetra-n-
Amyldisilane, 1,1,2,2-tetra-n-hexyldisilane, 1,1,2,2-tetracyclohexyldisilane, 1,1,2,2-tetraphenyldisilane, 1,1,2,
2-Tetramesityldisilane, 1,1,1-triethyl-
2-methyldisilane, 1,1,1-trimethyl-2-n-
Propyldisilane, 1,1,1-trimethyl-2-i-propyldisilane, 1,1,1-tri-n-butyl-2-methyldisilane, 1,1,1-tri-t-butyl-2-methyl Disilane, 1,1,1-tri-n-hexyl-2-methyldisilane, 1,1,1-tricyclohexyl-2-methyldisilane, 1,1,1-tri-n-heptyl-2-methyldisilane, 1,1,1-trimethyl-2-n-octyldisilane, 1,1,1-tri-n-decyl-2-methyldisilane, 1,1,1-trimethyl-2-phenyldisilane, 1,1,1 -Tri- (p-methylphenethyl) -2-
Methyldisilane, 1,1,1-trimethyl-2- (β-phenethyl) disilane, 1,1,1-tri-p-tolyl-2
-Methyldisilane, 1,1,1-triphenyl-2-ethyldisilane, 1,1,1-tri-t-butyl-2-phenyldisilane, 1,1,1-tri (phenyldimethylsilyl) -2- Methyldisilane, 1,1,1-tri (trimethylsilyl) -2-methyldisilane, 1-ethyl-2,2,
2-trimethyldisilane, 1-methyl-2,2,2-tri-n-propyldisilane, 1-methyl-2,2,2-tri-i-propyldisilane, 1-n-butyl-2,2,2 −
Trimethyldisilane, 1-t-butyl-2,2,2-trimethyldisilane, 1-n-hexyl-2,2,2-trimethyldisilane, 1-cyclohexyl-2,2,2-trimethyldisilane, 1-n- Heptyl-2,2,2-trimethyldisilane, 1-methyl-2,2,2-tri-n-octyldisilane, 1-n-decyl-2,2,2-trimethyldisilane, 1-methyl-2,2 , 2-Triphenyldisilane, 1- (p-methylphenethyl) -2,2,2-trimethyldisilane, 1-methyl-2,2,2-tri (β-phenethyl) disilane, 1-p-tolyl-2 , 2,2-Trimethyldisilane, 1-phenyl-2,2,2-triethyldisilane, 1-t-butyl-2,2,2-triphenyldisilane, 1- (phenyldimethylsilyl) -2,2,2 -Trimethyldisilane, 1- (tri Methylsilyl) -2,2,
2-trimethyldisilane, 1,1-diethyl-2,2-dimethyldisilane, 1,1-dimethyl-2,2-di-n-propyldisilane, 1,1-dimethyl-2,2-di-i-propyl Disilane, 1,1-di-n-butyl-2,2-dimethyldisilane, 1,1-di-t-butyl-2,2-dimethyldisilane, 1,1-di-n-hexyl-2,2- Dimethyldisilane, 1,1-dicyclohexyl-2,2-dimethyldisilane, 1,1-di-n-heptyl-2,2-dimethyldisilane, 1,1-dimethyl-2,2-di-n-octyldisilane, 1,1-di-n-decyl-2,2-dimethyldisilane, 1,1-dimethyl-2,2-diphenyldisilane, 1,1-di- (p-methylphenethyl) -2,2-dimethyldisilane, 1,1-dimethyl-2,2-di (β-phenethyl) disilane, 1,1 Di -p- tolyl-2,2
Dimethyldisilane, 1,1-diphenyl-2,2-diethyldisilane, 1,1-di-t-butyl-2,2-diphenyldisilane, 1,1-di (phenyldimethylsilyl)-
2,2-Dimethyldisilane, 1,1-bis (trimethylsilyl) -2,2-dimethyldisilane, 1,2-diethyl-
1,2-dimethyldisilane, 1,2-dimethyl-1,2-
Di-n-propyldisilane, 1,2-dimethyl-1,2-
Di-i-propyldisilane, 1,2-di-n-butyl-
1,2-dimethyldisilane, 1,2-di-t-butyl-
1,2-dimethyldisilane, 1,2-di-n-hexyl-
1,2-dimethyldisilane, 1,2-dicyclohexyl-
1,2-dimethyldisilane, 1,2-di-n-heptyl-
1,2-dimethyldisilane, 1,2-dimethyl-1,2-
Di-n-octyldisilane, 1,2-di-n-decyl-
1,2-dimethyldisilane, 1,2-dimethyl-1,2-
Diphenyldisilane, 1,2-di- (p-methylphenethyl) -1,2-dimethyldisilane, 1,2-dimethyl-
1,2-di (β-phenethyl) disilane, 1,2-di-p
-Tolyl-1,2-dimethyldisilane, 1,2-diphenyl-1,2-diethyldisilane, 1,2-di-t-butyl-1,2-diphenyldisilane, 1,2-di (phenyldimethylsilyl) Examples thereof include 1,2-dimethyldisilane and 1,2-bis (trimethylsilyl) -1,2-dimethyldisilane.

Among the above, those with an underline are the most preferable hydrodisilanes.

Further, as hydrotrisilanes,
Specifically, for example, trisilane , 1-methyltrisila
Down, 1-ethyl-trisilane, 1-n-propyl-trisilaheptane
Emissions, 1- (3,3,3-trifluoropropyl) Torishira
Down, 1-n-butyl trisilane, 1-t-Buchirutorishi
Orchid , 1- (1-methylpropyl) trisilane , 1-
(2-methylpropyl) trisilane , 1-amyltrishi
Orchid , 1-n -hexyltrisilane , 1-cyclohexyl
Lutrisilane , 1-n- heptyltrisilane , 1 -n-
Octyltrisilane , 1-n-nonyltrisilane , 1-
n-decyltrisilane , 1-n-dodecyltrisilane ,
1-phenyltrisilane , 1-p-tolyltrisilane ,
1-mesityl trisilane , 1-benzyltrisilane , 1
-Phenethyltrisilane , 1- (trimethylsilylmethyl
Le) trisilane , 2-methyltrisilane , 2-ethyl
Lisilane , 2-n- propyltrisilane , 2- (3,3,
3-trifluoropropyl) trisilane , 2-n-butyl
Rutrisilane , 2-t-butyltrisilane , 2- (1-
Methylpropyl ) trisilane , 2- (2 -methylpropyi)
Le) trisilane , 2 -amyltrisilane , 2-n-hexyl
Siltrisilane , 2-cyclohexyltrisilane , 2-
n-Heptyltrisilane , 2-n-octyltrisilane
Down, 2-n-nonyl trisilane, 2-n-Deshirutorishi
Orchid , 2-n-dodecyltrisilane , 2-phenyltri
Silane , 2-p -tolyltrisilane , 2-mesityltri
Silane , 2-benzyltrisilane , 2-phenethyltri
Silane , 2- (trimethylsilylmethyl) trisilane ,
1,1-dimethyltrisilane , 1,1-diethyltrisila
1,1,1 -di-n-propyltrisilane , bis (3,
3,3-trifluoropropyl) trisilane , 1,1-di
-N- butyl trisilane, 1,1-di -t- butyltri
Silane , 1,1-di (1-methylpropyl) trisila
Emissions, 1,1-di (2-methylpropyl) trisilane, 1,
1 -diamyltrisilane , 1,1-di-n-hexyl
Lisilane , 1,1-dicyclohexyltrisilane , 1,1
-Di-n-heptyltrisilane , 1,1-di-n-oct
Tilt trisilane , 1,1-di-n- nonyltrisilane ,
1,1-di-n-decyltrisilane , 1,1-di-n-do
Decyltrisilane , 1,1-diphenyltrisilane , 1,
1-di-p -tolyltrisilane , 1,1-dimesitylt
Rishiran, 1,1 dibenzyl trisilane, 1,1-diphenyl
Energy trisilane , 1,1-bis (trimethylsilyl)
Methyl) trisilane , 1,2-dimethyltrisilane , 1,
2-diethyltrisilane , 1,2-di-n-propylto
Lisilane , 1,2-bis (3,3,3-trifluoropro
Pill) trisilane , 1,2-di-n-butyltrisila
Emissions, 1,2--t- butyl trisilane, 1,2-di (1
-Methylpropyl) trisilane , 1,2-di (2-methyl)
Lupropyl) trisilane , 1,2-diamyltrisila
Emissions, 1,2 -n- hexyl trisilane, 1,2 dicyanamide
Black hexyl trisilane, 1,2-di -n- Hepuchiruto
Resilane , 1,2-di-n-octyltrisilane , 1,2
-Di-n-nonyltrisilane , 1,2-di-n-decyl
Trisilane , 1,2-di-n-dodecyltrisilane , 1,
2-diphenyltrisilane , 1,2-di-p-tolylt
Rishiran, 1,2-mesylate tilt Li silane, 1,2-Jibe
Benzyltrisilane , 1,2- diphenethyltrisilane ,
1,2-bis (trimethylsilylmethyl) trisilane ,
1,3-dimethyltrisilane , 1,3-diethyltrisila
Emissions, 1,3-di -n- propyl trimethoxy silane, bis (3,
3,3-trifluoropropyl) trisilane , 1,3-di
-N- butyl trisilane, 1,3-di -t- butyltri
Silane , di (1-methylpropyl) trisilane , di (2
-Methylpropyl ) trisilane , 1,3-diamyltri
Silane , 1,3-di-n-hexyltrisilane , 1,3-
Dicyclohexyltrisilane , 1,3-di-n-hepti
Rutrisilane , 1,3-di-n-octyltrisilane ,
1,3-di-n-nonyltrisilane , 1,3-di-n-de
Siltrisilane , 1,3-di-n-dodecyltrisila
Emissions, 1,3-diphenyl trisilane, 1,3-di -p- DOO
Rirutorishiran, 1,3-mesylate tilt Li silane, 1,3
- dibenzyl trisilane, 1,3-phenethyl Rishi
Orchid 1,3-bis (trimethylsilylmethyl) trishi
Orchid , 1-ethyl-1-methyltrisilane, 1-methyl-1-n-propyltrisilane, 1-methyl-1-
(3,3,3-trifluoropropyl) trisilane, 1-
Methyl-1-i-propyltrisilane, 1-n-butyl-1-methyltrisilane, 1-t-butyl-1-methyltrisilane, 1-methyl-1- (1-methylpropyl)
Trisilane, 1-methyl-1- (2-methylpropyl)
Trisilane, 1-amyl-1-methyltrisilane, 1-
n-hexyl-1-methyltrisilane, 1-cyclohexyl-1-methyltrisilane, 1-n-heptyl-1-
Methyltrisilane, 1-methyl-1-n-octyltrisilane, 1-methyl-1-n-nonyltrisilane, 1-
n-decyl-1-methyltrisilane, 1-n-dodecyl-1-methyltrisilane, 1-methyl-1-phenyltrisilane, 1-p-tolyl-1-methyltrisilane, 1
-Methyl-1-mesityltrisilane, 1-benzyl-1
-Methyltrisilane, 1-methyl-1-phenethyltrisilane, 1-methyl-1- (trimethylsilylmethyl)
Trisilane, 1- (p-methylphenethyl) -1-methyltrisilane, 1-ethyl-1-phenyltrisilane,
1-t-butyl-1-phenyltrisilane, 1-ethyl-2-methyltrisilane, 1-methyl-2-n-propyltrisilane, 1-methyl-2- (3,3,3-trifluoropropyl) ) Trisilane, 1-methyl-2-i-propyltrisilane, 1-n-butyl-2-methyltrisilane, 1-t-butyl-2-methyltrisilane, 1-methyl-2- (1-methylpropyl) ) Trisilane, 1-methyl-2- (2-methylpropyl) trisilane, 1-amyl-2-methyltrisilane, 1-n-hexyl-2-methyltrisilane, 1-cyclohexyl-2-methyltrisilane, 1 -N-heptyl-2-methyltrisilane, 1
-Methyl-2-n-octyltrisilane, 1-methyl-
2-n-nonyltrisilane, 1-n-decyl-2-methyltrisilane, 1-n-dodecyl-2-methyltrisilane, 1-methyl-2-phenyltrisilane, 1-p-tolyl-2- Methyltrisilane, 1-methyl-2-mesityltrisilane, 1-benzyl-2-methyltrisilane,
1-methyl-2-phenethyltrisilane, 1-methyl-
2- (trimethylsilylmethyl) trisilane, 1- (p
-Methylphenethyl) -2-methyltrisilane, 1-ethyl-2-phenyltrisilane, 1-t-butyl-2-
Phenyltrisilane, 1-ethyl-3-methyltrisilane, 1-methyl-3-n-propyltrisilane, 1-methyl-3- (3,3,3-trifluoropropyl) trisilane, 1-methyl-3 -I-propyltrisilane, 1-
n-butyl-3-methyltrisilane, 1-t-butyl-
3-methyltrisilane, 1-methyl-3- (1-methylpropyl) trisilane, 1-methyl-3- (2-methylpropyl) trisilane, 1-amyl-3-methyltrisilane, 1-n-hexyl- 3-methyltrisilane, 1-
Cyclohexyl-3-methyltrisilane, 1-n-heptyl-3-methyltrisilane, 1-methyl-3-n-octyltrisilane, 1-methyl-3-n-nonyltrisilane, 1-n-decyl- 3-methyltrisilane, 1-n
-Dodecyl-3-methyltrisilane, 1-methyl-3-
Phenyltrisilane, 1-p-tolyl-3-methyltrisilane, 1-methyl-3-mesityltrisilane, 1-benzyl-3-methyltrisilane, 1-methyl-3-phenethyltrisilane, 1-methyl -3- (trimethylsilylmethyl) trisilane, 1- (p-methylphenethyl)
-3-methyltrisilane, 1-ethyl-3-phenyltrisilane, 1-t-butyl-3-phenyltrisilane,
1,1,1-trimethyltrisilane , 1,1,1-triethyl
Lutrisilane , 1,1,1-tri-n- propyltrisila
Emissions, 1,1,1-tris (3,3,3-trifluoro propyl
Le) trisilane , 1,1,1-tri-n-butyltrisila
Emissions, 1,1,1--t- butyl trisilane, 1,1,1
-Tri (1-methylpropyl) trisilane , 1,1,1-
Tri (2-methylpropyl) trisilane , 1,1,1-to
Amyl trisilane, 1,1,1-tri -n- Hekishiruto
Lisilane , 1,1,1-tricyclohexyltrisilane ,
1,1,1-tri-n-heptyltrisilane , 1,1,1-
Tri-n-octyltrisilane , 1,1,1-tri-n-
Nonyl birds silane, 1,1,1--n- Deshirutorishi
Run , 1,1,1-tri-n-dodecyltrisilane , 1,
1,1-triphenyltrisilane , 1,1,1-tri-p
- tolyl trisilane, 1,1,1-mesylate tilt Li Sila
Emissions, 1,1,1-benzyl trisilane, 1,1,1 DOO
Lihue Ne tilt Li silane, 1,1,1-tris (trimethylene
Rusilylmethyl) trisilane , 1-ethyl-1,1-di
Methyltrisilane , 1-methyl-1,1-di-n-pro
Pyrtrisilane , 1-methyl-1,1-bis (3,3,3
-Trifluoropropyl) trisilane , 1-methyl-
1,1-di-i-propyltrisilane , 1-n-butyl
-1,1-dimethyltrisilane , 1-t-butyl- 1,1
- dimethyl trisilane, 1-methyl-1,1-di (1
Methylpropyl) trisilane , 1-methyl-1,1-di
(2-methylpropyl) trisilane , 1-amyl-1,
1-dimethyltrisilane , 1-n-hexyl-1,1-
Dimethyltrisilane , 1-cyclohexyl-1,1-di
Methyltrisilane , 1-n-heptyl-1,1-dimethyl
Lutrisilane , 1-methyl-1,1-di-n-octyl
Trisilane, 1-methyl-1,1--n- Nonirutori
Silane , 1-n-decyl-1,1-dimethyltrisila
Down, 1-n-dodecyl-1,1-dimethyl trisilane,
1-methyl-1,1-diphenyltrisilane , 1-p-
Tolyl-1,1-dimethyltrisilane , 1-methyl-1,
1 -Dimesityl trisilane , 1-benzyl-1,1-di
Methyltrisilane , 1-methyl-1,1-diphenethyl
Trisilane , 1-methyl-1,1-bis (trimethylsilane
Rylmethyl) trisilane , 1- (p- methylphenethyl)
) -1,1-Dimethyltrisilane , 1-ethyl -1,1
-Diphenyltrisilane , 1-t-butyl-1,1-di
Phenyl trisilane, 1,1,2-trimethyl silane, 1,1,2 triethyl silane, 1,1,2-tri -n- propyl trimethoxy silane, 1,1,2-tris (3,3,
3-trifluoropropyl) trisilane, 1,1,2-tri-n-butyltrisilane, 1,1,2-tri-t-butyltrisilane, 1,1,2-tri (1-methylpropyl)
Trisilane, 1,1,2-tri (2-methylpropyl) trisilane, 1,1,2-triamyltrisilane, 1,1,2
-Tri-n-hexyltrisilane, 1,1,2-tricyclohexyltrisilane, 1,1,2-tri-n-heptyltrisilane, 1,1,2-tri-n-octyltrisilane, 1, 1,2-tri-n-nonyltrisilane, 1,1,2
-Tri-n-decyltrisilane, 1,1,2-tri-n-
Dodecyltrisilane, 1,1,2-triphenyltrisilane, 1,1,2-tri-p-tolyltrisilane, 1,1,2
-Trimesityl trisilane, 1,1,2-tribenzyl trisilane, 1,1,2-triphenethyl trisilane, 1,
1,2-tris (trimethylsilylmethyl) trisilane, 1,1,3-trimethyltrisilane, 1,1,3-triethyltrisilane, 1,1,3-tri-n-propyltrisilane, 1,1,3 -Tris (3,3,3-trifluoropropyl) trisilane, 1,1,3-tri-n-butyltrisilane, 1,1,3-tri-t-butyltrisilane, 1,
1,3-tri (1-methylpropyl) trisilane, 1,
1,3-tri (2-methylpropyl) trisilane, 1,
1,3-triamyltrisilane, 1,1,3-tri-n-
Hexyltrisilane, 1,1,3-tricyclohexyltrisilane, 1,1,3-tri-n-heptyltrisilane,
1,1,3-tri-n-octyltrisilane, 1,1,3-
Tri-n-nonyltrisilane, 1,1,3-tri-n-decyltrisilane, 1,1,3-tri-n-dodecyltrisilane, 1,1,3-triphenyltrisilane, 1,1 , 3-
Tri-p-tolyltrisilane, 1,1,3-trimesityltrisilane, 1,1,3-tribenzyltrisilane, 1,
1,3-triphenethyltrisilane, 1,1,3-tris (trimethylsilylmethyl) trisilane, 1,2,3-trimethyltrisilane, 1,2,3-triethyltrisilane, 1,2,3-tri- n-propyltrisilane, 1,2,
3-tris (3,3,3-trifluoropropyl) trisilane, 1,2,3-tri-n-butyltrisilane, 1,2,
3-tri-t-butyltrisilane, 1,2,3-tri (1
-Methylpropyl) trisilane, 1,2,3-tri (2-
Methylpropyl) trisilane, 1,2,3-triamyltrisilane, 1,2,3-tri-n-hexyltrisilane,
1,2,3-tricyclohexyltrisilane, 1,2,3-
Tri-n-heptyltrisilane, 1,2,3-tri-n-
Octyltrisilane, 1,2,3-tri-n-nonyltrisilane, 1,2,3-tri-n-decyltrisilane, 1,
2,3-tri-n-dodecyltrisilane, 1,2,3-triphenyltrisilane, 1,2,3-tri-p-tolyltrisilane, 1,2,3-trimethylsilyltrisilane, 1, Two,
3-tribenzyltrisilane, 1,2,3-triphenethyltrisilane, 1,2,3-tris (trimethylsilylmethyl) trisilane, 1,1-diethyl-2-methyltrisilane, 1,1-dimethyl-2 -N-propyltrisilane, 1,1-dimethyl-2-i-propyltrisilane,
1,1-di-n-butyl-2-methyltrisilane, 1,1
-Di-t-butyl-2-methyltrisilane, 1,1-di-n-hexyl-2-methyltrisilane, 1,1-dicyclohexyl-2-methyltrisilane, 1,1-di-n
-Heptyl-2-methyltrisilane, 1,1-dimethyl-2-n-octyltrisilane, 1,1-di-n-decyl-2-methyltrisilane, 1,1-dimethyl-2-phenyltrisilane 1,1-di (p-methylphenethyl) -2-methyltrisilane, 1,1-dimethyl-2-
(Β-phenethyl) trisilane, 1,1-di-p-tolyl-2-methyltrisilane, 1,1-diphenyl-2-
Ethyltrisilane, 1,1-di-t-butyl-2-phenyltrisilane, 1,1-di (phenyldimethylsilyl) -2-methyltrisilane, 1,1-bis (trimethylsilyl) -2-methyltrisilane Silane, 1,1-diethyl-3-methyltrisilane, 1,1-dimethyl-3-n-
Propyltrisilane, 1,1-dimethyl-3-i-propyltrisilane, 1,1-di-n-butyl-3-methyltrisilane, 1,1-di-t-butyl-3-methyltrisilane, 1,1-di-n-hexyl-3-methyltrisilane, 1,1-dicyclohexyl-3-methyltrisilane, 1,1-di-n-heptyl-3-methyltrisilane, 1,1-dimethyl- 3-n-octyltrisilane,
1,1-di-n-decyl-3-methyltrisilane, 1,1
-Dimethyl-3-phenyltrisilane, 1,1-di-
(P-methylphenethyl) -3-methyltrisilane,
1,1-dimethyl-3- (β-phenethyl) trisilane, 1,1-di-p-tolyl-3-methyltrisilane,
1,1-diphenyl-3-ethyltrisilane, 1,1-di-t-butyl-3-phenyltrisilane, 1,1-di (phenyldimethylsilyl) -3-methyltrisilane,
1,1-bis (trimethylsilyl) -3-methyltrisilane, 1,2-diethyl-3-methyltrisilane, 1,2
-Dimethyl-3-n-propyltrisilane, 1,2-dimethyl-3-i-propyltrisilane, 1,2-di-n
-Butyl-3-methyltrisilane, 1,2-di-t-butyl-3-methyltrisilane, 1,2-di-n-hexyl-3-methyltrisilane, 1,2-dicyclohexyl-3-methyl Trisilane, 1,2-di-n-heptyl-
3-methyltrisilane, 1,2-dimethyl-3-n-octyltrisilane, 1,2-di-n-decyl-3-methyltrisilane, 1,2-dimethyl-3-phenyltrisilane, 1, 2-di (p-methylphenethyl) -3-methyltrisilane, 1,2-dimethyl-3- (β-phenethyl) trisilane, 1,2-di-p-tolyl-3-methyltrisilane, 1,2 -Diphenyl-3-ethyltrisilane, 1,2-di-t-butyl-3-phenyltrisilane, 1,2-di (phenyldimethylsilyl) -3-methyltrisilane, 1,2-bis (trimethylsilyl) -3
-Methyltrisilane and the like.

Among the above, those with an underline are the preferred hydrotrisilanes.

In the first embodiment of the present invention, hydrosilanes are reacted with a mixture containing the metallocene compound and the silyl compound as a catalyst. The reaction is usually a dehydrogenative condensation reaction and is carried out under the following conditions. ..

The reaction temperature is 0 to 250 ° C., preferably 25.
~ 210 ° C.

By selecting or changing the reaction temperature within the above range, the properties of the obtained polysilanes can be adjusted according to the purpose, as described later.

The reaction time varies depending on the reaction temperature and the amount of catalyst, but is usually 5 minutes to 24 hours, preferably 30 minutes to 3 hours.

The reaction may be carried out in the presence or absence of a solvent. When a solvent is used, a hydrocarbon solvent such as toluene, xylene, heptane, decane, dodecane, an ether solvent such as diethyl ether, isopropyl ether, methylbutyl ether, dimethoxyethane, tetrahydrofuran, dioxane, diglyme, dimethylformamide, hexamethylphosphine. An amide solvent such as organic triamide, an ester solvent such as ethyl acetate and butyl acetate, and a sulfoxide such as dimethyl sulfoxide are used.

The reaction is preferably carried out in an atmosphere of an inert gas such as argon or nitrogen.

The structure of the polysilanes thus obtained has, as repeating units, the following general formulas (15), (16) and /
Or (17)

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

(In the formula, R ¹⁹ is hydrogen, an alkyl group, an alkyl group having a substituent, a phenyl group or a phenyl group having a substituent, or an RR′R ″ Si type silyl having an alkyl group or a phenyl group as a substituent. R ²⁰ is hydrogen, an alkyl group, an alkyl group having a substituent, a phenyl group or a phenyl group having a substituent, or an RR′R ″ Si type silyl group having an alkyl group or a phenyl group as a substituent. However, R, R'and R "are hydrogen and have 1 to 1 carbon atoms.
2 alkyl groups, aralkyl groups, or aryl groups having 6 to 12 carbon atoms, which may be the same or different. )including.

The structure of the product is IR, ¹ HNMR, ¹³
Confirmed by CNMR, ²⁹ SiNMR, UV, GPC and the like.

The above general formulas (15), (16) and (1)
The composition ratio of the unit represented by 7) varies depending on the reaction temperature. For example, when the reaction temperature is low (0 to 60 ° C.), polysilane having a large number of straight chain structures or monocyclic structures and a small number of branched structures or bridged structures can be obtained. At this time, the degree of polymerization is 2 or more, but it is usually 20 to 100. Also, n
/ M is usually 0 to 10, preferably 0 to 5, and o / m is usually 0 to 10, preferably 0 to 5.

Further, as the reaction temperature increases, the values of n and / or o tend to increase, and 180 to 2
At 50 ° C., a polysilane having a small number of straight chain structures or monocyclic structures and a large number of branched structures, bridge structures or condensed polycyclic structures can be obtained. The degree of polymerization is 2 or more, but usually 6 to 2000. In this case, since m, n, and o may be 0 respectively, the range of possible values of n / m and o / n cannot be shown unconditionally, but n / m is usually 0.
~ 1000, preferably 0-100, o / n is usually 0
It is about 1000, preferably about 0 to 100.

At a temperature midway (60 to 180 ° C.),
The degree of polymerization is 2 or more, but is usually 10 to 1000, and n / m is usually 0 to 100, preferably 0 to 20, o
/ N is usually 0 to 100, preferably 0 to 20.

The ratio of m, n and o can be adjusted depending on the kind of hydrosilane used and the ratio of two or more kinds of hydrosilane used.

In the second embodiment of the present invention, a mixture containing (A) a metallocene compound represented by the general formula (1) and (B) ′ a metal hydride represented by the general formula (6) is used as a catalyst. ..

The metallocene compound represented by the general formula (1) is the same as that used in the first aspect of the present invention.

Examples of the metal hydride represented by the general formula (6) include LiH , NaH , KH , CaH.
₂ , AlH ₃ , MeAlH ₂ , EtAlH ₂ , n-PrAl
_{H 2, i-PrAlH 2,} n-BuAlH 2, i-BuA
1H ₂ , sec-BuAlH ₂ , t-BuAlH ₂ , Me _{2
AlH, Et 2 AlH, n-} Pr 2 AlH, i-Pr 2 A
_{lH, n-Bu 2 AlH,} i-Bu 2 AlH, sec-B
_{u 2 AlH, t-Bu 2} AlH, LiAlH 4, LiAl
(Et) ₂ H ₂ , LiAl (n-Pr) ₂ H ₂ , LiAl (i-
Pr) ₂ H ₂ , LiAl (n-Bu) ₂ H ₂ , LiAl (i-B
u) ₂ H ₂ , LiAl (sec-Bu) ₂ H ₂ , LiAl (t-
Bu) ₂ H ₂ , LiAl (Et) ₃ H, LiAl (n-Pr) ₃
H, LiAl (i-Pr) 3 H, LiAl (n-Bu) 3 H,
LiAl (i-Bu) ₃ H, LiAl (sec-Bu) ₃ H,
LiAl (OMe) ₃ H, LiAl (OEt) ₃ H, LiAl
_{(O-t-Bu) 3} H, NaAl (OCH 2 CH 2 -OMe) 3
_{H 2, BH 3, [(} CH 3) 2 CHCH (CH 3)] 2 BH, LiB
_{H 4, LiB (sec-Bu} ) 3 H, LiB (Et) 3 H, L
i (9-BBN) H, NaBH 4, KBH 4, Me 4 NB
H ₄ , Et ₄ NBH ₄ , LiD, NaD, KD, CaD ₂ ,
_{AlD 3, MeAlD 2, EtAlD 2} , n-PrAl
_{D 2, i-PrAlD 2,} n-BuAlD 2, i-BuA
_{lD 2, sec-BuAlD 2,} t-BuAlD 2, Me 2
AlD, Et ₂ AlD, n-Pr ₂ AlD, i-Pr ₂ A
_{lD, n-Bu 2 AlD,} i-Bu 2 AlD, sec-B
_{u 2 AlD, t-Bu 2} AlD, LiAlD 4, LiAl
(Et) ₂ D ₂ , LiAl (n-Pr) ₂ D ₂ , LiAl (i-
Pr) ₂ D ₂ , LiAl (n-Bu) ₂ D ₂ , LiAl (i-B
u) ₂ D ₂ , LiAl (sec-Bu) ₂ D ₂ , LiAl (t-
Bu) ₂ D ₂ , LiAl (Et) ₃ D, LiAl (n-Pr) ₃
D, LiAl (i-Pr) 3 D, LiAl (n-Bu) 3 D,
LiAl (i-Bu) ₃ D, LiAl (sec-Bu) ₃ D,
LiAl (OMe) ₃ D, LiAl (OEt) ₃ D, LiAl
_{(O-t-Bu) 3} D, NaAl (OCH 2 CH 2 OMe) 3 D
₂ , BD ₃ , [(CH ₃ ) ₂ CHCH (CH ₃ )] ₂ BD, LiBD
₄ , LiB (sec-Bu) ₃ D, LiB (Et) ₃ D, Li
(9-BBN) D, NaBD ₄ , KBD ₄ , Me ₄ NBD ₄ ,
Et ₄ NBD _{4 and the} like can be mentioned.

Among the above, those with an underline are the most preferable metal hydrides.

The metal hydride can be used alone or in combination of two or more selected from the above.

The metallocene compound and the metal hydride are used in a proportion of usually 0.01 to 10 mol, preferably 0.1 to 5 mol, and usually 0.005 to 50 mol, preferably 0.005 to 50 mol of the metallocene compound, relative to 100 mol of the hydrosilane. 0.05-20mo
It is l.

As additives to the catalyst, 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-12-crown-4, dibenzo-15-crown-5, dibenzo-18-crown are added. Crown ethers such as -6 and diamines such as tetramethylethylenediamine may be added. The use ratio of the additive is usually 0.005 to 50 per 100 mol of hydrosilanes.
mol, preferably 0.05 to 20 mol.

In the second embodiment of the present invention, polysilanes are produced by reacting hydrosilanes with a mixture containing the metallocene compound and metal hydride as a catalyst.

As the hydrosilanes, usually, hydromonosilanes, hydrodisilanes, hydrotrisilanes, or a mixture of two or more of them is used. The hydromonosilanes, hydrodisilanes and hydrotrisilanes used are the same as those used in the first aspect of the present invention.

In the second embodiment of the present invention, hydrosilanes are reacted with a mixture containing the above metallocene compound and metal hydride as a catalyst. This reaction is usually a dehydrogenative condensation reaction and is carried out under the following conditions. ..

The reaction temperature is 0 to 250 ° C., preferably 25
~ 210 ° C.

By selecting or changing the reaction temperature within the above range, the properties of the obtained polysilane can be adjusted according to the purpose, as described later.

The reaction time varies depending on the reaction temperature and the amount of catalyst, but is usually 5 minutes to 24 hours, preferably 30 minutes to 3 hours.

The reaction may be carried out in the presence or absence of a solvent. When using a solvent, a hydrocarbon solvent such as toluene, xylene, heptane, decane, dodecane, an ether solvent such as diethyl ether, isopropyl ether, methylbutyl ether, dimethoxyethane, tetrahydrofuran, dioxane, diglyme, dimethylformamide, hexamethylphosphine. Amide solvents such as folic triamide, ester solvents such as ethyl acetate and butyl acetate, and sulfoxides such as dimethyl sulfoxide are used.

The reaction is preferably carried out in an atmosphere of an inert gas such as argon or nitrogen.

The structural units of the polysilanes thus obtained include those represented by the general formulas (15), (16) and / or (17).

The structure of the product is IR, ¹ HNMR, ¹³
Confirmed by CNMR, ²⁹ SiNMR, UV, GPC and the like.

The above general formulas (15), (16) and (1)
The composition ratio of the unit represented by 7) varies depending on the reaction temperature. For example, when the reaction temperature is low (0 to 60 ° C.), polysilane having a large number of straight chain structures or monocyclic structures and a small number of branched structures or bridged structures can be obtained. At this time, the degree of polymerization is 2 or more, but it is usually 20 to 100. Also, n
/ M is usually 0 to 10, preferably 0 to 5. o / m
Is usually 0 to 10, preferably 0 to 5.

Further, as the reaction temperature increases, the values of n and / or o tend to increase, and the value of 180-2
At 50 ° C., a polysilane having a small number of straight chain structures or monocyclic structures and a large number of branched structures, bridge structures or condensed polycyclic structures can be obtained. The degree of polymerization is 2 or more, but usually 6 to 2000. In this case, since n, m, and o may be 0, respectively, the range of possible values of n / m and o / n cannot be shown unconditionally, but n / m is usually 0.
~ 1000, preferably 0-100, o / n is usually 0
It is about 1000, preferably about 0 to 100.

At a temperature midway (60 to 180 ° C.),
The degree of polymerization is 2 or more, but is usually 10 to 1000, and n / m is usually 0 to 100, preferably 0 to 20, o
/ M is usually 0 to 100, preferably 0 to 20.

The ratio of m, n and o can be adjusted depending on the kind of hydrosilane used and the ratio of two or more kinds of hydrosilane used.

According to the present invention, when a polysilane is produced from a hydrosilane, a polymer having a higher degree of polymerization can be produced more efficiently than when a known catalyst is used, which is extremely useful industrially. ..

[0078]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 In a 100 ml glass flask equipped with a magnetic stirrer, Cp ₂ HfCl ₂ (166) was used as a catalyst under an argon atmosphere.
mg, 0.437 mmol) and (Me ₃ Si) ₃ SiLi.
THF ₃ (369 mg, 0.784 mmol) was charged.
PhSiH ₃ (5.0 ml, 40 mmol) was then added at room temperature.

Immediately after the addition, vigorous gas generation was observed and the reaction product turned yellowish brown. The vigorous gas evolution continued for about 10 minutes, after which it became mild. After 23 hours, the reaction product was purified by passing through a column of Florisil (55 g) with the solvent toluene (500 ml).

When toluene was distilled off under reduced pressure, white solid polysilane (4.2 g) was obtained. Yield 96%
(% By weight based on PhSiH ₃ ).

When the physical properties of the obtained polysilane were examined, the following results were obtained.

GPC: Mw = 6800, Mn = 3900 IR: 915 cm ⁻¹ , 2104 cm ^{−1 1} H NMR: δ 4.1 to 5.3 (1H), 6.7 to 7.8
(5.5H) UV (THF): 258 nm, 295 nm (Shoulder) From the above analysis results, the composition of the constitutional units of the obtained polysilane was determined. It was found that the ratio of the given units was n / m = 0.1.

[0084] When the exception stirring for 2 hours and the Example 2 the reaction temperature to 110 ° C. was produced polysilane in the same manner as in Example 1, a yellow powder polysilane (about 100% yield; and reference PhSiH ₃ %) Was obtained.

GPC: Mw = 2300, Mn = 1500 IR: 915 cm ⁻¹ , 2100 cm ^{−1 1} H NMR: δ 4.0 to 5.9 (1H), 6.6 to 8.0
(6.8H) UV (THF): 254 nm, 309 nm (shoulder) From the above analysis results, the composition of the constitutional units of the obtained polysilane was determined. The ratio of the given units was found to be n / m = 2.78.

Example 3 Polysilane was produced in the same manner as in Example 1 except that the reaction temperature was stirred at 100 ° C. for 1 hour and then at 200 ° C. for 2 hours. ;
% By weight based on PhSiH ₃ ) was obtained.

[0087] GPC: Mw = 1100, Mn = 1000 IR: 2100cm -1 1 HNMR: δ4.5~6.0 (1H), 6.5~8.1
(12H) UV (THF): 254 nm (absorption tail continued to 370 nm) From the above analysis results, the composition of the constituent units of the obtained polysilane was determined. It was found that the ratio of units represented by () was n / m = 5.1.

Example 4 Cp ₂ ZrCl ₂ (182 mg, 0.623 m as catalyst)
mol) and (Me ₃ Si) ₃ SiLi THF ₃ (372 m
g, 0.790 mmol) was used and polysilane was produced in the same manner as in Example 1 except that the mixture was stirred at 110 ° C. for 2 hours.
% by weight based on hSiH ₃ ) was obtained.

[0089] GPC: Mw = 1500, Mn = 1000 IR: 915cm -1, 2100cm -1 1 HNMR: δ3.9~5.9 (1H), 6.6~8.1
(8.7H) UV (THF): 258 nm, 309 nm (Shoulder) From the above analysis results, the composition of the constitutional units of the obtained polysilane was determined. It was found that the ratio of the given units was n / m = 1.41.

Example 5 Cp ₂ ZrCl ₂ (174 mg, 0.594 m as catalyst)
mol) and Ph ₃ SiK (252 mg, 0.843 mmo
When polysilane was produced in the same manner as in Example 1 except that l) was used, colorless viscous polysilane (yield 9
3%; wt% based on PhSiH ₃ ) was obtained.

GPC: Mw = 3300, Mn = 2500 IR: 915 cm ⁻¹ , 2106 cm ^{−1 1} H NMR: δ 4.1 to 5.3 (1H), 6.7 to 7.8
(5.5H) UV (THF): 256 nm, 292 nm (Shoulder) From the above analysis results, the composition of the constitutional unit of the obtained polysilane was determined. It was found that the ratio of the given units was n / m = 0.2.

Example 6 Cp ₂ TiCl ₂ (148 mg, 0.594 m as catalyst)
mol) and Ph ₃ SiNa (238 mg, 0.843 mm)
Polysilane was produced in the same manner as in Example 1 except for using ol), and colorless viscous polysilane (yield 91%; weight% based on PhSiH ₃ ) was obtained.

GPC: Mw = 2800, Mn = 2200 IR: 915 cm ⁻¹ , 2106 cm ^{−1 1} H NMR: δ 4.2 to 5.3 (1H), 6.7 to 7.9
(5.9H) UV (THF): 252 nm, 293 nm (shoulder) From the above analysis results, the composition of the constitutional units of the obtained polysilane was determined. It was found that the ratio of the given units was n / m = 0.18.

Example 7 In a 100 ml glass flask equipped with a magnetic stirrer, Cp ₂ HfCl ₂ (195
mg, 0.514 mmol) and KH (60 mg, 1.5 m
mol) and 18-crown-6 (64 mg, 0.24 m)
mol) was added. Here, PhSiH ₃ (5.0 ml,
(40 mmol) was added and heated to 100 ° C., gas generation was observed, and the reaction product turned yellowish brown.

After 6 hours, the reaction product was purified by passing through a column of Florisil (55 g) with the solvent toluene (500 ml).

When toluene was distilled off under reduced pressure, pale yellow viscous polysilane (3.9 g) was obtained. Yield is 90
% (Wt% based on PhSiH ₃ ).

GPC: Mw = 3500, Mn = 2500 IR: 915 cm ⁻¹ , 2104 cm ^{−1 1} H NMR: δ 4.1 to 5.4 (1H), 6.6 to 7.8
(7.4H) UV (THF): 258 nm, 300 nm (Shoulder) From the above analysis results, the composition of the constituent units of the obtained polysilane was determined, and the composition was expressed by the general formula (15) and the general formula (16). It was found that the ratio of the given units was n / m = 2.08.

Example 8 In a 100 ml glass flask equipped with a magnetic stirrer, under an argon atmosphere, Cp ₂ HfCl ₂ (210) was used as a catalyst.
mg, 0.554 mmol) and KH (60 mg, 1.5 m
mol) and NaH (26 mg, 1.1 mmol) and 18
-Crown-6 (64 mg, 0.24 mmol) was charged. Here, PhSiH ₃ (5.0 ml, 40 mmol)
Was added and heated at 100 ° C. for 1 hour and then at 200 ° C. for 2 hours. When the reaction product was subjected to the same purification treatment as in Example 7, yellow powdery polysilane (yield 73%; PhS
% by weight based on iH ₃ ) was obtained.

[0099] GPC: Mw = 940, Mn = 900 IR: 2100cm -1 1 HNMR: δ5.2~5.9 (1H), 6.4~8.1
(33H) UV (THF): 254 nm (absorption tail continued up to 380 nm) From the above analysis results, the composition of the constitutional unit of the obtained polysilane was determined. It was found that the ratio of units represented by () was n / m = 5.6.

Example 9 Cp ₂ ZrCl ₂ (182 mg, 0.623 m as catalyst)
mol) and LiAlH ₄ (9 mg, 0.2 mmol), and here, PhSiH ₃ (5.0 ml, 40 mmol)
THF solution (5.0 ml) was added, and the mixture was stirred at room temperature for 24 hours.

When the reaction product was treated for purification in the same manner as in Example 7, white viscous polysilane (yield ˜100) was obtained.
%; Wt% based on PhSiH ₃ ) was obtained.

GPC: Mw = 5600, Mn = 3500 IR: 915 cm ⁻¹ , 2106 cm ^{−1 1} H NMR: δ 4.1 to 5.4 (1H), 6.6 to 7.9
(5.6H) UV (THF): 254 nm, 293 nm (Shoulder) From the above analysis results, the composition of the constituent units of the obtained polysilane was determined, and the composition was expressed by the general formula (15) and the general formula (16). It was found that the ratio of the given units was n / m = 0.12.

Example 10 Cp ₂ TiCl ₂ (148 mg, 0.594 m as catalyst)
(mol) was used to produce polysilane in the same manner as in Example 9 to obtain colorless viscous polysilane (yield 96%; weight% based on PhSiH ₃ ).

GPC: Mw = 2900, Mn = 2300 IR: 915 cm ⁻¹ , 2106 cm ^{−1 1} H NMR: δ 4.2 to 5.3 (1H), 6.7 to 7.9
(5.7H) UV (THF): 252 nm, 292 nm (Shoulder) From the above analysis results, the composition of the constitutional units of the obtained polysilane was determined. It was found that the ratio of the given units was n / m = 0.14.

Example 11 Cp ₂ HfCl ₂ (210 mg, 0.554 m as catalyst)
mol) and KD (65 mg, 1.6 mmol) and 18-
When polysilane was produced in the same manner as in Example 7 except that Crown-6 (192 mg, 0.726 mmol) was used, a pale yellow viscous polysilane (3.7 g) was obtained. The yield was 85% (weight% based on PhSiH ₃ ).

GPC: Mw = 3200, Mn = 2100 IR: 915 cm ⁻¹ , 2106 cm ^{−1 1} H NMR: δ 4.2 to 5.5 (1H), 6.6 to 7.9
(6.9H) UV (THF): 254 nm, 302 nm (Shoulder) From the above analysis results, the composition of the constituent units of the obtained polysilane was determined, and the composition was expressed by the general formula (15) and the general formula (16). It was found that the ratio of the given units was n / m = 2.63.

Example 12 Cp ₂ HfCl ₂ (143 mg, 0.376 m as catalyst)
mol) and KH (84 mg, 2.1 mmol) and 18-
Crown -6 (618 mg, 2.34 mmol) using, _{here, n-HexSiH 8 (3.6g,} 31mmo
l) is added, 100 ° C. for 1 hour, 150 ° C. for 1 hour, 2
Heated at 00 ° C. for 2 hours.

When the reaction product was subjected to the same purification treatment as in Example 7, a viscous pale yellow polysilane (yield 83
%; Wt% based on n-HexSiH ₈ ) was obtained.

[0109] GPC: Mw = 1700, Mn = 1600 IR: 2064cm -1 1 HNMR: δ0.8~2.0 (96H), 4.9~5.2
(1H) UV (THF): 265 nm From the above analysis results, the composition of the constituent units of the obtained polysilane was determined. The ratio of the units represented by the general formula (15) and the general formula (16) was n. It was found that /m=6.3.

Example 13 Cp ₂ HfCl ₂ (64 mg, 0.17 mmo as a catalyst)
1) and KH (30 mg, 0.76 mmol) and 18-crown-6 (249 mg, 0.942 mmol) were used, where n-HexSiH ₂ SiH ₃ (2.5 g, 1
7 mmol) and added at 100 ° C. for 1 hour and 150 ° C. for 1 hour.
Heated for hours.

When the reaction product was subjected to the same purification treatment as in Example 7, a dark red viscous polysilane (yield: 75
%; Wt% based on n-HexSiH ₂ SiH ₃ ) was obtained.

GPC: Mw = 14000, Mn = 460
^{0 IR: 2106cm -1 1 HNMR:} δ1.0~2.2 (21H), 3.6~5.0
(1H) UV (THF): 428nm

Claims (2)

[Claims] 1. A method for producing polysilanes by reacting hydrosilanes, wherein (A) the following general formula (1): LL'MCl ₂ (1) as a catalyst [wherein M is Ti, Represents Zr or Hf. L and L ′ are unsubstituted cyclopentadienyl and have 1 to 6 carbon atoms.
A cyclopentadienyl substituted with an alkyl group of the following general formula (2): embedded image R ¹ R ² R ³ Si— (2) (wherein R ¹ , R ² and R ³ are hydrogen and carbon number) An alkyl group having 1 to 12 or an aralkyl group, or a carbon number of 6 to 1
Selected from two aryl groups, which may be the same or different. } Cyclopentadienyl substituted with a silyl group, unsubstituted indenyl, indenyl substituted with an alkyl group having 1 to 6 carbon atoms, or indenyl substituted with a silyl group represented by the general formula (2) above. And may be the same as or different from each other.
Further, between L and L'is an alkylene having 1 to 4 carbon atoms, or the following general formula (3): {In the formula, R ⁷ and R ⁸ are selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, or an aryl group having 6 to 12 carbon atoms, and these may be the same or different. And may be crosslinked with silylene], and (B) the following general formula (4): R ⁹ R ¹⁰ R ¹¹ SiA (4) [wherein R ⁹ , R ¹⁰ and R ¹¹ each have 1 to 12 carbon atoms.
A linear or branched alkyl group or aralkyl group, an aryl group having 6 to 12 carbon atoms, or a compound represented by the following general formula (5): R ¹² R ¹³ R ¹⁴ Si- (5) {wherein R ¹² , R ¹³ and R ¹⁴ are selected from an alkyl group or an aryl group having 1 to 8 carbon atoms and may be the same or different. } And are the same or different. A represents Li, Na, or K. ] The method of using the mixture containing the silyl compound represented by these. 2. A method for producing polysilanes by reacting hydrosilanes, wherein as a catalyst, (A) the following general formula (1): LL′MCl ₂ (1) [wherein M is Ti , Zr, or Hf. L and L ′ are unsubstituted cyclopentadienyl and have 1 to 6 carbon atoms.
Cyclopentadienyl substituted with an alkyl group represented by the following general formula (2): embedded image R ¹ R ² R ³ Si— (2) {wherein R ¹ , R ² and R ³ are hydrogen and carbon number An alkyl group having 1 to 12 or an aralkyl group, or a carbon number of 6 to 1
Selected from two aryl groups, which may be the same or different. } Cyclopentadienyl substituted with a silyl group, unsubstituted indenyl, indenyl substituted with an alkyl group having 1 to 6 carbon atoms, or indenyl substituted with a silyl group represented by the general formula (2) above. And may be the same as or different from each other.
In addition, an alkylene having 1 to 4 carbon atoms between L and L ', or the following general formula (3): {In the formula, R ⁷ and R ⁸ are selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, or an aryl group having 6 to 12 carbon atoms, and these may be the same or different. }, Which may be crosslinked with silylene], and (B) ′ represented by the following general formula (6): A′Xn (6) (wherein A ′ is Li , Na, K, Ca, Al, R ⁴
_(3-n) Al, LiAl, LiAlR ⁵ _(4-n) , NaAlR ⁵
_(4-n) , B, R ⁴ _(3-n) B, LiB, LiBR ⁵ , NaB,
Represents KB or R ⁶ B, R ⁴ represents an alkyl group having 1 to ⁵ carbon atoms, R ⁵ represents an alkyl or alkoxyl group having 1 to 8 carbon atoms, and R ⁶ represents a quaternary ammonium group having 1 to 4 carbon atoms. Shown respectively. However, when a plurality of R ⁴ , R ⁵ and R ⁶ are present, they may be the same or different. Moreover, X is H or D, and n is an integer of 1-4. The manufacturing method of polysilanes characterized by using the mixture containing the metal hydride represented by these.