Photovoltaic element

A photovoltaic element produced from a product resulting from decomposition of a silicon polymer having an organic substituent of the group consisting of a hydrocarbon group, a halogenated hydrocarbon group, and a silyl group R.sup.3 R.sup.4 R.sup.5 Si- (wherein R.sup.3 -R.sup.5 each are identical or different, including C.sub.1 -C.sub.8 alkyl groups and C.sub.6 -C.sub.10 aryl groups). The inventive photovoltaic element is substantially pollution-free and capable of quantity production at a relatively large unit size.

 

What is claimed is:

1. A photovoltaic element which comprises a semiconducting material resulting from decomposition of a silicon polymer having an organic substituent.

2. A photovoltaic element according to claim 1 wherein said organic substituent is selected from the group consisting of a hydrocarbon group, a halogenated hydrocarbon group, and a silyl group R.sup.3 R.sup.4 R.sup.5 Si-, wherein R.sup.3 -R.sup.5 each are identical or different, including C.sub.1 -C.sub.8 alkyl groups and C.sub.6 -C.sub.10 aryl groups.

3. A photovoltaic element according to claim 1 wherein said silicon polymer has at least one of the repeating units of the formula ##STR6## in the above formulae (I) and (II) above, R.sup.1, R.sup.2 and R' each are hydrogen, C.sub.1 -C.sub.12 hydrocarbon group, halogenated hydrocarbon group, or silyl group R.sup.3 R.sup.4 R.sup.5 Si- and may be crosslinked within and between each repeating unit.

4. A photovoltaic element according to claim 3 wherein said repeating unit or units contained in said polymer essentially has (have) an organic substituent from the group consisting of a hydrocarbon group, a halogenated hydrocarbon groupsand a silyl group R.sup.3 R.sup.4 R.sup.5 Si-, wherein R.sup.3 -R.sup.5 each are identical or different, including C.sub.1 -C.sub.8 alkyl groups and C.sub.6 -C.sub.10 aryl groups.

5. A process for the production of a semiconductor material for a photovoltaic element resulting from decomposition of a silicon polymer having organic substituents, said decomposition involving at least one of the following modes of reaction:

(1) dissociation of all or part of the organic side chain substituents in the silicon polymer;

(2) incorporation of all or part of the organic substituents in between the Si--Si bonds in the polymer skeleton to form a main chain;

(3) decoupling and recoupling of the Si--Si bonds in the polymer skeleton to effect recombination of the main chain skeleton;

(4) decoupling and recoupling between the Si atom and the side-chain organic substituent in the polymer skeleton, leading to changes in the polymer structure;

(5) decoupling of the Si--Si bonds in the polymer skeleton, resulting in dissociation of atom groups including the Si atom;

(6) formation of new Si--Si bonds simultaneous with or subsequent to the reactions (1)-(5) above;

(7) formation of new Si--Si bonds, resulting in the above reactions (1)-(5);

(8) molecular or part thereof other than those of silicon polymer coexistent in the decomposing atmosphere are incorporated into decomposed silicon polymer by way of covalent bonding, ion bonding, ligand bonding, physical adsorption or physical entrapment;

(9) molecules or part thereof other than those of silicon polymer coexistent in the decomposing atmosphere induce the above reactions (1)-(7); and

(10) molecules or part thereof other than those of silicon polymer coexistent in the decomposing atmosphere induce the above reactions (1)-(7) and are also incorporated into decomposed silicon polymer by way of covalent bonding, ligand bonding, physical adsorption or physical entrapment.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a photovoltaic element useful inter alia for the production of solar cells.

2. Prior Art

During recent years there has been a growing demand for photovoltaic elements, specifically as solar cells, thanks to their remarkable environmental friendliness and contribution to energy saving, However, difficulties have been encountered in the production of solar cells made from monocrystalline silicon because this material is not only so costly but also the process of making such solar cells is so complicated as to prohibit practical commercial availability. Solar cells made from polycrystalline silicon are also known but this material is more difficult to prepare. Amorphous silicon solar cells are susceptible to initial deterioration and are costly to make due to the need for large-seale vacuum devices. Solar cells formed from gallium arsenide, cadmium sulfide, cadmium tellurium, and like semiconducting compounds pose a pollution problem.

SUMMARY OF THE INVENTION

With the foregoing difficulties and problems of the prior art in view, the present invention seeks to provide a photovoltaic element which can be produced in quantities at a relatively large unit size with utmost ease and which is substantially pollution-free.

It has now been found that such a photovoltaic element can be easily and conveniently produced from a product resulting from decomposition of a silicon polymer having an organic substituent.

Therefore, a photovoltaic element provided in accordance with the invention comprises a semiconducting material resulting from decomposition of a silicon polymer having an organic substituent.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a cross-sectional view utilized to explain the construction of a photovoltaic element 10 embodying the invention which comprises a metallic film layer 11, a decomposed silicon polymer layer 12, a molybdenum layer 13, and a quartz base layer 14.

DETAILED DESCRIPTION OF THE INVENTION

A starting silicon polymer used in the invention contains an organic substituent group which includes a hydrocarbon group, a halogenated hydrocarbon group, and a silyl group R.sup.3 R.sup.4 R.sup.5 Si- (wherein R.sup.3 -R.sup.5 are identical or different, including C.sub.1 -C.sub.8 alkyl groups and C.sub.6 -C.sub.10 aryl groups). The hydrocarbon group encompasses C.sub.1 -C.sub.12, preferably C.sub.1 -C.sub.8 alkyl, cycloalkyl, alkenyl and cycloalkenyl groups, C.sub.7 -C.sub.12 aralkyl groups, C.sub.6 -C.sub.12 aryl groups, as well as divalent or trivalent substituents derived therefrom. The halogenated hydrocarbon group is suitably a halogenated alkyl group. The silyl group includes trialkyl silyl, aryldialkyl silyl, triaryl, and diarylalkyl silyl groups.

The term silicon polymer as used herein designates such a silicon polymer which has at least one repeating unit of the formulae ##STR1## said one repeating unit essentially having an organic substituent. The inventive silicon polymer may further contain a repeating unit of the formula ##STR2##

In the formulae (I) and (II) above, R.sup.1, R.sup.2, and R' each are hydrogen, C.sub.1 -C.sub.12 hydrocarbon group, halogenated hydrocarbon group, or silyl group R.sup.3 R.sup.4 R.sup.5 Si- and may be crosslinked within and between each repeating unit.

The hydrocarbon group R.sup.1, R.sup.2, or R' exemplarily includes C.sub.1 -C.sub.12, preferably C.sub.1 -C.sub.8 alkyl, cycloalkyl, alkenyl and cycloalkenyl groups, C.sub.7 -C.sub.12 aralkyl groups and C.sub.6 -C.sub.12 aryl groups. In case the repeating units are crosslinked therewithin or therebetween, and they include divalent or polyvalent groups derived from R.sub.1, R.sub.2, or R'. The alkyl groups include methyl, ethyl, n-propyl, isolpropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, 1,2-dimethylpropylo, n-hexyl, 1,1,2-trimethylpropyl, 1-methylpentyl, 1-ethylbutyl, n-heptyl, 1-methylhexyl, 1,2,2-trimethylbutyl, 1,1-dimethylpentyl, n-octyl, 2-ethylhexyl, 1-methylheptyl, 1-ethylhexyl, 1,1-dimethylhexyl, n-nonyl, 1-methyloctyl, 1,1-dimethylheptyl, n-decyl, 1-ethylactyl, 1-methyl-1-ethylheptyl or the like. The cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-bicyclo-[2,2,1]heptyl, exo-2-bicyclo[2,2,1]heptyl, cyclooctyl, 1-bicyclo[2,2,2]octyl, 2-bycyclo[2,2,2]octyl, 1-adamantyl, 2-adamantyl or the like. The alkenyl groups include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-methyl-2-propenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, 2-methyl-2-butenyl, 1,2-dimethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 2,3-dimethyl-2-butenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl or the like. The cycloalkenyl groups include 1-cyclopentenyl, 2-cyclopentene-1-il, 1-cyclohexenyl, 2-cyclohexene-1-il, 3-cyclohexene-1-il, 1-cycloheptenyl, 2-cycloheptene-1-il, 3-cycloheptene-1-il, 2-bicyclo[2,2,1]heptene-1-il, 2-bicyclo[2,2,1]heptene-2-il, 5-bicyclo[2,2,1]heptene-2-il, 7- bicyclo[2,2,1]heptene-2-il, 1-cyclooctenyl, 2-cyclooctene-1-il, 3-cyclooctene-1-il, 2-bicyclo[2,2,2]octene-1-il, 2-bicyclo[2,2,2]octene-2-il, 2-bicyclo[2,2,2]octene-5-il, 2-bicyclo[2,2,2]octene-6-il or the like. The aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, cumyl or the like. The aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl or the like. The silyl group exemplarily includes trimethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, phenyldimethyl, triphenylsilyl or the like. The halogenated hydrocarbon group is a C.sub.1 -C.sub.12 preferably C.sub.1 -C.sub.8 halogenated alkyl group in which halogen is fluorine, chlorine, bromine, and iodine, with fluorine and chlorine being particularly preferred. The number of halogen substitution in the alkyl group is 1-12, preferably 1-6 in which 3,3,3-trifluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichlorobutyl groups are included.

The unit of each of the formulae (I)-(III) may be of a block or random structure.

The ratios of the units (I)-(III) with organic substituents in the silicon polymer taken into account are: unit (II).noteq.0 if unit (I)=0; unit (I).noteq.0 if unit (II)=0; unit (II)/unit (I) if unit (I).noteq.0 is 0-1,000, preferably less than 1,000 above 0, more preferably 0.01-100; unit (III)/unit (I) if unit (I).noteq.0 is 0-1,000, preferably less than 1,000 above 0, more preferably 0.01-100; unit (III)/unit (II) if unit (I).noteq.0 and unit (II).noteq.0 is 0-1,000, preferably less than 1,000 above 0, more preferably 0.1-100; and the ratio of each of unit (I)/unit (II) and unit (III)/unit (II) if unit (II).noteq.0 is 0-1,000, preferably less than 1,000 above 0, more preferably 0.1-100.

The silicon polymer is normally liquid or solid, and its polymerization degree is greater than 2, preferably in the range of 6-2,000, and its molecular weight is usually in the range of 100-ten million, preferably 100-one million by weight average (Mw), and usually in the range of 100-one million, preferably 300-500,000 by number average (Wn).

The silicon polymer used in the invention may be prepared by any known suitable methods; for example, by the Kipping method in which monomers of halogenosilanes are subjected to Wurtz condensation reaction in an inert solvent and with use of an alkali metal; by the dehydrogenative condensation in which monomers of hydrosilanes are subjected to condensation in the presence of a transition metal catalyst; and by electrolytic polymerization in which monomers of halogenosilanes or hydrosilanes are subjected to condensation by electrolytic reduction.

A preferred process for the production of the silicon polymer used in the invention is the dehydrogenative condensation of one or more hydrosilanes of the formulae ##STR3## wherein R.sup.1 and R.sup.2 are identical or different, including hydrogen, C.sub.1 -C.sub.12 alkyl, cycloalkyl and halogenated alkyl groups, C.sub.7 -C.sub.12 aralkyl and halogenated aralkyl groups, C.sub.6 -C.sub.12 aryl groups and silyl groups of the formula (VII) hereinafter shown; ##STR4## wherein R.sup.6 and R.sup.10 each are identical or different, including hydrogen, C.sub.1 -C.sub.12 alkyl, cycloalkyl and halogenated alkyl groups, C.sub.7 -C.sub.12 aralkyl and halogenated aralkyl groups and C.sub.6 -C.sub.12 aryl groups, and either one of R.sup.6 -R.sup.10 is invariably hydrogen; and ##STR5## wherein R.sup.11 and R.sup.17 each are identical or different, including hydrogen, C.sub.1 -C.sub.12 alkyl, cycloalkyl and halogenated alkyl groups, C.sub.7 -C.sub.12 aralkyl and halogenated aralkyl groups, C.sub.6 -C.sub.12 aryl groups and silyl groups of the formula (VIII) hereinafter shown.

The above condensation reaction is carried out in the presence of a catalyst chosen from the group consisting of:

(a) at least one metal or metallic compound of Groups 3B-7B and 8 in the Periodic Table,

(b) a mixture of the above metal or metallic compound (a) and a silyl compound of the formula (VIII) and

(c) a mixture of a above and a metal hydride of the formula (IX) given below.

The resulting condensates are subjected to thermal decomposition.

The silyl group referred to in formula (IV) above is represented by the formula

R.sup.3 R.sup.4 R.sup.5 Si- (VII)

wherein R.sup.3 -R.sup.5 each are identical or different, including C.sub.1 -C.sub.8 alkyl groups and C.sub.6 -C.sub.10 aryl groups.

The silyl group referred to in formula (VI) above is represented by the formula

R.sup.18 R.sup.19 R.sup.20 SiA (VIII)

wherein R.sup.18 -R.sup.20 each are identical or different, including C.sub.1 -C.sub.12 alkyl groups, C.sub.7 -C.sub.12 aralkyl groups, C.sub.6 -C.sub.12 aryl groups and silyl groups of formula (VII), and A is lithium, sodium, or potassium.

The metal hydride referred to above as a catalyst component is represented by the formula

A'Xn (IX)

wherein A' is lithium, sodium, potassium, calcium, aluminum, R.sup.21.sub.(4-n), boron, R.sup.21.sub.(3-n) B, LiB, LiBR.sup.22, NaB, KB or R.sup.23 B where R.sup.21 is a C.sub.1 -C.sub.5 alkyl group, R.sup.22 is a C.sub.1 -C.sub.8 alkyl or alkoxy group and R.sup.23 is hydrogen or a tertiary ammonium having a C.sub.1 -C.sub.4 alkyl group; X is hydrogen or heavy hydrogen; and n is an integer of 1-4, and where n is 1-3, R.sup.21, R.sup.22 and R.sup.23 each may be different.

Turning back to the hydromonosilane of formula (IV), R.sup.1 and R.sup.2 each more specifically are hydrogen, a C.sub.1 -C.sub.12, preferably C.sub.1 -C.sub.8 alkyl group, a C.sub.3 -C.sub.12, preferably C.sub.5 -C.sub.6 cycloalkyl group, and a C.sub.1 -C.sub.12, preferably C.sub.1 -C.sub.8 halogenated alkyl group in which halogen is fluorine, chlorine, bromine, or iodine, fluorine being particularly preferred. The number of halogen substitution in the alkyl group is 1-12, preferably 1-6 of which 3,3,3-trifluoropropyl group is particularly preferred. Specific examples of the hydromonosilane include silane, methylsilane, ethylsilane, n-propylsilane, (3,3,3-trifluoropropyl)silane, n-butylsilane, t-butylsilane, (1-methylpropyl)silane, (2-methylpropyl)silane, n-hexylsilane, cyclohexylsilane, n-heptylsilane, n-octylsilane, n-nonylsilane, n-decylsilane, n-dodecylsilane, phenylsilane, p-tolylsilane, methylsilane, benzylsilane, phenethylsilane, (trimethylsilylmethyl)silane, dimethylsilane, diethylsilane, di-n-propylsilane, di-n-butylsilane, di-n-hexylsilane, di-n-octylsilane, diphenylsilane, dibenzylsilane, diphenethylsilane, methylphenylsilane, p-tolylmethylsilane, benzylmethylsilane, methylphenethylsilane or the like. Further examples include hydromonosilane monomers such as bis(3,3,3-trifluoropropyl)silane, di-n-butylsilane, di-t-butylsilane, di(1-methylpropyl)silane, di(2-methylpropyl)silane, dipentylsilane, dicyclohexylsilane, di-n-heptylsilane, di-n-nonylsilane, di-n-decylsilane, di-n-dodecylsilane, di-p-tolylsilane, dimethylsilane, 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, methylmesitylsilane, (p-methylphenetyl)silane, ethylphenylsilane and t-butylphenylsilane.

The hydrodisilane identified by formula (V) is preferably chosen from the group consisting of disilane, methyldisilane, ethyldisilane, n-propyldisilane, (3,3,3-trifluoropropyl)disilane, n-butyldisilane, t-butyldisilane, (1-methylpropyl)disilane, (2-methylpropyl)disilane, pentyldisilane, n-hexyldisilane, cyclohexyldisilane, n-heptyldisilane, n-octyldisilane, n-nonyldisilane, n-decyldisilane, n-dodecyldisilane, phenyldisilane, p-tolyldisilane, mesityldisilane, methyl(trimethylsilylmethyl)disilane, benzyldisilane, phenethyldisilane, 1,1-dimethyldisilane, 1,1-diethyldisilane, 1,1-di-n-propyldisilane, 1,1-di-n-butyldisilane, 1,1-di-n-amyldisilane, 1,1-di-n-hexyldisilane, 1,1-dicyclohexyldisilane, 1,1-diphenyldisilane, 1,1-dimesityldisilane, 1,2-dimethyldisilane, 1,2-dimethyldisilane, 1,2-di-n-propyldisilane, 1,2-di-n-butyldisilane, 1,2-di-n-amyldisilane, 1,2-di-n-hexyldisilane, 1,2-dicyclohexyldisilane, 1,2-diphenyldisilane, 1,2-dimesityldisilane or the like, and further includes 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-(.beta.-phenethyl)disilane, 1-p-tolyl-1-methyldisilane, 1-phenyl-1-ethyldisilane, 1-t-butyl-1-phenyldisilane, 1-ethyl-2-methyldisilane, 1-methyl-2-n-propyldisilane, 1-methyl-2-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-(.beta.-phenethyl)disilane, 1-p-tolyl-2-methyldisilane, 1-phenyl-2-ethyldisilane, 1-t-butyl-2-phenyldisilane, 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, 1,1,2-tri-n-amyldisilane, 1,1,2-tri-n-hexyldisilane, 1,1,2-tricyclohexyldisilane, 1,1,2-triphenyldisilane, 1,1,2-trimethyldisilane, 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-(.beta.-phenethyl)disilane, 1,1-di-p-tolyl-2-methyldisilane, 1,1-diphenyl-2-ethyldisilane, 1,1-di-t-butyl-2-phenyldisilane, 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(.beta.-phenethyl)disilane, 1-p-tolyl-2,2-dimethyldisilane, 1-phenyl-2,2-diethyldisilane, 1-t-butyl-2,2-diphenyldisilane, 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-tetramethyldisilane, 1,1,2,2-tetramethyldisilane, 1,1,2,2-tetra-npropyldisilane, 1,1,2,2-tetra-n-butyldisilane, 1,1,2,2-tetra-namyldisilane, 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-methyldisilane, 1,1,1-tri-n-hexyl-2-methyldisilane, 1,1,1-tricyclohexyl-2-methyldisilane, 1,1,1-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-(.beta.-phenethyl)disilane, 1,1,1-tri-p-tolyl-2-methyldisilane, 1,1,1-triphenyl-2-ethyldisilane, 1,1,1-tri-t-butyl-phenyldisilane, 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(.beta.-phenethyl)disilane, 1-p-tolyl-2,2,2-trimethyldisilane, 1-phenyl-2,2,2-triethyldisilane, 1-t-butyl-2,2,2-triphenyldisilane, 1,1-diethyl-2,2-dimethyldisilane, 1,1-dimethyl-2,2-di-n-propyldisilane, 1,1-dimethyl-2,2-di-i-propyldisilane, 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-din-decyl-2,2-dimethyldisilane, 1,1-dimethyl-2,2-diphenyldisilane, 1,1-di-(p-methylphenethyl)-2,2-dimethyldisilane, 1,1-dimethyl-2,2-di(.beta.-phenethyl)disilane, 1,1-di-p-tolyl-2,2-dimethyldisilane, 1,1-didiphenyl-2,2-diethyldisilane, 1,1-di-t-butyl-2,2-diphenyldisilane, 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-din-decyl-1,2-dimethyldisilane, 1,2-dimethyl-1,2-diphenyldisilane, 1,2-di-(p-methylphenethyl)-1,2-dimethyldisilane, 1,2-dimethyl-1,2-di(.beta.-phenethyl)disilane, 1,2-di-p-tolyl-1,2-dimethyldisilane, 1,2-didiphenyl-1,2-diethyldisilane, 1,2-di-t-butyl-1,2-diphenyldisilane or the like.

The hydrotrisilane used in the invention is identified by formula (VI) above wherein R.sup.11 and R.sup.17 each are a C.sub.1 -C.sub.12, preferably C.sub.1 -C.sub.8 alkyl group, a C.sub.3 -C.sub.12, preferably C.sub.5 -C.sub.6 cycloalkyl group such as cyclopentyl and cyclohexyl, a C.sub.1 -C.sub.12, preferably C.sub.1 -C.sub.8 hydrogenated alkyl group containing, as halogen, fluorine, chlorine, bromine, and iodine, of which fluorine is particularly preferred. The number of halogen substitution in the alkyl group is 1-12, preferably 1-6, preferably such as 3,3,3-trifluoropropyl group.

The hydrotrisilane used in the invention is identified by formula (VI) above wherein R.sup.11 and R.sup.17 each are a C.sub.1 -C.sub.12, preferably C.sub.1 -C.sub.8 alkyl group, a C.sub.3 -C.sub.12, preferably C.sub.5 -C.sub.6 cycloalkyl group such as cyclopentyl and cyclohexyl, a C.sub.1 -C.sub.12, preferably C.sub.1 -C.sub.8 hydrogenated alkyl group containing, as halogen, fluorine, chlorine, bromine, and iodine, of which fluorine is particularly preferred. The number of halogen substitution in the alkyl group is 1-12, preferably 1-6, preferably such as 3,3,3-trifluoropropyl group.

The formula (VI) monomers preferably include trisilane, 1-methyltrisilane, 1-ethyltrisilane, 1-1-n-propyltrisilane, 1-(3,3,3-trifluoropropyl)trisilane, 1-n-butyltrisilane, 1-t-butyltrisilane, 1-(1-methylpropyl)trisilane, 1-(2-methylpropyl)trisilane, 1-amyltrisilane, 1-n-hexyltrisilane, 1-cyclohexyltrisilane, 1-n-heptyltrisilane, 1-n-octyltrisilane, 1-n-nonyltrisilane, 1-n-decyltrisilane, 1-n-dodecyltrisilane, 1-phenyltrisilane, 1-p-tolyltrisilane, 1-mesityltrisilane, 1-benzyltrisilane, 1-phenethyltrisilane, 1-(trimethylsilylmethyl)trisilane, 2-methyltrisilane, 2-ethyltrisilane, 2-n-propyltrisilane, 2-(3,3,3-trifluoropropyl)trisilane, 2-n-butyltrisilane, 2-t-butyltrisilane, 2-(1-methylpropyl)trisilane, 2-(2-methylpropyl)trisilane, 2-amyltrisilane, 2-n-hexyltrisilane, 2-cyclohexyltrisilane, 2-n-heptyltrisilane, 2-n-octyltrisilane, 2-n-nonyltrisilane, 2-n-decyltrisilane, 2-n-dodecyltrisilane, 2-phenyltrisilane, 2-p-tolyltrisilane, 2-mesityltrisilane, 2-benzyltrisilane, 2-phenethyltrisilane, 2-(trimethylsilylmethyl)trisilane, 1,1-dimethyltrisilane, 1,1-diethyltrisilane, 1,1-di-n-propyltrisilane, bis(3,3,3-trifluoropropyl)trisilane, 1,1-di-n-butyltrisilane, 1,1-di-t-butyltrisilane, di(1-methylpropyl)trisilane, di(2-methylpropyl)trisilane, 1,1-diamyltrisilane, 1,1-di-n-hexyltrisilane, 1,1-dicyclohexyltrisilane, 1,1-di-n-heptyltrisilane, 1,1-di-n-octyltrisilane, 1,1-di-n-nonyltrisilane, 1,1-di-n-decyltrisilane, 1,1-di-n-dodecyltrisilane, 1,1-diphenyltrisilane, 1,1-di-p-tolyltrisilane, 1,1-dimesityltrisilane, 1,1-dibenzyltrisilane, 1,1-diphenethyltrisilane, 1,1-bis(trimethylsilylmethyl)trisilane, 1,2-dimethyltrisilane, 1,2-diethyltrisilane, 1,2-di-n-propyltrisilane, bis(3,3,3-trifluoropropyl)trisilane, 1,2-di-n-butyltrisilane, 1,2-di-t-butyltrisilane, di(1-methylpropyl)trisilane, di(2-methylpropyl)trisilane, 1,2-diamyltrisilane, 1,2-di-n-hexyltrisilane, 1,2-dicyclohexyltrisilane, 1,2-di-n-heptyltrisilane, 1,2-di-n-octyltrisilane, 1,2-di-n-nonyltrisilane, 1,2-di-n-decyltrisilane, 1,2-di-n-dodecyltrisilane, 1,2-diphenyltrisilane, 1,2-di-p-tolyltrisilane, 1,2-dimesityltrisilane, 1,2-dibenzyltrisilane, 1,2-diphenethyltrisilane, 1,2-bis(trimethylsilylmethyl)trisilane, 1,3-dimethyltrisilane, 1,3-diethyltrisilane, 1,3-di-n-propyltrisilane, bis(3,3,3-trifluoropropyl)trisilane, 1,3-di-n-butyltrisilane, 1,1-di-t-butyltrisilane, di(1-methylpropyl)trisilane, di(2-methylpropyl)trisilane, 1,3-diamyltrisilane, 1,3-di-n-hexyltrisilane, 1,3-dicyclohexyltrisilane, 1,3-di-n-heptyltrisilane, 1,3-di-n-octyltrisilane, 1,3-di-n-nonyltrisilane, 1,3-di-n-decyltrisilane, 1,3-di-n-dodecyltrisilane, 1,3-diphenyltrisilane, 1,3-di-p-tolyltrisilane, 1,3-dimesityltrisilane, 1,3-dibenzyltrisilane, 1,3-diphenethyltrisilane, 1,3-bis(trimethylsilylmethyl)trisilane, 1,1,1-trimethyltrisilane, 1,1,1-triethyltrisilane, 1,1,1-tri-n-propyltrisilane, 1,1,1-tris(3,3,3-trifluoropropyl)trisilane, 1,1,1-tri-n-butyltrisilane, 1,1,1-tri(1-methylpropyl)trisilane, 1,1,1-tri(2-metylpropyl)trisilane, 1,1,1-tri-n-amyltrisilane, 1,1,1-tri-n-hexyltrisilane, 1,1,1-tricyclohexyltrisilane, 1,1,1-tri-n-heptyltrisilane, 1,1,1-tri-n-octyltrisilane, 1,1,1-tri-n-nonyltrisilane, 1,1,1-tri-n-decyltrisilane, 1,1,1-tri-n-dodecyltrisilane, 1,1,1-triphenyltrisilane, 1,1,1-tri-p-tolyltrisilane, 1,1,1-trimesityltrisilane, 1,1,1-tribenzyltrisilane, 1,1,1-triphenethyltrisilane, 1,1,1-tris(trimethylsilylmethyl)trisilane, 1-ethyl-1,1-dimethyltrisilane, 1-methyl-1,1-di-n-propyltrisilane, 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-dimethyltrisilane, 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-dimethyltrisilane, 1-n-heptyl-1,1-dimethyltrisilane, 1-methyl-1,1-di-n-octyltrisilane, 1-methyl-1,1-di-n-nonyltrisilane, 1-n-decyl-1,1-dimethyltrisilane, 1-n-dodecyl-1,1-dimethyltrisilane, 1-methyl-1,1-diphenyltrisilane, 1-p-tolyl-1,1-dimethyltrisilane, 1-methyl-1,1-dimesityltrisilane, 1-benzyl-1,1-dimethyltrisilane, 1-methyl-1,1-diphenethyltrisilane, 1-methyl-1,1-bis(trimethylsilylmethyl)trisilane, 1-(p-methylphenethyl)-1,1-dimethyltrisilane, 1-ethyl-1,1-diphenyltrisilane, 1-t-butyl-1,1-diphenyltrisilane or the like, and further exemplarily include 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-mesityl-1-methyltrisilane, 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-melthyltrisilane, 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, 1,1,2-trimethyltrisilane, 1,1,2-triethyltrisilane, 1,1,2-tri-n-propyltrisilane, 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-trimesityltrisilane, 1,1,2-tribenzyltrisilane, 1,1,2-triphenethyltrisilane, 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-trimesityltrisilane, 1,2,3-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-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-(.beta.-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, 1,1-diethyl-3-methyltrisilane, 1,1-dimethyl-3-n-propyltrisilane, 1,1-dimethyl-3-i-propyltrisilane, 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-(.beta.-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-methyltrisilane, 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-(.beta.-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, (trimethylsilyl)methyldisilane, 1-(phenyldimethylsilyl)-1-methyldisilane, 1-(trimethylsilyl)-1-methyldisilane, 1-(phenyldimethylsilyl)-2-methyldisilane, 1-(trimethylsilyl)-2-methyldisilane, 1-bis(phenyldimethylsilyl)-2-methyldisilane, 1-bis(trimethylsilyl)-2-methyldisilane, 1-(phenyldimethylsilyl)-2,2-dimethyldisilane, 1-(trimethylsilyl)-2,2-dimethyldisilane, 1,1,1-tri(phenyldimethylsilyl)-2-methyldisilane, 1,1,1-tri(trimethylsilyl)-2-methyldisilane, 1-(phenyldimethylsilyl)-2,2,2-methyldisilane, 1-(trimethylsilyl)-2,2,2-methyldisilane, 1,1-bis(phenyldimethylsilyl)-2,2-methyldisilane, 1,1-bis(trimethylsilyl)-2,2-methyldisilane, 1,2-bis(phenyldimethylsilyl)-1,2-methyldisilane, 1,2-bis(trimethylsilyl)-1,2-methyldisilane or the like.

The above silane monomers of formulae (IV), (V) and (VI) may be used singly or in any combination.

Turning back to each to the catalysts (a)-(c) referred to above for use in the dehydrogenative condensation of the starting silane monomers, the metal of Group 3B of the Periodic Table includes samarium, europium, and ytterbium; the metal of Group 4B includes titanium, zirconium, and hafnium; the metal of Group 5B includes vanadium, niobium, and tantalum; the metal of Group 6B includes chromium, molybdenum, and tungsten; the metal of Group 7B includes manganese, technetium, and rhenium; the metal of Group 8B includes iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Compounds of these metals may be also used.

Eligible metallic compounds of the Group 4B metal are halogen compounds, acetylacetonate, alkoxy compounds, aryloxy compounds, alkoxyhalogen compounds, aryloxyhalogen compounds and such compounds which have conjugated .pi.-bond substituents such as cyclopentadienyl, alkylcyclopentadienyl, indenyl and like substituted cyclopentadienyl groups.

Examples of titanium compounds include (.eta.-cycloheptatrienyl)(.eta.-cyclopentadienyl)titanium, titanium hydride, dicarbonylbis(.eta.-cyclopentadienyl)titanium, bis(.eta.-pentamethylcyclopentadienyl)titanium, titanium trichloride, chlorobis(.eta.-cyclopentadienyl)titanium, dichloro(.eta.-cyclopentadienyl)titanium, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, trichloromethyltitanium, methyltriisopropoxytitanium, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, dihydridebis(.eta.-pentamethylcyclopentadiethyl)titanium, trichloro(.eta.-cyclopentadienyl)titanium, dichlorobis (.eta.-cyclopentadienyl)titanium, dichlorobis (.eta.-methylcyclopentadienyl)titanium, dichlorobis (.eta.-dimethylcyclopentadienyl)titanium, dichlorobis (.eta.-trimethylcyclopentadienyl)titanium, dichlorobis (.eta.-pentamethylcyclopentadienyl)titanium, dichlorobis (.eta.-trifluoromethylcyclopentadienyl)titanium, dichlorobis(.eta.-trimethylsilylcyclopentadienyl)titanium, dichloro(.eta.-pentamethylcyclopentadienyl)(.eta.-cyclopentadienyl)titaniu m, dichloro(.eta.-trifluoromethylcyclopentadienyl)(.eta.-cyclopentadienyl)tit anium, dichloromethylenebis(.eta.-cyclopentadienyl)titanium, dichloroethylenebis(.eta.-cyclopentadienyl)titanium, dichloropropylenebis(.eta.-cyclopentadienyl)titanium, dichlorodimethylsilylenebis(.eta.-cyclopentadienyl)titanium, dichlorobis(.eta.-indenyl)titanium, dichlorobis(.eta.-methylindenyl)titanium, dichlorobis(.eta.-dimethylindenyl)titanium, dichlorobis(.eta.-trimethylsilylindeyl)titanium, dichloromethylenebis(.eta.-indenyl)titanium, dichloroethylenebis(.eta.-indenyl)titanium, dichloropropylenebis(.eta.-indenyl)titanium, dimethylbis(.eta.-cyclopentadienyl)titanium, dimethylbis (.eta.-methylcyclopentadienyl) titanium, dimethylbis (.eta.-pentamethylcyclopentadienyl) titanium, dimethylbis (.eta.-trimethylsilylcyclopentadienyl) titanium, dimethylbis (.eta.-indenyl) titanium, diphenylbis(.eta.-cyclopentadienyl)titanium, diphenylbis(.eta.-methylcyclopentadienyl)titanium, dibenzylbis(.eta.-cyclopentadienyl)titanium, bis(trimethylsilylmethyl)bis(.eta.-cyclopentadienyl)titanium, dimethoxybis(.eta.-cyclopentadienyl)titanium, diethoxybis(.eta.-cyclopentadienyl)titanium, dibutoxybis(.eta.-cyclopentadienyl)titanium and diphenoxibis(.eta.-cyclopentadienyl)titanium.

Examples of zirconium compounds include bis(.eta.-cyclooctatetraene)zirconium, zirconium hydroxide, bis(.eta.-cyclopentadienyl)(.eta.-1,3-butadiene)zirconium, dicarbonylbis(.eta.-cyclopentadienyl)zirconium, chlorobis(.eta.-cyclopentadienyl)zirconium, benzylbis(.eta.-cyclopentadienyl)zirconium, trimethylsilylmethylbis(.eta.-cyclopentadienyl)zirconium, zirconium tetrachloride, zirconium acetylacetonato, zirconiumtetraethoxide, zirconiumtetrabutoxide, tetraallylzirconium, trichloro(.eta.-pentamethylcyclopentadienyl)zirconium, tribromo(.eta.-cyclopentadienyl)zirconium, bis(.eta.-cyclopentadienyl)dihydride zirconium, chlorobis(.eta.-cyclopentadienyl)hydride zirconium, bis(tetrahydroborate)bis(.eta.-cyclopentadienyl)zirconium, dichlorobis(.eta.-cyclopentadienyl)zirconium, dichlorobis(.eta.-methylcyclopentadienyl)zirconium, dichlorobis(.eta.-dimethylcyclopentadienyl)zirconium, dichlorobis(.eta.-trimethylcyclopentadienyl)zirconium, dichlorobis(.eta.-pentamethylcyclopentadienyl)zirconium, dichlorobis(.eta.-trifluoromethylcyclopentadienyl)zirconium, dichlorobis(.eta.-trimethylsilylcyclopentadienyl)zirconium, dichloro(.eta.-pentamethylcyclopentadienyl)(.eta.-cyclopentadienyl)zirconi um, dichloro(.eta.-trifluromethylcyclopentadienyl)(.eta.-cyclopentadienyl)zirc onium, dichloromethylenebis(.eta.-cyclopentadienyl)zirconium, dichloroethylenebis(.eta.-cyclopentadienyl)zirconium, dichloropropylenebis(.eta.-cyclopentadienyl)zirconium, dichlorodimethylsilylenebis(.eta.-cyclopentadienyl)zirconium, dichlorobis(.eta.-indenyl)zirconium, dichlorobis(.eta.-methylindenyl)zirconium, dichlorobis(.eta.-dimethylindenyl)zirconium, dichlorobis(.eta.-trimethylsilylindenyl)zirconium, dichloromethylenebis(.eta.-indenyl)zirconium, dichloroethylenebis(.eta.-indenyl)zirconium, dichloropropylenebis(.eta.-indenyl)zirconium, dimethylbis(.eta.-cyclopentadienyl)zirconium, dimethylbis(.eta.-pentamethylcyclopentadienyl)zirconium, dimethylbis(.eta.-indenyl)zirconium, diphenylbis(.eta.-cyclopentadienyl)zirconium, diphenylbis(.eta.-methylcyclopentadienyl)zirconium, dibenzylbis(.eta.-cyclopentadienyl)zirconium, bis(trimethylsilylmethyl)bis(.eta.-cyclopentadienyl)zirconium, dimethoxybis(.eta.-cyclopentadienyl)zirconium, diethoxybis(.eta.-cyclopentadienyl)zirconium, dibutoxybis(.eta.-cyclopentadienyl)zirconium and diphenoxybis(.eta.-cyclopentadienyl)zirconium.

Examples of hafnium compounds include bis(.eta.butadiene)[1,2-bis(dimethylphosphino)ethane]hafnium, dicarbonylbis(.eta.-cyclopentadienyl)hafnium, trimethylsilylmethylbis(.eta.-isopropylcyclopentadienyl)hafnium, tetrabenzylhafnium, trichloro(.eta.-cyclopentadienyl)hafnium, chlorobis(.eta.-cyclopentadienyl)hydride hafnium, dihydridobis(.eta.-cyclopentadienyl)hafnium, bis(tetrahydroborate)bis(.eta.-methylcyclopentadienyl)hafnium, dichlorobis(.eta.-cyclopentadienyl)hafnium, dichlorobis(.eta.-methylcyclopentadienyl)hafnium, dichlorobis(.eta.-dimethylcyclopentadienyl)hafnium, dichlorobis(.eta.-trimethylcyclopentadienyl)hafnium, dichloro(.eta.-pentamethylcyclopentadienyl)(.eta.-cyclopentadienyl)hafnium , dichloro(.eta.-trifluoromethylcyclopentadienyl)(.eta.-cyclopentadienyl)ha fnium, dichlomethylenebis(.eta.-cyclopentadienyl)hafnium, dichloroethylenebis(.eta.-cyclopentadienyl)hafnium, dichlopropylenebis(.eta.-cyclopentadienyl)hafnium, dichlorodimethylsilylenebis(.eta.-cyclopentadienyl)hafnium, dichlorobis(.eta.-indenyl)hafnium, dichlorobis(.eta.-methylindenyl)hafnium, dichlorobis(.eta.-dimethylindenyl )hafnium, dichlorobis(.eta.-trimethylindenyl)hafnium, dichloromethylenebis(.eta.-indenyl)hafnium, dichloroethylenebis(.eta.-indenyl)hafnium, dichloropropylenebis(.eta.-indenyl)hafnium, dimethylbis(.eta.-cyclopentadienyl)hafnium, dimethylbis(.eta.-pentamethylcyclopentadienyl)hafnium, dimethylbis(.eta.-indenyl)hafnium, diphenylbis(.eta.-cyclopentadienyl)hafnium, diphenylbis(.eta.-methylcyclopentadienyl)hafnium, dibenzylbis(.eta.-cyclopentadienyl)hafnium, bis(trimethylsilylmethyl)bis(.eta.-cyclopentadienyl)hafnium, dimethoxybis(.eta.-cyclopentadienyl)hafnium, diethoxybis(.eta.-cyclopentadienyl)hafnium, dibutoxybis(.eta.-cyclopentadienyl)hafnium and diphenoxybis(.eta.-cyclopentadienyl)hafnium.

Examples of cobalt compounds include halogen compounds, acetate, sulfur-containing organic compounds, carbonyl compounds, phosphorus-containing organic compounds, and such compounds which have conjugated .pi.-bond substituents such as cyclopentadienyl, alkylcyclopentadienyl, indenyl and like substituted cyclopentadienyl groups. Such cobalt compounds exemplarily include hexacarbonylbis(tributylphosphine)dicobalt, hexacarbonyl-.mu.-(diphenylacetylene)dicobalt, tetracarbonylbis(.mu.-butadiene)dicobalt, dodecarbonyltetracobalt, hydridotetracarbonylcobalt, tetracarbonyl(trimethylsilyl)cobalt, (.eta.-allyl)tricarbonylcobalt, hydrido(dinitrogen)tris(triphenylphosphine)cobalt, tetrakis(trimethylphosphine)methylcobalt, dicarbonyl(.eta.-cyclopentadienyl)cobalt, bis[(.mu.-carbonyl)(.eta.-cyclopentadienyl)cobalt], tris[(.mu.-carbonyl)(.eta.-cyclopentadienyl)cobalt], dicarbonyl(.eta.-pentamethylcyclopentadienyl)cobalt, bis(trimethylphosphido)(.eta.-cyclopentadienyl)cobalt, chlorotris(triphenylphosphine)cobalt, (.eta.-cyclopentadienyl)bis(triphenylphosphine)cobalt, (.eta.-cyclopentadienyl)bis(.eta.-ethylene)cobalt, (.eta.-cyclopentadienyl)(.eta.-1,5-cyclooctadiene)cobalt, (.eta.-cyclopentadienyl)(.eta.-cyclohexadiene)cobalt, cobalt acetate, cobalt(acetylacetonato), cobalt chloride, cobalt bromide, cobalt iodide, cobalt thiocyanate, bis(.eta.-cyclopentadienyl)cobalt, carbonyl(.eta.-cyclopentadienyl)diiodocobalt, (.eta.-cyclopentadienyl)(triphenylphosphine)diiodocobalt, bis(.eta.-cyclopentadienyl)cobalt tribromide, (.eta.-cyclopentadienyl)(.eta.-cyclohexadienyl)cobalt iodide and (.eta.-benzene)(.eta.-cyclopentadienyl)cobalt tetrafluoroborate.

Examples of nickel compounds are halogen compounds, acetate, nitrogen-containing organic compounds, sulfur-containing organic compounds, carbonyl compounds, phosphorus-containing compounds and such compounds which have conjugated .pi.-bond substituents such as cyclopentadienyl, alkylcyclopentadienyl, indenyl and like substituted cyclopentadienyl groups. Specific examples include tetracarbonylnickel, dicarbonylbis(triphenylphosphine)nickel, bis(1,5-cyclooctadiene)nickel, (.eta.-ethylene)bis(triphenylphosphine)nickel, tetrakis(triphenylphosphine)nickel, tetrakis(t-butyl isocyanide)nickel, .mu.-(dinitrogen)bis[bis(tricyclohexylphosphine)nickel], nickelacetate, nickel(acetylacetonato), nickel chloride, nickel bromide, dichloro[1,2-bis(diphenylphosphino)ethane]nickel, trans-bis(1,3-butadiynyl)bis(tributylphosphine)nickel, dimethylbis(trimethylphosphine)nickel, diethyl(2,2'-bipyridyl)nickel, trans-bromo(phenyl)bis(triethylphosphine)nickel, tetramethylenebis(triphenylphosphine)nickel, trans-chloro(hydride)bis(tricyclohexylphosphine)nickel, bis(.eta.-cyclopentadienyl)nickel, chloro(.eta.-cyclopentadienyl)(triphenylphosphine)nickel, methyl(.eta.-cyclopentadienyl)(triphenylphosphine)nickel, (.eta.-allyl)(.eta.-cyclopentadienyl)nickel, (.eta.-1,5-cyclooctadiene)(.eta.-cyclopentadienyl)nickeltetrafluoro borate, bis(.eta.-allyl)nickel, (.eta.-allyl)bromo(triphenylphosphine)nickel, and bis(.eta.-cyclopentadienyl)di(.mu.-carbonyl)dinickel.

Examples of ruthenium compounds include ruthenium carbon, ruthenium alumina, dodecacarbonyltri ruthenium, tetra-.mu.-hydridedodecacarbonyltetraruthenium, tetracarbonyl(trimethylphosphido)ruthenium, pentakis(trimethylphosphido)ruthenium, tricarbonyl(cyclooctatetraene)ruthenium, tricarbonyl(1,5-cyclooctadiene)ruthenium, tetracarbonylbis(.eta.-cyclopentadienyl)diruthenium, tetracarbonylbis(.eta.-pentamethylcyclopnetadienyl)diruthenium, dicarbonyltris(triphenylphosphine)ruthenium, diacetatodicarbonylbis(triphenylphosphine)ruthenium, di-.mu.-chlorobis(chlorotricarbonylruthenium), dichlorotris(triphenylphosphine)ruthenium, carbonylchlorohydridotris(triphenylphosphine)ruthenium, dihydridotetrakis(triphenylphosphine)ruthenium, trans-dichlorotetrakis(t- butyl isocyanide)ruthenium, bis(.eta.-cyclopentadienyl)ruthenium, chloro(.eta.-cyclopentadienyl)bis(triphenylphosphine)ruthenium, hydrido(.eta.-cyclopentadienyl)bis(triphenylphosphine)ruthenium, cyclopentadienyltris(trimethylphosphine)rutheniumhexafluorophosphate, chlorodicarbonyl(.eta.-cyclopentadienyl)ruthenium, hydrido(cyclopentadienyl)(1,5-cyclooctadiene)ruthenium, chloro(cyclopentadienyl)(1,5-cyclooctadiene)ruthenium, tricarbonyl(pentamethylcyclopentadienyl)rutheniumtetrafluoroborate, ruthenium(acetylacetonate), ruthenium chloride, dichloro(pentamethylcyclopentadienyl)ruthenium, dichloro(pentamethylcyclopentadienyl)(triphenylphosphine)ruthenium, tetrahydridotris(triphenylphosphine)ruthenium, trichloro(pentamethylcyclopentadienyl)ruthenium, trihydro(pentamethylcyclopentadienyl)(triphenylphosphine) ruthenium and dichloro(.eta.-allyl)(cyclopentadienyl)ruthenium.

Examples of rhodium compounds include rhodium carbon, rhodium alumina, rhodium silica, octacarbonyldirhodium, dodecacarbonyltetrarhodium, rhodium(dicarbonyl)(acetylacetonato), di-.mu.-chlorotetracarbonyldirhodium, hydridotetracarbonylrhodium, chlorotris(triphenylphosphine)rhodium, tetrakis(trimehtylphosphine)rohdium chloride, trans-[chlorocarbonylbis(tricyclohexylphosphine)rhodium], hydridotris(triisopropylphosphine)rhodium, hydridotetrakis(triphenylphosphine)rhodium, hydridotetrakis(triisopropylphosphido)dirhodium, di-.mu.-chloro-tetra(.eta.-ethylene)dirhodium, di-.mu.-chlorotetrakis(cyclooctene)dirhodium, di-.mu.-chlorobis(cyclooctadiene)dirhodium, di-.mu.-chloro-bis(.mu.-tetraphenylcyclobutadiene)dirhodium, 2,4-pentandionatobis(ethylene)rhodium, bis(cycloocta-1,5-diene)rhodium, 1,5-cyclooctadienebis(acetonitrile)rhodiumtetrafluoro borate, diammine cyclooctadienerhodiumhexafluorophosphate, rhodium acetate, rhodium(acetylacetonate), rhodium chloride, rhodium bromide, di-.mu.-chlorodichlorobis(pentamethylcyclopentadienyl)dirhodium, di-.mu.-carbonyl-bis(pentamethylcyclopentadienyl)dirhodium, tris(acetonitrile)pentamethlcycclopentadienylrhodiumdihexafluorophosphate, (1,4-butandiel)(.eta.-pentamethylcyclopentadienyl)(triphenylphosphine)rhod ium, di-.mu.-chloro-tetralkis(.eta.-allyl)dirhodium, tris(.eta.-allyl)rhodium, hydridooctaethylporphyrinatorhodium, dimethyl-di-.mu.-methylenebis(pentamethylecyclopentadienyl)dirhodium and dihydridobis(triethylsilyl)pentamethylcyclopentadienylrhodium.

Examples of palladium compounds include palladium carbon, palladium alumina, tetrakis(triphenylphosphine)palladium, bis(tricyclohexylphosphine)palladium, tetrakis(triethylphosphido)palladium, carbonyltris(triphenylphosphine)pall adium, (.eta.-ethylene)bis(triphenylphosphine)palladium, bis(cycloocta-1,5-diene)palladium, tris(dibenzylideneacetone)dipalladium, dichloro-.mu.-bis[bis(diphenylphosphino)methane]dipalladium, palladium acetate, palladium(acetylacetonato),palladium chloride, palladium iodide, dichlorobis(benzonitrile)palladium, dichloro(1,5-cyclooctadiene)palladium, dichlorobis(triphenylphosphine)palladium, di-.mu.-chloro-dichlorobis(isocyanido)dipalladium, di-.mu.-chloro-dichlobis(tripehnylphosphine)dipalladium, trans-[bis(t-butylisocyanide)dichloropalladium], chloromethyl(1,5-cyclooctadiene)palladium, dimethylbis(triethylphosphine)palladium, trans-[bromo(methyl)bis(triethylphosphine)palladium], trans-chloro(phenylethynyl)bis(tributylphosphine)palladium, cyclopentadienyl(phenyl)(triethylphosphine)palladium, .eta.-allyl(pentamethylcyclopentadienyl)palladium, .eta.-allyl(1,5-cyclooctadiene)palladiumtetrafluoroborate and di-.mu.-chlorobis(.eta.-allyl)dipalladium.

Examples of iridium compounds include dodecacarbonyltetrairidium, hexacarbonylhexairidium, di-.mu.-chlorotetrakis(cyclooctene)diiridium, di-.mu.-chlorotetrakis(ethylene)diiridium, di-.mu.-chlorobis(1,5-cyclooctadiene)diiridium, chlorotris(triphenylphosphine)iridium, chlorocarbonylbis(triphenylphosphine)iridium, chloroethylenebis(triphenylphosphine)iridium, chloro(dinitrogen)bis(tripenylphosphine)iridium, (pentamethylcyclopentadienyl)dicarbonyliridium, pentamethylcyclopentadienylbis(ethylene)iridium, carbonylhydridetris(triphenylphosphine)iridium, chlorodicarbonyl(p-toluidine)iridium, carbonylmethylbis(triphenylphosphine)iridium, iridium(acetylacetonato), iridium chloride, tris(.eta.-allyl)iridium, di-.mu.-chlorodichlorobis(pentamethylcyclopentadienyl)diiridium, trichlorotris(triethylphosphine)iridium, dihydrido(pentamethylcyclopentadienyl)trimethylphosphineiridium and pentahydridebis(trimethylphosphine)iridium.

Examples of platinum compounds include platinum carbon, platinum alumina, bis(dibenzilidene acetone)platinum, tris(ethylene)platinum, tetrakis(triphenylphosphine)platinum, tris(triphenylphosphine)platinum, tetrakis(triphenylphosphido)platinum, carbonyltris(tripehnylphosphine)platinum, bis(triphenylphosphine)(diphenylacetylene)platinum, bis(triphenylphosphine)(trans-stilbene)platinum, bis[carbonyl(pentamethylcyclopentadienyl)platinum], .mu.-[bis-(diphenylphosphino)methane]-bis(chloroplatinum), platinum(acetylacetonato), platinum dichloride, platinum dibromide, cis-bis(benzonitryl)dichloroplatinum, cis-dichlorobis(acetonitryl)platinum, trans-dichlorobis(acetonitryl)platin um, dichloro(.eta.-1,5-cyclooctadiene)platinum, cis-dichlorobis(tributylphosphine)platinum, trans-dichlorobis(tributylphosphine)platinum, cis-[dichloro(phenylisocyanide)(triphenylphosphine)platinum], cis-[dichloro(diaminocarbene)(triethylphosphine)platinum], trichloro(.eta.-ethylene)potassium platinate, di-.mu.-chloro-dichloro(ethylene)diplatinum, bis(1,5-cyclooctadiene)platinum, trans-hydridechlorobis(triethylphosphine)platinum, dimethyl(1,5-cyclooctadiene)platinum, trans-[iodo(methyl)bis(triethylphosphine)platinum], cis-[chloro(methyl)bis(dimethylphenylphosphine)platinum]dibutylbis(triphen ylphosphine)platinum and platinum tetrachloride.

The above listed metals and their compounds may be used in combination.

The silyl compound used as the catalyst in the dehydrogenative condensation of a starting monomer includes phenyldimethylsilyllithium, diphenylmethylsilyllithium, t-butyldiphenylsilyllithium, triphenylsilyllithium, tris(trimethylsilyl)silyllithium, trimethylsilylsodium, triethylsilylsodium, tri-n-propylsilylsodium, tri-i-propylsilylsodium, tri-n-butylsilylsodium, tri-n-hexylsilylsodium, triphenylsilylsodium, ethyldimethylsilylsodium, n-propyldimethylsilylsodium, i-propyldimethylsilylsodium, n-butyldimethylsilylsodium, t-butyldimethylsilylsodium, n-hexyldimethlsilylsodium, cyclohexyldimethylsilylsodium, n-octyldimethylsilylsodium, n-decyldimethylsilylsodium, phenyldimethylsilylsodium, benzyldimethylsilylsodium, phenethyldimethylsilylsodium, di-n-butylmethlsilylsodium, diphenylmethylsilylsodium, t-butyldiphenylsilylsodium, tris(trimethylsilyl)silisodium, trimethylsilylpotassium, triethylsilylpotassium, tri-n-propylsilylpotassium, tri-i-propylsilylpotassium, tri-n-butylsilylpotassium, tri-n-hexylsilylpotassium, triphenylsilylpotassium, ethyldimethylsilylpotassium, n-propyldimethylsilylpotassium, i-propyldimethylsilylpotassium, n-butyldimethylsilylpotassium, t-butyldimethylsilylpotassium, n-hexyldimethylsilylpotassium, cyclohexyldimethylsilylpotassium, n-octyldimethylsilylpotassium, n-decyldimethylsilylpotassium, phenyldimethylsilylpotassium, benzyldimthylsilylpotassium, phenethyldimethylsilylpotassium, di-n-butylmethylsilylpotassium, diphenylmethylsilylpotassium, t-butyldiphenylsilylpotassium and tris(trimethylsilyl)silylpotassium. Two or more of these silyl compounds may be combined. The silyl compounds may contain ligands such as ether and tetrahydrofuran.

The metal (heavy) hydride of formula (IX) exemplarily includes LiH, NaH, KH, CaH.sub.2, AlH.sub.3, MeAlH.sub.2, EtAlH.sub.2, i-PrAlH.sub.2, n-BuAlH.sub.2, i-BuAlH.sub.2, sec-BuAlH.sub.2, t-BuAlH.sub.2, Me.sub.2 AlH.sub.2, Et.sub.2 AlH, n-Pr.sub.2 AlH, i-Pr.sub.2 AlH, n-Bu.sub.2 AlH, i-Bu.sub.2 AlH, sec-Bu.sub.2 AlH, t-Bu.sub.2 AlH, LiAlH.sub.4, LiAl(Et).sub.2 H.sub.2, LiAl(n-Pr).sub.2 H.sub.2, LiAl(i-Pr).sub.2 H.sub.2, LiAl(n-Bu).sub.2 H.sub.2, LiAl(i-Bu).sub.2 H.sub.2, LiAl(sec-Bu).sub.2 H.sub.2, LiAl(t-Bu).sub.2 H.sub.2, LiAl(Et).sub.3 H, LiAl(n-Pr).sub.3 H, LiAl(i-Pr).sub.3 H, LiAl(n-Bu)2H, LiAl(i-Bu)3H, LiAl(sec-Bu)3H, LiAl(OMe)3H, LiAl(OEt).sub.3 H, LiAl(O-t-Bu).sub.3 H, NaAl(OCH.sub.2 CH.sub.2 -OMe).sub.3 H, BH.sub.3, [(CH.sub.3).sub.2 CHCH(CH.sub.3)].sub.2 BH, LiBH.sub.4, LiB(sec-Bu).sub.3 H, LiB(Et)3H, Li(9-BBN)H, NaBH.sub.4, KBH.sub.4, Me.sub.4 NBH.sub.4, Et.sub.4 NBH.sub.4, LiD, NaD, KD, CaD.sub.2, AlD.sub.3, MeAlD.sub.2, EtAlD.sub.2, n-PrAlD.sub.2, i-PrAlD.sub.2, n-BuAlD.sub.2, i-BuAlD.sub.2, sec-BuAlD.sub.2, t-BuAlD.sub.2, Me.sub.2 AlD, Et.sub.2 AlD, n-Pr.sub.2 AlD, i-Pr.sub.2 AlD, n-Bu.sub.2 AlD, i-Bu.sub.2 AlD, sec-Bu.sub.2 AlD, t-Bu.sub.2 AlD, LiAlD.sub.4, LiAl(Et).sub.2 D.sub.2, LiAl(n-Pr).sub.2 D.sub.2, LiAl(i-Pr).sub.2 D.sub.2, LiAl(n-Bu).sub.2 D.sub.2, LiAl(i-Bu).sub.2 D.sub.2, LiAl(sec-Bu).sub.2 D.sub.2, LiAl(t-Bu).sub.2 D.sub.2, LiAl(Et).sub.3 D, LiAl(n-Pr).sub.3 D, LiAl(i-Pr).sub.3 D, LiAl(n-Bu).sub.3 D, LiAl(i-Bu).sub.3 D, LiAl(sec-Bu).sub.3 D, LiAl(OMe).sub.3 D, LiAl(OEt).sub.3 D, LiAl(O-t-Bu).sub.3 D, NaAl(OCH.sub.2 CH.sub.2 OMe).sub.3 D, BD.sub.3, [(CH.sub.3).sub.2 CHCH(CH.sub.3)].sub.2 BD, LiBD.sub.4, LiB(sec-Bu).sub.3 D, LiB(Et).sub.3 D, Li(9-BBN)D, NaBD.sub.4, KBD.sub.4, Me.sub.4 NBD.sub.4 and Et.sub.4 NBD.sub.4. Two or more of these metal hydrides may be combined at will.

The metal and/or metallic compound is/are used in an amount usually of 0.01-10 mols, preferably 0.1-10 mols, preferably 0.1-5 mols per 100 mols of the hydrosilane monomer. The silyl compound and the metal hydride are usually used in an amount of 0.005-50 mols, preferably 0.05-20 mols per 100 mols of the hydrosilane monomer. The ratio of the metal and/or metallic compound to the silyl compound is usually in the range of 1/0.01-1/100, preferably 1/0.1 -1/50 by mol. The ratio of the metal and/or metallic compound to the metal hydride is usually in the range of 1/0.01-1/100, preferably 1/0.1-1/50 by mol.

The catalyst used in the invention may be added with crown ethers such as 12-crown-4,15-crown-5, 18-crown-6, dibenzo-12-crown-4, dibenzo-15-crown-5 and dibenzo-18-crown-6, and diamines such as tetramethyl ethylene diamine. These additives are usually used in an amount of 0.005-50, preferably 0.05-20 mols per 100 mols of the hydrosilane monomer.

The dehydrogenative condensation reaction according to the invention is usually effected at a temperature of 0.degree.-250.degree. C., preferably 25.degree.-210.degree. C., at a pressure usually of 1 mmHg-200 kg/cm.sup.2, preferably atmospheric to 100 kg/cm.sup.2 for a timelength of usually 5 minutes to 24 hours, preferably 30 minutes to 3 hours though dependent upon the reaction temperature and the amount of catalyst and starting monomer. The reaction may be carried out in the presence or absence of catalysts and with use of solvents such as hydrocarbon solvents including toluene, xylene, heptane, decane and dodecane, ether solvents including diethylether, isopropylether, methylbutylether, dimethoxyethane, tetrahydrofuran and dioxane, amide solvents including dimethylformamide and hexamethylphosphoric amide, ester solvents including ethylacetate and butylacetate and sulfoxides including dimethylsulfoxide.

The catalyst components and the monomer components may be simultaneously admixed, or the latter may be added to the former or vice versa. The solvents and the additives may be added at any suitable time point.

The dehydrogenative condensation reaction is preferably conducted in an atmosphere of inert gas such as argon and nitrogen regardless of the use of solvents.

The Kipping method employed for the production of silicon polymers according to the invention comprises reacting one or more of halogenosilanes of the group consisting of a halogenomonosilane of the formula (IV), (V) and (VI) hereinabove identified, in the presence of an alkali metal and/or an alkaline earth metal to form a condensation product and subjecting the resulting condensation product to thermal decomposition.

The halogenomonosilane of formula (IV) preferably includes tetrachlorosilane, i-propyltrichlorosilane, t-butyltrichlorosilane, (1-methylpropyl)trichlorosilane, cyclohexyltrichlorosilane, (1,1,2-trimethylpropyl)trichlorosilane, .alpha.-phenethyltrichlorosilane, cumyltrichlorosilane, (trimethylsilyl)trichlorosilane, di-i-propyldichlorosilane, di-t-butyldichlorosilane, di(1-methylpropyl)dichlorosilane, dicyclohexyldichlorosilane, di-.alpha.-phenethyldichlorosilane, bis(trimethylsilyl)dichlorosilane or the like, and further exemplarily includes tetrabromosilane, i-propyltribromosilane, t-butyltribromosilane, (1-methylpropyl)tribromosilane, cyclohexyltribromosilane, (1,1,2-trimethylpropyl)tribromosilane, .alpha.phenethyltribromosilane, cumyltribromosilane, (trimethylsilyl)tribromosilane, di-i-propyltribromosilane, di-t-butyltribromosilane, di(1-methylpropyl)tribromosilane, dicyclohexyltribromosilane, di-.alpha.-phenethyltribromosilane, bis(trimethylsilyl)tribromosilane, tetraiodosilane, i-propyltriiodosilane, t-butyltriiodosilane, (1-methylpropyl)triiodosilane, cyclohexyltriiodosilane, (1,1,2-trimethylpropyl)triiodosilane, .alpha.-phenethyltriiodosilane, cumyltriiodosilane, (trimethylsilyl)triiodosilane, di-i-propyldiiodosilane, di-t-butyldiiodosilane, di(1-methylpropyl)diiodosilane, dicyclohexyltriiodosilane, di-.alpha.-phenethyltriiodosilane, bis(trimethylsilyl)triiodosilane and the like.

The halogenodisilane of formula (V) preferably includes hexachlorosisilane, i-propylpentachlorodisilane, t-butylpentachlorodisilane, (1-methylpropyl)pentachlorodisilane, cyclohexylpentachlorodisilane, (1,1,2-trimethylpropyl)pentachlorodisilane, .alpha.-phenethylpentachlorodisilane, cumylpentachlorodisilane, (trimethylsilyl)pentachlorodisilane, 1,1-di-i-propyltetrachlorodisilane, 1,1-di-t-butyltetrachlorodisilane, 1,1-di(1-methylpropyl)tetrachlorodisilane, 1,1-dicyclohexyltetrachlorodisilane, 1,1-di-.alpha.-phenethyltetrachlorodisilane, 1,1-bis(trimethylsilyl)tetrachlorodisilane, 1,1-di-i-propyltetrachlorodisilane, 1,1-di-t-butyltetrachlorodisilane, 1,2-di(1-methylpropyl)tetrachlorodisilane, 1,2-dicyclohexyltetrachlorodisilane, 1,2-di-.alpha.-phenethyltetrachlorodisilane, 1,2-bis(trimethylsilyl)tetrachlorodisilane or the like, and further exemplarily includes 1,1,1-tri-i-propyltrichlorodisilane, 1,1,1-tri-t-butyltrichlorodisilane, 1,1,1-tri(1-methylpropyl)trichlorodisilane, 1,1,1-tricyclohexyltrichlorodisilane, 1,1,1-tri-.alpha.-phenethyltrichlorodisilane, 1,1,1-tris(trimethylsilyl)trichlorodisilane, 1,1,1-tri-i-propyltrichlorodisilane, 1,1,1-tri-t-butyltrichlorodisilane, 1,1,2-tri(1-methylpropyl)trichlorodisilane, 1,1,2-tricyclohexyltrichlorodisilane, 1,1,2-tri-.alpha.-phenethyltrichlorodisilane, 1,1,2-tris(trimethylsilyl)trichlorodisilane, hexabromodisilane, i-propylpentabromodisilane, t-butylpentabromodisilane, (1-methylpropyl)pentabromodisilane, cyclohexylpentabromodisilane, (1,1,2-trimethylpropyl)pentabromodisilane, .alpha.-phenethylpentabromodisilane, cumylpentabromodisilane, (trimethylsilyl)pentabromodisilane, 1,1-di-i-propyltetrabromodisilane, 1,1-di-t-butyltetrabromodisilane, 1,1-di(1-methylpropyl)tetrabromodisilane, 1,1-dicyclohexyltetrabromodisila ne, 1,1-di-.alpha.-phenethyltetrabromodisilane, 1,1-bis(trimethylsilyl)tetrabromodisilane, 1,1-di-i-pr