High-molecular-weight polysilane and method for producing same
View Patent ↗There is provided a highly conductive and good silicon thin film which is obtained by applying a coating-type polysilane composition prepared by use of a polysilane having a large weight average molecular weight to a substrate, followed by baking. A polysilane having a weight average molecular weight of 5,000 to 8,000. The polysilane may be a polymer of cyclopentasilane. A silicon film obtained by applying a polysilane composition in which the polysilane is dissolved in a solvent to a substrate, and baking the substrate at 100° C. to 425° C. The cyclopentasilane may be polymerized in the presence of a palladium catalyst supported on a polymer. The palladium catalyst supported on a polymer may be a catalyst in which palladium as a catalyst component is immobilized on a functional polystyrene. The palladium may be a palladium compound or a palladium complex. The palladium-immobilized catalyst may be formed by microencapsulating a zero-valent palladium complex or a divalent palladium compound with a functional polystyrene. The zero-valent palladium complex may be a tetrakis(triphenylphosphine)palladium (0) complex.
1. A method for producing a polymer of cyclopentasilane, comprising polymerizing the cyclopentasilane in the presence of a palladium catalyst comprises a zero-valent palladium complex or a divalent palladium compound microencapsulated with functional polystyrene.
2. The method according to claim 1 , wherein the palladium catalyst microencapsulated with the functional polystyrene comprises the divalent palladium compound bonded to the functional polystyrene.
3. The method according to claim 1 , wherein the functional polystyrene comprises a polystyrene having a polyethylene oxide group with a hydroxy group at a terminal thereof or a polystyrene having a diphenylphosphino group.
4. The method according to claim 1 , wherein the method further comprises: reacting a cyclic silane of Formula (1):
(SiR 1 R 2 ) n (1)
wherein R 1 and R 2 are each a hydrogen atom, a C 1-6 alkyl group, or a substituted or unsubstituted phenyl group (provided that both R 1 and R 2 are not simultaneously hydrogen atoms), and n is an integer of 4 to 6, with a hydrogen halide in an organic solvent in a presence of an aluminum halide to obtain a cyclic silane of Formula (2):
(SiR 3 R 4 ) n (2)
wherein R 3 and R 4 are each a halogen atom, and n is an integer of 4 to 6, and reducing the cyclic silane of Formula (2) with hydrogen or lithium aluminum hydride to obtain a cyclic silane of Formula (3):
(SiH 2 ) n (3)
wherein n is an integer of 4 to 6, and the cyclic silane of Formula (3) includes the cyclopentasilane.
5. The method according to claim 4 , wherein both R 1 and R 2 are phenyl groups.
6. The method according to claim 4 , wherein both R 3 and R 4 are chlorine atoms.
7. The method according to claim 4 , wherein the cyclic silane of Formula (3) contains the cyclopentasilane in an amount of 80% or more by moles.
8. The method according to claim 1 , wherein the palladium catalyst comprises the zero-valent palladium complex.
9. The method according to claim 8 , wherein the zero-valent palladium complex is a tetrakis(triphenylphosphine)palladium (0) complex.
10. A method for producing a polymer of cyclopentasilane, comprising polymerizing the cyclopentasilane in the presence of a palladium catalyst supported on a polystyrene having a polyethylene oxide group with a hydroxy group at a terminal thereof or a polystyrene having a diphenylphosphino group.
11. The method according to claim 10 , wherein the palladium catalyst comprises a divalent palladium compound.
12. The method according to claim 10 , wherein the palladium catalyst comprises a zero-valent palladium complex.
13. The method according to claim 12 , wherein the zero-valent palladium complex is a tetrakis(triphenylphosphine)palladium (0) complex.
14. A method for producing a polymer of cyclopentasilane, comprising:
reacting a cyclic silane of Formula (1):
(SiR 1 R 2 ) n (1)
wherein R 1 and R 2 are each a hydrogen atom, a C 1-6 alkyl group, or a substituted or unsubstituted phenyl group (provided that both R 1 and R 2 are not simultaneously hydrogen atoms), and n is an integer of 4 to 6, with a hydrogen halide in an organic solvent in a presence of an aluminum halide to obtain a cyclic silane of Formula (2):
(SiR 3 R 4 ) n (2)
wherein R 3 and R 4 are each a halogen atom, and n is an integer of 4 to 6;
reducing the cyclic silane of Formula (2) with hydrogen or lithium aluminum hydride to obtain a cyclic silane of Formula (3):
(SiH 2 ) n (3)
wherein n is an integer of 4 to 6; and
polymerizing the cyclic silane of Formula (3) in the presence of a palladium catalyst supported on a polymer, wherein the cyclic silane of Formula (3) includes the cyclopentasilane.
15. The method according to claim 14 , wherein both R 1 and R 2 are phenyl groups.
16. The method according to claim 15 , wherein both R 3 and R 4 are chlorine atoms.
17. The method according to claim 14 , wherein the cyclic silane of Formula (3) contains the cyclopentasilane in an amount of 80% or more by moles.
18. The method according to claim 14 , wherein the functional polystyrene comprises a polystyrene having a polyethylene oxide group with a hydroxy group at a terminal thereof or a polystyrene having a diphenylphosphino group.
19. The method according to claim 18 , wherein the palladium catalyst comprises a divalent palladium compound.
20. The method according to claim 18 , wherein the palladium catalyst comprises a zero-valent palladium compound.