USRE44683EExpiredUtilityPatentIndex 78
Composition, preparation of polycarbosilanes and their uses

Assignee: SHEN QIONGHUAPriority: Jan 13, 2006Filed: May 7, 2012Granted: Dec 31, 2013
Est. expiryJan 13, 2026(expired)· nominal 20-yr term from priority
Inventors:SHEN QIONGHUA
C08G 77/60
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Claims
Abstract

The invention provides branched copolymers as precursors for preparing silicon carbide (SiC) ceramics represented by the general formulae: [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn , Formula Type-I wherein n is the degree of polymerization, 0.1≦x<0.8, 0.2≦y<0.9 and x+y=1; and R=methyl or H, R 1 and R 2 are randomly composed of hydrogen (H), allyl, methyl (Me), phenyl (Ph), propargyl or vinyl. Another branched copolymer is represented by the general formula: [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn [SiR 3 R 4 CH 2 ] zn Formula Type-II wherein n is the degree of polymerization, 0.1≦x<0.8, 0≦y<0.8, 0.2≦z<0.8 and x+y+z=1; and R=methyl or H, R 1 and R 2 are randomly composed of hydrogen (H), methyl (Me) and phenyl; R 3 and R 4 are randomly composed of H, allyl, methyl, phenyl (Ph), propargyl, and vinyl. The invention also provides methods for the preparation of such branched copolymers.
Claims

exact text as granted — not AI-modified
What is claimed is: 
     
       1. A polycarbosilane, having a general formula:
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn ,
 
 
       where n is the degree of polymerization, ˜ represents a branched chain, 0.1≦x&lt;0.8, 0.2≦y&lt;0.9 and x+y=1, wherein R is selected from a group consisting of: a methyl (Me) and hydrogen (H), wherein each of R 1  and R 2  are independently selected from a group consisting of: allyl, hydrogen (H), methyl (Me), phenyl (ph), propargyl and vinyl. 
     
     
       2. The polycarbosilane of  claim 1 , wherein R 1  and R 2  are the same. 
     
     
       3. A polycarbosilane, having a general formula:
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn [SiR 3 R 4 CH 2 ] zn  
 
 
       where n is the degree of polymerization, ˜ represents branched chain, 0.1≦x&lt;0.8, 0≦y &lt;0.8, 0.2≦z&lt;0.8 and x+y+z=1, wherein R is selected from a group consisting of: hydrogen (H) and methyl (Me), wherein each of R 1  and R 2  are independently selected from a group consisting of: hydrogen (H), methyl (Me), and phenyl (ph) and wherein each of R 3  and R 4  are independently selected from a group consisting of: hydrogen, allyl, methyl, phenyl (ph), a propargyl and vinyl. 
     
     
       4. The polycarbosilane of  claim 3 , wherein R 1  and R 2  are the same. 
     
     
       5. The polycarbosilane of  claim 3 , wherein R 3  and R 4  are the same. 
     
     
       6. A method for preparing a carbosilane copolymer having a general formula:
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn ,
 
 where n is the degree of polymerization,
 ˜ represents branched chain, 
 0.1≦x&lt;0.8, 0.2≦y&lt;0.9 and x+y=1, 
 
 wherein R is selected from a group consisting of hydrogen (H) and methyl (Me), 
 wherein R 1  and R 2  are selected from a group consisting of hydrogen (H), allyl, methyl (Me), phenyl (Ph), propargyl or and vinyl, 
 the method comprising: a one-step Grignard reaction in an organic solvent between halocarbosilane co-monomers in the presence of magnesium, 
 wherein the co-monomers have a general formula:
   X p Si(R 3 ) q CH r ,X s    
 
 where X is a halogen, R 3  is a hydrogen atom or a monovalent hydrocarbon, 1≦p≦3, 1≦q≦2, 1≦r≦2 and 1s≦2. 
 
     
     
       7. The method according to  claim 6 , wherein X is chlorine. 
     
     
       8. The method according to  claim 6 , wherein R is methyl. 
     
     
       9. The method according to  claim 6 , wherein the organic solvent is tetrahydrofuran. 
     
     
       10. The method according to  claim 6 , wherein a catalyst is added to the Grignard reaction, the catalyst being selected from a group consisting of zinc, NaSCN and CuCN. 
     
     
       11. The method according to  claim 6 , wherein the Grignard reaction is carried out at a temperature between about 68° C. and about 74° C. 
     
     
       12. A method for preparing a carbosilane copolymer having a general formula:
   ([Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn [SiR 3 R 4 CH 2 ] zn  
 
 where n is the degree of polymerization,
 ˜ represents branched chain, 
 0.1≦x&lt;0.8, 0≦y≦0.8, 0.2≦z&lt;0.8 and x+y+z=1, 
 
 wherein R is selected from a group consisting of: hydrogen (H) and methyl (Me), wherein R 1  and R 2  are selected from the group consisting of hydrogen (H), methyl (Me), or and phenyl (Ph), wherein R 3  and R 4  are selected from the group consisting of hydrogen (H), allyl, methyl (Me), phenyl (Ph), propargyl or and vinyl, the method comprising: a one-step Grignard reaction in an organic solvent between halocarbosilane co-monomers in the presence of magnesium, wherein the co-monomers have a general formula:
   X p Si(R 5 ) q CH r ,X S    
 
 where X is a halogen, R 5  is a hydrogen atom or a monovalent hydrocarbon, 1≦p≦3, 1≦q≦2, 1≦r≦2 and 1≦s≦2. 
 
     
     
       13. The method according to  claim 12 , wherein X is chlorine. 
     
     
       14. The method according to  claim 12 , wherein R is methyl. 
     
     
       15. The method of  claim 12 , wherein the organic solvent is tetrahydrofuran. 
     
     
       16. The method according to  claim 12 , wherein a catalyst is added to the Grignard reaction, the catalyst being selected from a group consisting of zinc, NaSCN and CuCN. 
     
     
       17. The method according to  claim 12 , wherein the Grignard reaction is carried out at a temperature between about 68° C. and about 74° C. 
     
     
       18. A method for preparing a copolymer carbosilane having a general formula:
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn ,
 
 where n is the degree of polymerization, ˜ represents branched chain 0.1≦x&lt;0.8, 0.2≦y&lt;0.9 and x+y=1, wherein R is selected from a group consisting of: a methyl (Me) and hydrogen (H), wherein each of R 1  and R 2  is independently selected from a group consisting of: allyl, hydrogen (H), methyl (Me), phenyl (ph), propargyl and vinyl, the method comprising: a Grignard reaction between halocarbosilanes co-monomers and a reduction reaction to replace a functional group in a resulting copolymer, wherein the functional group is selected from a group consisting of halogens and methoxy groups, and the halocarbosilane co-monomers having a general formula:
   X p Si(R 3 ) q CH r ,X s    
 
 where X is a halogen, R 3  is a hydrogen atom or a monovalent hydrocarbon, 1≦p≦3, 1≦q≦2, 1≦r≦2 and 1≦s≦2. 
 
     
     
       19. The method according to  claim 18 , wherein the functional group is selected from a group consisting of halogens and methoxy groups. 
     
     
       20. The method according to  claim 18 , wherein a catalyst is added to the Grignard reaction, the catalyst being selected from a group consisting of zinc, NaSCN and CuCN. 
     
     
       21. The method according to  claim 18 , wherein the Grignard reaction is carried out at a temperature between about 68° C. and about 74° C. 
     
     
       22. The method according to  claim 18 , wherein the reduction reaction is carried out at a temperature between about 50° C. and about 70° C. 
     
     
       23. A method for preparing a copolymer carbosilane having a general formula as
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn [SiR 3 R 4 CH 2 ] zn  
 
 where n is the degree of polymerization, ˜ represents branched chain 0.1≦x≦0.8, 0≦y&lt;0.8, 0.2≦z&lt;0.8 and x+y+z=1, wherein R is selected from a group consisting of: hydrogen (H), and methyl (Me), wherein R 1  and R 2  are selected from the group consisting of hydrogen (H), methyl (Me), or and phenyl (Ph), wherein R 3  and R 4  are selected from the group consisting of hydrogen (H), allyl, methyl (Me), phenyl (Ph), propargyl or and vinyl, the method comprising: a Grignard reaction between halocarbosilanes co-monomers and a reduction reaction to replace a functional group in a resulting copolymer, wherein the functional group is selected from a group consisting of halogens and methoxy groups, and the halocarbosilane co-monomers having a general formula:
   X p Si(R 5 ) q CH r ,X s    
 
 where X is a halogen, R 5  is a hydrogen atom or a monovalent hydrocarbon, 1≦p≦3, 1≦q≦2, 1≦r≦2 and 1≦s≦2. 
 
     
     
       24. The method according to  claim 23 , wherein the functional group is selected from a group consisting ofa halogens and methoxy groups group. 
     
     
       25. The method according to  claim 23 , wherein a catalyst is added to the Grignard reaction, the catalyst being selected from a group consisting of zinc, NaSCN and CuCN. 
     
     
       26. The method according to  claim 23 , wherein the Grignard reaction is carried out at a temperature between about 68° C. and about 74° C. 
     
     
       27. The method according to  claim 23 , wherein the reduction reaction is carried out at a temperature between about 50° C. and about 70° C. 
     
     
       28. A method for preparing a polycarbosilane having a general formula:
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn ,
 
 where n is the degree of polymerization, 
 ˜ represents branched chain, 0.1≦x&lt;0.8 0.1≦x≦0.8, 0.2≦y&lt;0.9 and x+y=1, wherein R is selected from a group consisting of: hydrogen (H) and methyl (Me), wherein R 1  and R 2  are selected from a group consisting of hydrogen (H), allyl, methyl (Me), phenyl (Ph), propargyl or and vinyl, the method comprising: a partial methoxylation of a trihalocarbosilane, a Grignard reaction of between the partially methoxylated trihalocarbosilane and a reduction of the partially methoxylated trihalocarbosilane a halocarbosilane co-monomer in the presence of magnesium, and a reduction reaction to replace functional groups in a resulting copolymer, wherein the functional group is selected from a group consisting of halogens and methoxy groups. 
 
     
     
       29. The method according to  claim 28 , wherein the partially methoxylated trihalocarbosilane has two general formula: Cl 3-m (OMe) m SiCH 2 Cl, where 1.5≦m≦2.5, and (OMe) p Cl 2-p SiCHCl 2 , where 0&lt;p≦1. 
     
     
       30. The method according to  claim 28 , wherein a catalyst is added to the Grignard reaction, the catalyst being selected from a group consisting of zinc, NaSCN and CuCN. 
     
     
       31. The method according to  claim 28 , wherein the Grignard reaction is carried out at a temperature between about 68° C. and about 74° C. 
     
     
       32. The method according to  claim 28 , wherein the reduction reaction is carried out at a temperature between about 50° C. and about 70° C. 
     
     
       33. A method for preparing a polycarbosilane having a general formula:
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn [SiR 3 R 4 CH 2 ] zn  
 
 where n is the degree of polymerization,
 ˜ represents branched chain, 
 
 0.1≦x&lt;0.8, 0≦y&lt;0.8 0.1≦x≦0.8, 0≦y≦0.8, 0.2≦z&lt;0.8 and x+y+z=1, wherein R is selected from a group consisting of: hydrogen (H), and methyl (Me), wherein R 1  and R 2  are selected from the group consisting of hydrogen (H), methyl (Me), or and phenyl (Ph), wherein R 3  and R 4  are selected from the group consisting of hydrogen (H), allyl, methyl (Me), phenyl (Ph), propargyl or and vinyl, the method comprising a partial methoxylation of a trihalocarbosilane, a Grignard reaction of between the partially methoxylated trihalocarbosilane and a halocarbosilane co-monomer in the presence of magnesium, and a reduction of the partially methoxylated trihalocarbosilane reaction to replace functional groups in a resulting copolymer, wherein the functional group is selected from a group consisting of halogens and methoxy groups. 
 
     
     
       34. The method according to  claim 33 , wherein the partially methoxylated trihalocarbosilane includes the general formula: Cl 3-m (OMe) m SiCH 2 Cl, where 1.5≦m≦2.5, and (OMe) p Cl 2-p SiCHCl 2 , where 0&lt;p≦1. 
     
     
       35. The method according to  claim 33 , wherein a catalyst is added to the Grignard reaction, the catalyst being selected from a group consisting of zinc, NaSCN and CuCN. 
     
     
       36. The method according to  claim 33 , wherein the Grignard reaction is carried out at a temperature between about 68° C. and about 74° C. 
     
     
       37. The method according to  claim 33 , wherein the reduction reaction is carried out at a temperature between about 50° C. and about 70° C. 
     
     
       38. A polycarbosilane, having a general formula:
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn [SiR 3 R 4 CH 2 ] zn  
   where n is the degree of polymerization, ˜ represents branched chain, 0.1≦x&lt;0.8, 0≦y&lt;0.8, z=0.05 and x+y+z=1, wherein R is selected from a group consisting of: hydrogen (H) and methyl (Me), wherein R 1  is selected from a group consisting of: hydrogen (H), methyl (Me), and phenyl (ph), wherein R 2  is selected from a group consisting of: methyl and phenyl, wherein R 3  is selected from a group consisting of: hydrogen, allyl, methyl, phenyl (ph), a propargyl and vinyl, and wherein R 4  is selected from a group consisting of: allyl, methyl, phenyl, propargyl and vinyl, and wherein at least one of R 1  and R 3  is a hydrogen.   
     
     
       39. The polycarbosilane of claim 38, wherein R 1  and R 2  are the same. 
     
     
       40. The polycarbosilane of claim 38, wherein R 3  and R 4  are the same. 
     
     
       41. A method for preparing a copolymer carbosilane having a general formula as
   [Si(˜)RC(˜)H] xn [SiR 1 R 2 CH 2 ] yn [SiR 3 R 4 CH 2 ] zn  
   where n is the degree of polymerization, ˜ represents branched chain 0.1≦x≦0.8, 0≦y&lt;0.8, z=0.05 and x+y+z=1, wherein R is selected from a group consisting of: hydrogen (H), and methyl (Me), wherein R 1  is selected from the group consisting of hydrogen (H), methyl (Me), and phenyl (Ph), wherein R 2  is selected from a group consisting of methyl and phenyl, wherein R 3  is selected from the group consisting of hydrogen (H), allyl, methyl (Me), phenyl (Ph), propargyl and vinyl, and wherein R 4  is selected from a group consisting of allyl, methyl, phenyl, propargyl and vinyl, the method comprising: a Grignard reaction between a partially methoxylated trihalocarbosilane and halocarbosilane co-monomer in the presence of Mg, and a reduction reaction to replace functional groups in a resulting copolymer, wherein the functional group is selected from a group consisting of halogens and methoxy groups.   
     
     
       42. The method according to claim 41, wherein the halocarbosilane co-monomer has a general formula:
   X p Si(R 5 ) q CH r ,X s      where X is a halogen, R 5  is a hydrogen atom or a monovalent hydrocarbon, 1≦p≦3, 1≦q≦2, 1≦r≦2 and 1≦s≦2.   
     
     
       43. The method according to claim 41, wherein the partially methoxylated trihalocarbosilane includes the general formula:
   Cl 3-m (OMe) m SiCH 2 Cl, where 1.5≦m≦2.5, and (OMe) p Cl 2-p SiCHCl 2 , where 0&lt;p≦1.
   
     
     
       44. The method according to claim 41, wherein a catalyst is added to the Grignard reaction, the catalyst being selected from a group consisting of zinc, NaSCN and CuCN. 
     
     
       45. The method according to claim 41, wherein the Grignard reaction is carried out at a temperature between about 68° C. and about 74° C. 
     
     
       46. The method according to claim 41, wherein the reduction reaction is carried out at a temperature between about 50° C. and about 70° C. 
     
     
       47. The method according to claim 18, wherein the functional group is a halogen group.
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