Claims
- 1. A method of producing polysilazanes useful as preceramic polymers and containing at least one newly formed Si--N bond which comprises:
- (a) providing a precursor containing at least one Si--N bond, catalytically cleaving an Si--N bond in the precursor in the presence of a transition metal catalyst effective to activate Si--N bonds, such cleavage being carried out in the presence of hydrogen or a hydrogen donor, and reacting the cleavage product to produce an initial polysilazane product; or
- (b) providing one or more reactants which contain an Si--H bond and an N--H bond, and causing reaction to occur between such Si--H and N--H bonds in the presence of a transition metal catalyst effective to activate Si--H and N--H bonds, to produce an initial polysilazane product having at least two Si--N bonds.
- 2. The method of claim 1, wherein in said type (a) reaction, said initial polysilazane product results from reaction of said cleavage product is reacted with a second such cleavage product or with a compound containing an Si--H bond, an N--H bond, or both.
- 3. The method of claim 1, wherein a compound having an M--H bond reacts with either the cleavage product in said type (a) reaction or with a reactant in said type (b) reaction or both, wherein M is B, Al, Ga, In, Ge, Pb, Sn or S.
- 4. The method of claim 1, wherein the transition metal catalyst is a homogeneous catalyst selected from the group consisting of H.sub.4 Ru.sub.4 (CO).sub.12, Fe(CO).sub.5, Rh.sub.6 (CO).sub.16, Co.sub.2 (CO).sub.8, (Ph.sub.3 P).sub.2 Rh(CO)H, H.sub.2 PtCl.sub.6, nickel cyclooctadiene, Os.sub.3 (CO).sub.12, Ir.sub.4 (CO).sub.12, (Ph.sub.3 P).sub.2 Ir(CO)H, NiCl.sub.2, Ni(OAc).sub.2, Cp.sub.2 TiCl.sub.2, (Ph.sub.3 P).sub.3 RhCl, H.sub.2 Os.sub.3 (CO).sub.10, Pd(Ph.sub.3 P).sub.4, Fe.sub.3 (CO).sub.12, Ru.sub.3 (CO).sub.12, ZnCl.sub.2, RuCl.sub.3, NaHRu.sub.3 (CO).sub.11, PdCl.sub.2, Pd(OAc).sub.2, (.phi.CH).sub.2 PdCl.sub.2, and mixtures thereof, or a heterogeneous catalyst selected from the group consisting of Pt/C, Pt/BaSO.sub.4, Cr, Pd/C, Co/C, Pt black, Co black, Ru black, Ra--Ni, Pd black, Ir/Al.sub.2 O.sub.3, Pt/SiO.sub.2, Ru/TiO.sub.2, Rh/La.sub.2 O.sub.3, Pd/Ag alloy, LaNi.sub.5, PtO.sub.2, and mixtures thereof.
- 5. The method of claim 1, wherein said transition metal catalyst is a palladium catalyst.
- 6. The method of claim 1, wherein the reaction temperature is between about -78.degree. C. and about 250.degree. C.
- 7. The method of claim 1, wherein the polysilazanes produced are in a tractable preceramic polymer composition having either an Mn greater than about 10,000 D, an Mw greater than about 16,000 D, an Mz greater than about 40,000 D, a polysilazane species having a molecular weight higher than about 50,000 D, or combinations thereof.
- 8. A method of preparing silazanes and siloxazanes suitable as preceramic polymers, comprising the steps of:
- (a) providing a linear, branched or cyclic starting material having the structure --R'.sub.2 Si--A-- in its molecule, in which A is hydrogen, NR, or Si and wherein said starting material is oligomeric, polymeric or copolymeric;
- (b) providing a transition metal catalyst effective to activate Si--N, Si--Si and/or Si--H bonds; and
- (c) reacting the starting material in the presence of such catalyst with (1) hydrogen or a hydrogen donor where A is NR and the starting material is part of a silazane or (2) H--X--R where A is hydrogen or Si, wherein:
- the R groups are independently selected from the group consisting of: hydrogen; boryl; hydrocarbyl including lower alkyl, alkenyl, alkynyl, aryl, lower alkyl substituted aryl, cycloaliphatic; silyl or polysilyl; said hydrocarbyl or silyl optionally substituted with amino, hydroxyl, an ether moiety or an ester moiety, lower alkoxy, a fused aromatic radical of 8 to 20 carbon atoms, or an organometallic radical;
- the R' moieties are independently selected from the group consisting of: hydrogen; amino; hydrocarbyl including lower alkyl, alkoxy, alkenyl, alkynyl, aryl, lower alkyl substituted aryl, cycloaliphatic; silyl or polysilyl; said hydrocarbyl or silyl optionally substituted with amino, hydroxyl, an ether moiety or an ester moiety, lower alkoxy, or a fused aromatic radical of 8 to 20 carbon atoms, and wherein R and R' may be part of an oligomeric or polymeric structure; and
- X is selected from the group consisting of NR, NR--NR, and NR--R--NR.
- 9. The method of claim 8, wherein the starting material is of the following structures, where x is an integer from 0 to 4 inclusive, y is an integer from 0 to 4 inclusive, z is an integer from 0 to 2 inclusive, the sum of x, y and z is 4, a and b are integers from 0 to 2 inclusive, the sum of a and b is 2, and m is an integer defining the number of monomer units in the oligomer, polymer or copolymer. ##STR37##
- 10. The method of claim 8, wherein the starting material is of the formula R'.sub.a SiH.sub.b wherein a is an integer from 0 to 2 inclusive, b is an integer from 2 to 4 inclusive, and the sum of a and b is 4.
- 11. The method of claim 1, wherein said reaction is of type (b), said one or more reactants includes a siloxane, and said silazane products include siloxazanes.
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. application Ser. No. 908,685, filed Mar. 4, 1986 (PCT/US86/00548), which is a continuation-in-part of U.S. application Ser. No. 727,415, filed Apr. 26, 1985, now issued as U.S. Pat. No. 4,612,383.
ORIGIN OF INVENTION
The Government has certain rights in this invention as it was funded in Part under Contract Nos. N00014-84-C-0392 and N00014-85-C-0668 awarded by the Office of Naval Research.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
102e Date |
371c Date |
PCT/US86/02266 |
10/24/1986 |
|
|
12/1/1986 |
12/1/1986 |
US Referenced Citations (7)
Continuation in Parts (2)
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Number |
Date |
Country |
Parent |
908685 |
Mar 1986 |
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Parent |
727415 |
Apr 1985 |
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