US5322913A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Polysilazanes and related compositions, processes and uses
Assignee: SRI International Inc
•
Filing: 1990-06-19
•
Granted: 1994-06-21
•
Expires: 2010-06-19
Abstract
Abstract Silazanes and related compounds are prepared by (a) providing a precursor containing at least one Si-N bond, cleaving an Si-N bond in the precursor in the presence of hydrogen or a hydrogen donor, and reacting the cleavage product with a second cleavage product or with a compound containing an Si-H bond, an N-H bond, or both, to produce an initial silazane product having at least one newly formed Si-N bond or (b) providing one or more reactants which contain an Si-H bond and an N-H bond, and causing reaction to occur between the two bonds in the presence of a transition metal catalyst to form an initial silazane product having newly formed Si-N bonds. Further products may result from additional reaction of either type. Novel compounds, including siloxazanes and high molecular weight polysilazanes, are provided. The compounds may be pyrolyzed to yield ceramic materials such as silicon nitride, silicon carbide and silicon oxynitride. In a preferred embodiment, substantially pure silicon nitride and articles prepared therefrom are provided. Fibers, coatings, binders, and the like may be prepared from the novel materials.
Inventors
- 👤 Yigal D. Blum
- 👤 Richard M. Laine
- 👤 Kenneth B. Schwartz
- 👤 Robert M. Platz
- 👤 David J. Rowcliffe
- 👤 Allen L. Dodge
- 👤 Jonathan M. McLeod
- 👤 Daryl L. Roberts
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 12:48
CPC Classifications
C; C04; C04B; C04B35/00; C04B35/515; C04B35/58; C04B35/584; C04B35/589; C04B35/01; C04B35/16; C04B35/18; C04B35/185; C04B35/56; C04B35/565; C04B35/571; C04B35/622; C04B35/626; C04B35/63; C04B35/6303; C04B35/6316; C04B41/00; C04B41/45; C04B41/4505; C04B41/455; C04B41/4554; C07; C07F; C07F7/00; C07F7/02; C07F7/08; C07F7/10; C07F7/21; C08; C08G; C08G77/00; C08G77/04; C08G77/38; C08G77/382; C08G77/398; C08G77/48; C08G77/54; C08G77/60; C08G77/62; C08G79/00
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
46 words
A tractable preceramic polysilazane 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, or containing a polysilazane species having a molecular weight higher than about 50,000 D, or a combination thereof.
Claim 2
Dependent Claim
46 words
A tractable preceramic polysilazane 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, or containing a polysilazane species having a molecular weight higher than about 50,000 D, or a combination thereof.
Claim 3
Dependent Claim
47 words
The polysilazane composition of claim 1 having either an Mn greater than about 20,000 D, an Mw greater than about 32,000 D, an Mz greater than about 80,000 D, containing a polysilazane species having a molecular weight of at least about 500,000 D, or a combination thereof.
Claim 4
Dependent Claim
74 words
Silazanes prepared by the process comprising providing at least one reactant which contains 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 to produce an initial silazane product having at least two Si--N bonds, and wherein said at least one reactant additionally includes an Si--N bond, and said initial silazane product includes two distinguishable Si--N bond species.
Claim 5
Dependent Claim
74 words
Silazanes prepared by the process comprising providing at least one reactant which contains 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 to produce an initial silazane product having at least two Si--N bonds, and wherein said at least one reactant additionally includes an Si--N bond, and said initial silazane product includes two distinguishable Si--N bond species.
Claim 6
Dependent Claim
230 words
Silazanes prepared by the process comprising the steps of: (a) providing a starting material having the structural formula R' a SiHb: (b) providing a transition metal catalyst; and (c) reacting the starting material in the presence of said 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, a fused aromatic radical of 8 to 20 carbon atoms, or an organometallic radical, and wherein R and R' may be part of an oligomeric or polymeric structure; X is selected from the group consisting of SiR2, NR, NR--NR, and NR--R--NR; and wherein a is 0 or 1 or b is 3 or 4.
Claim 7
Dependent Claim
230 words
Silazanes prepared by the process comprising the steps of: (a) providing a starting material having the structural formula R' a SiHb: (b) providing a transition metal catalyst; and (c) reacting the starting material in the presence of said 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, a fused aromatic radical of 8 to 20 carbon atoms, or an organometallic radical, and wherein R and R' may be part of an oligomeric or polymeric structure; X is selected from the group consisting of SiR2, NR, NR--NR, and NR--R--NR; and wherein a is 0 or 1 or b is 3 or 4.
Claim 8
Dependent Claim
141 words
The polysilazane composition of claim 1, comprising silazanes containing structural units of the formula ##STR32## wherein a is 0 or 1, b is 1 or 2, the sum of a and b is 2, m is an integer defining the number of monomer units in the structure, and the R' moieties are independently selected from the group consisting of: hydrogen; amino; hydrocarbyl including lower alkyl, alkoxy, alkenyl, alkynyl, 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, said silazanes being substantially free of Si--C bonds and having either an Mn greater than about 10,000 D, an Mw greater than about 16,000 D, or an Mz greater than about 40,000 D.
Claim 9
Dependent Claim
156 words
Oligomeric or polymeric siloxazanes containing recurring units having the structural formula ##STR33## wherein the R groups 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, a fused aromatic radical of 8 to 20 carbon atoms, or an organometallic radical, and wherein R and R' may be part of an oligomeric or polymeric structure; the R moieties are independently selected from the group consisting of: hydrogen; amino; hydrocarbyl including lower alkyl, alkoxy, alkenyl, alkynyl, 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, said silazanes being substantially free of Si--C bonds.
Claim 10
Dependent Claim
156 words
Oligomeric or polymeric siloxazanes containing recurring units having the structural formula ##STR33## wherein the R groups 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, a fused aromatic radical of 8 to 20 carbon atoms, or an organometallic radical, and wherein R and R' may be part of an oligomeric or polymeric structure; the R moieties are independently selected from the group consisting of: hydrogen; amino; hydrocarbyl including lower alkyl, alkoxy, alkenyl, alkynyl, 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, said silazanes being substantially free of Si--C bonds.
Claim 11
Dependent Claim
13 words
Fibers spun from the silazanes of claims 1, 2, 3, 4 or 5.
Claim 12
Dependent Claim
8 words
Fibers spun from the siloxazanes of claim 6.
Claim 13
Dependent Claim
87 words
A tractable silazane composition prepared by the process comprising 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, such cleavage being carried out in the presence of hydrogen or a hydrogen donor, and reacting the cleavage product to produce an initial silazane product, wherein said initial silazane product has an Mn greater than about 10,000 D, an Mw greater than about 16,000 D, or an Mz greater than about 40,000 D.
Claim 14
Dependent Claim
87 words
A tractable silazane composition prepared by the process comprising 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, such cleavage being carried out in the presence of hydrogen or a hydrogen donor, and reacting the cleavage product to produce an initial silazane product, wherein said initial silazane product has an Mn greater than about 10,000 D, an Mw greater than about 16,000 D, or an Mz greater than about 40,000 D.
Claim 15
Dependent Claim
151 words
A tractable silazane composition prepared by the process comprising causing both of the following reaction types (a) and (b) to occur simultaneously: (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, such cleavage being carried out in the presence of hydrogen or a hydrogen donor, and reacting the cleavage product to produce a first initial silazane product; and (b) providing at least one reactant which contains 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 to produce a second initial silazane product having at least two Si--N bonds, wherein said second initial silazane product has an Mn greater than about 10,000 D, an Mw greater than about 16,000 D, or an Mz greater than about 40,000 D.
Claim 16
Dependent Claim
151 words
A tractable silazane composition prepared by the process comprising causing both of the following reaction types (a) and (b) to occur simultaneously: (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, such cleavage being carried out in the presence of hydrogen or a hydrogen donor, and reacting the cleavage product to produce a first initial silazane product; and (b) providing at least one reactant which contains 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 to produce a second initial silazane product having at least two Si--N bonds, wherein said second initial silazane product has an Mn greater than about 10,000 D, an Mw greater than about 16,000 D, or an Mz greater than about 40,000 D.
Claim 17
Dependent Claim
83 words
Silazanes containing structural units of the formula ##STR34## wherein a is 0 or 1, b is 1 or 2, the sum of a and b is 2, and 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; said hydrocarbyl 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.
Claim 18
Dependent Claim
83 words
Silazanes containing structural units of the formula ##STR34## wherein a is 0 or 1, b is 1 or 2, the sum of a and b is 2, and 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; said hydrocarbyl 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.
References Cited (Backward Citations)
US2579416A
Cited
US2579417A
Cited
US2564674A
Cited
US2579418A
Cited
US2968530A
Cited
US3007886A
Cited
US3193399A
Cited
US3140288A
Cited
US3393218A
Cited
US3356513A
Cited
US3518289A
Cited
US3530092A
Cited
US3853567A
Cited
US3892583A
Cited
US4097294A
Cited
US4115427A
Cited
US4177230A
Cited
US4200666A
Cited
US4255549A
Cited
US4293676A
Cited
US4292422A
Cited
US4340619A
Cited
US4404153A
Cited
US4312970A
Cited
USRE31727E
Cited
US4395460A
Cited
US4397828A
Cited
US4471132A
Cited
US4540803A
Cited
US4543344A
Cited
US4482669A
Cited
US4482689A
Cited
US4594330A
Cited
US4595775A
Cited
US4535007A
Cited
US4668642A
Cited
EP0175383A2
Cited
US4666872A
Cited
US4689382A
Cited
US4612383A
Cited
US4656300A
Cited
US4675424A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1997-06-20 | 1997-12-20 | 1998-06-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2001-06-20 | 2001-12-20 | 2002-06-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2005-06-20 | 2005-12-20 | 2006-06-21 | $7700.00 | Window Closed / Lapsed |