Metathesis-curable composition with a reaction control agent
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/80
C08F-004/00
출원번호
US-0430592
(2003-05-06)
발명자
/ 주소
Angeletakis,Christos
출원인 / 주소
Kerr Corporation
대리인 / 주소
Wood, Herron &
인용정보
피인용 횟수 :
5인용 특허 :
32
초록▼
A composition curable by a metathesis reaction upon mixing its components and comprising an olefin-containing substrate, a metathesis catalyst, and a reaction control agent for slowing the progress of the metathesis reaction. The metathesis catalyst is a ruthenium or osmium curbene complex catalyst,
A composition curable by a metathesis reaction upon mixing its components and comprising an olefin-containing substrate, a metathesis catalyst, and a reaction control agent for slowing the progress of the metathesis reaction. The metathesis catalyst is a ruthenium or osmium curbene complex catalyst, such as one containing an alkylidene ligand with basicity higher than that of tricyclohexylphosphine (PCy3) and a neutral electron donor ligand with a basicity lower than that of PCy3, whereby the catalyst initiates the metathesis reaction of the composition upon mixing with the substrate. The reaction control agent is an organic compound that contains carbon-carbon double and/or triple bonds and one or more Group 14 atoms and is present in an amount effective to slow the progress of the metathesis reaction. The olefin containing substrate may be, for example, one or a combination of a di-, tri-or quadri-functional polydimethylsiloxane end-capped with norbornenylethyl groups or a polydimethylsiloxane tethered and end-capped with norbornenylethyl groups.
대표청구항▼
The invention claimed is: 1. A composition capable of undergoing a metathesis reaction upon mixing its components, the components comprising: an olefin-containing substrate comprising at least one oligomer or polymer having a backbone of >50% linear siloxane units, the oligomer or polymer functi
The invention claimed is: 1. A composition capable of undergoing a metathesis reaction upon mixing its components, the components comprising: an olefin-containing substrate comprising at least one oligomer or polymer having a backbone of >50% linear siloxane units, the oligomer or polymer functionalized with olefin groups capable of undergoing a metathesis reaction, wherein the at least one oligomer or polymer is selected from the group consisting of: a telechelic oligomer or polymer end-capped with the olefin groups, an oligomer or polymer tethered and end-capped with the olefin groups, a tri-functional oligomer or polymer end-capped with the olefin groups, and a quadri-functional oligomer or polymer end-capped with the olefin groups, and combinations thereof; and a metal carbene complex catalyst capable of initiating the metathesis reaction in the composition, wherein the catalyst has the structure: wherein: M is ruthenium or osmium, X is an alkylidene ligand with basicity higher than that of tricyclohexylphosphine (PCy3), X1 is a neutral electron donor ligand with a basicity lower than that of tricyclohexylphosphine, X2 and X3 are either the same or different and are any anionic ligand, and R1 and R2 are either the same or different and are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C 1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, wherein each of the substituents is substituted or unsubstituted; and a reaction control agent for slowing the progress of the metathesis reaction after mixing the composition components and having the structure: wherein: G is selected from the group consisting of: L3, L is a hydrocarbon fragment containing a double or triple bond, L1-L0 are each independently selected from the group consisting of L, alkyl, aryl, aralkyl or haloalkyl, A is a Group 14 atom, n=0-20, and m=0-20. 2. The composition of claim 1 wherein the substrate comprises a polysiloxane tethered and end-capped with cycloalkenyl groups capable of undergoing a metathesis reaction. 3. The composition of claim 2 wherein the cycloalkenyl groups are norbornenyl groups. 4. The composition of claim 2 wherein the cycloalkenyl groups are norbornenylethyl groups. 5. The composition of claim 1 wherein the substrate comprises a polysiloxanc end-capped with cycloalkenyl groups capable of undergoing a metathesis reaction. 6. The composition of claim 5 wherein the cycloalkenyl groups are norbornenyl groups. 7. The composition of claim 5 wherein the cycloalkenyl groups are norbornenylethyl groups. 8. The composition of claim 1 wherein X1 is a phosphine, phosphite, phosphinite or phosphonite. 9. The composition of claim 8 wherein X1 is a phosphine of the formula PR3R4R5 wherein R 3, R4, and R5are each an alkyl, aralkyl or aryl. 10. The composition of claim 9 wherein X1 is a phosphine of the formula PR3R4R5 wherein R 3R4, and R5 are each n-butyl. 11. The composition of claim 1 wherein R1 is phenyl and R2 is hydrogen. 12. The composition of claim 1 wherein the X has the structure: wherein Mes is mesityl and R1 is hydrogen or phenyl. 13. The composition of claim 1 wherein the X has the structure: wherein Mes is mesityl. 14. The composition of claim 1 wherein the catalyst has the structure: wherein Bu is butyl, Ph is phenyl and Mes is mesityl. 15. The composition of claim 1 wherein L is a hydrocarbon fragment containing an allyl group, a vinyl group, an ethynyl group or a propargyl group. 16. The composition of claim 15 wherein the reaction control agent includes at least two L groups. 17. The composition of claim 15 wherein the reaction control agent includes at least three L groups. 18. The composition of claim 1 wherein A is silicon. 19. The composition of claim 1 wherein the reaction control agent is tetraallyl silane. 20. A composition capable of undergoing a metathesis reaction upon mixing of its components, the components comprising: an olefin-containing substrate comprising at least one oligomer or polymer having a backbone of >50% linear siloxane units, the oligomer or polymer functionalized with olefin groups capable of undergoing a metathesis reaction, wherein the at least one oligomer or polymer is selected from the group consisting of: a telechelic oligomer or polymer end-capped with the olefin groups, an oligomer or polymer tethered and end-capped with the olefin groups, a tri functional oligomer or polymer end-capped with the olefin groups, and a quadri-functional oligomer or polymer end-capped with the olefin grouns, and combinations thereof; and a metal carbene complex catalyst capable of initiating the metathesis reaction in the composition, wherein the catalyst has the structure: wherein: M is ruthenium or osmium, X is an alkylidene ligand with basicity higher than that of tricyclohexylphosphine (PCy3), X1 is a neutral electron donor ligand with a basicity lower than that of tricyclohexylphosphine, X2 and X3 are either the seine or different and are any anionic ligand, and R1 and R2 are either the same or different and are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C 1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, wherein each of the substituents is substituted or unsubstituted; and a reaction control agent for preventing completion of the metathesis reaction in the absence of an elevated temperature of at least 30째 C. above a mixing temperature of the composition components and having the structure: wherein: G3 is selected from the group consisting of: L 3, L is a hydrocarbon fragment containing a double or triple bond, L1-L9 are each independently selected from the group consisting of L, alkyl, aryl, aralkyl or haloalkyl, A is a Group 14 atom, n=0-20, and m=0-20. 21. The composition of claim 20 wherein the substrate comprises a polysiloxane tethered and end-capped with cycloalkenyl groups capable of undergoing a metathesis reaction. 22. The composition of claim 21 wherein the cycloalkenyl groups are norbornenyl groups. 23. The composition of claim 21 wherein the cycloalkenyl groups are norbornenylethyl groups. 24. The composition of claim 20 wherein the substrate comprises a polysiloxane end-capped with cycloalkenyl groups capable of undergoing a metathesis reaction. 25. The composition of claim 24 wherein the cycloalkenyl groups are norbornenyl groups. 26. The composition of claim 24 wherein the cycloalkenyl groups are norbornenylethyl groups. 27. The composition of claim 20 wherein X1 is a phosphine, phosphite, phosphinite or phosphonite. 28. The composition of claim 27 wherein X1 is a phosphine of the formula PR3R4R5 wherein R 3, R4, and R5 are each an alkyl, aralkyl or aryl. 29. The composition of claim 28 wherein X1 is a phosphine of the formula PR3R4R5 wherein R 3, R4, and R5 are each n-butyl. 30. The composition of claim 20 wherein R1 is phenyl and R2 is hydrogen. 31. The composition of claim 20 wherein the X has the structure: wherein Mes is mesityl and R1 is hydrogen or phenyl. 32. The composition of claim 20 wherein the X has the structure: wherein Mes is mesityl. 33. The composition of claim 20 wherein the catalyst has the structure: wherein Bu is butyl, Ph is phenyl and Mes is mesityl. 34. The composition of claim 20 wherein L is a hydrocarbon fragment containing an allyl group, a vinyl group, an ethynyl group or a propargyl group. 35. The composition of claim 34 wherein the reaction control agent includes at least two L groups. 36. The composition of claim 34 wherein the reaction control agent includes at least three L groups. 37. The composition of claim 20 wherein A is silicon. 38. The composition of claim 20 wherein the reaction control agent is tetraallyl silane. 39. A composition capable of undergoing a metathesis reaction upon mixing of its components, the components comprising: an olefin-containing compound comprising at least one oligomer or polymer having a backbone of >50% linear siloxane units, the oligomer or polymer functionalized with olefin groups capable of undergoing a metathesis reaction, wherein the at least one oligomer or polymer is selected from the group consisting of: a telechelic oligomer or polymer end-capped with the groups, an oligomer or polymer tethered and end-capped with the groups, a tri-functional oligomer or polymer end-capped with the groups, and a quadri-functional oligomer or polymer end-capped with the groups, and combinations thereof; a ruthenium carbene complex catalyst capable of initiating the metathesis reaction in the composition, wherein the catalyst has the formula: wherein Ph is phenyl, X is an alkylidene ligand having a basicity higher than that of tricyclohexylphosphine (PCy3), and X1 is a phosphine, phosphite, phosphinite or phosphonite having a basicity lower than that of PCy3; and a reaction control agent for slowing the progress of the metathesis reaction after mixing the composition components and having the structure: wherein: G is selected from the group consisting of: L3, L is a hydrocarbon fragment containing an allyl group, a vinyl group, an ethynyl group or a propargyl group, L1-L9 are each independently selected from the group consisting of L, alkyl, aryl, aralkyl or haloalkyl, A is a Group 14 atom, n=0-20, and m=0-20. 40. The composition of claim 39 wherein the cycloalkenyl groups are norbornenyl groups. 41. The composition of claim 39 wherein the cycloalkenyl groups are norbornenylethyl groups. 42. The composition of claim 39 wherein X1 is a phosphine of the formula PR3R4R5 wherein R 3, R4, and R5 are each an alkyl, aralkyl or aryl. 43. The composition of claim 42 wherein X1 is a phosphine of the formula PR3R4R5 wherein R 3, R4, and R5 are n-butyl. 44. The composition of claim 39 wherein the X has the structure: wherein Mes is mesityl and R1 is hydrogen or phenyl. 45. The composition of claim 39 wherein the X has the structure: wherein Mes is mesityl. 46. The composition of claim 39 wherein the reaction control agent includes at least two L groups. 47. The composition of claim 39 wherein the reaction control agent includes at least three L groups. 48. The composition of claim 39 wherein A is silicon. 49. The composition of claim 39 wherein the reaction control agent is tetraallyl silane.
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