Metathesis-curable composition
View Patent ↗One-part and two-part compositions curable by a metathesis reaction comprising a resin containing a substrate with at least two cycloolefin groups per molecule curable by a metathesis reaction with a metathesis catalyst. These compositions may optionally contain a reaction control agent for slowing the progress of the metathesis reaction. The metathesis catalyst can be a ruthenium carbene complex catalyst. The substrate may be, for example, a difunctional or trifunctional carboxylate ester containing norbornenyl end groups.
1. A composition comprising at least 0.1 wt. % of a substrate containing at least two cycloolefin groups capable of undergoing a metathesis reaction and a metal carbene complex catalyst capable of initiating the metathesis reaction, wherein the substrate has the formula:
wherein:
a=1–100, c=0 or 1 and d=2–4,
when d=2 or 3, Z and Q are the same or different and are each a linear, branched, cyclic or polycyclic organic residue optionally containing siloxane groups (Si—O—Si) and optionally containing heteroatoms selected from the group consisting of B, N, O, Si, P, and S,
when d=4, Z is C and Q is a linear, branched, cyclic or polycyclic organic residue optionally containing siloxane groups (Si—O—Si) and optionally containing heteroatoms selected from the group consisting of B, N, O, Si, P, and S, and
D is a cycloolefinic residue and is different than Q or Z; and
wherein the catalyst has a structure selected from:
wherein:
M is ruthenium or osmium,
X is an alkylidene ligand with basicity higher than that of tricyclohexylphosphine (PCy 3 ),
X 1 is either PCy 3 or a neutral electron donor ligand with basicity lower than that of PCy 3 ,
X 2 and X 3 are either the same or different and are any anionic ligand,
Z is oxygen (O) or sulfur (S),
R 1 and R 2 are either the same or different and are each independently hydrogen or a substituent selected from the group consisting of C 1 –C 20 alkyl, C 2 –C 20 alkenyl, C 2 –C 20 alkynyl, aryl, C 1 –C 20 carboxylate, C 1 –C 20 alkoxy, C 2 –C 20 alkenyloxy, C 2 –C 20 alkynyloxy, aryloxy, C 2 –C 20 alkoxycarbonyl, C 1 –C 20 alkylthio, C 1 –C 20 alkylsulfonyl and C 1 –C 20 alkylsulfinyl, wherein each of the substituents is substituted or unsubstituted
R 4 is a substituent selected from the group consisting of C 1 –C 20 alkyl, C 2 –C 20 alkenyl, C 2 –C 20 alkynyl, aryl, C 1 –C 20 carboxylate, C 1 –C 20 alkoxy, C 2 –C 20 alkenyloxy, C 2 –C 20 alkynyloxy, aryloxy, C 2 –C 20 alkoxycarbonyl, C 1 –C 20 alkylthio, C 1 –C 20 alkylamino, C 1 –C 20 alkylsulfonyl and C 1 –C 20 alkylsulfinyl, wherein each of the substituents is substituted or unsubstituted, and
R 5 , a, b, c, and d are either the same or different and are each independently hydrogen or a substituent selected from the group consisting of C 1 –C 20 alkyl, C 2 –C 20 alkenyl, C 2 –C 20 alkynyl, aryl, C 1 –C 20 carboxylate, C 1 –C 20 alkoxy, C 2 –C 20 alkenyloxy, C 2 –C 20 alkynyloxy, aryloxy, C 2 –C 20 alkoxycarbonyl, C 1 –C 20 alkylthio, C 1 –C 20 alkylsulfonyl and C 1 –C 20 alkylsulfinyl, wherein each of the substituents is substituted or unsubstituted.
2. The composition of claim 1 wherein the substrate comprises a dinorbornenyl dicarboxylate ester.
3. The composition of claim 1 wherein D is a norbornenyl group; a=1, c=0, and d=2; and Z is a fragment selected from the group consisting of:
where e=1–30
where f=1–50
where g>0, h>0, and g+h=2–30
where j>0, k>0, and j+k=2–30
where p=1–30 and
4. The composition of claim 1 wherein Z is a polyether fragment.
5. The composition of claim 4 wherein the polyether fragment comprises one or more of butylene oxide units, ethylene oxide units or propylene oxide units.
6. The composition of claim 1 wherein Z is a polyester diol consisting of diacid units and alkylene oxide units.
7. The composition of claim 1 wherein Z is a polyester diol consisting of units of adipic acid and units of an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide.
8. The composition of claim 1 wherein D is a cycloolefinic residue selected from the group consisting of norbornenyl, norbornenylethyl, cyclopentenyl, 7-oxanorbornenyl, norbornadienyl, and 7-oxanorbornadienyl.
9. The composition of claim 1 wherein the catalyst has structure (a) and wherein X 1 is a phosphine, phosphite, phosphinite or phosphonite.
10. The composition of claim 9 wherein X 1 is a phosphine of the formula PR 3 R 4 R 5 wherein R 3 , R 4 , and R 5 are each an alkyl, aralkyl or aryl.
11. The composition of claim 10 wherein X 1 is a phosphine of the formula PR 3 R 4 R 5 wherein R 3 , R 4 , and R 5 are each n-butyl.
12. The composition of claim 1 wherein the catalyst has structure (a) and wherein R 1 is phenyl and R 2 is hydrogen.
13. The composition of claim 1 wherein X has the structure:
wherein Mes is mesityl and R′ is hydrogen or phenyl.
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 further comprising a reaction control agent for slowing the progress of the metathesis reaction after mixing the substrate and the catalyst at a mixing temperature and having the structure:
wherein:
G is selected from the group consisting of: L 3 ,
L is a hydrocarbon fragment containing a double or triple bond,
L 1 –L 9 are each independently selected from the group consisting of L, alkyl, aryl, aralkyl or haloalkyl,
A is a Group 14 atom, and
each of n and m=0–20.
16. The composition of claim 15 wherein L is a hydrocarbon fragment containing an allyl group, a vinyl group, an ethynyl group or a propargyl group.
17. The composition of claim 16 wherein the reaction control agent includes at least two L groups.
18. The composition of claim 16 wherein the reaction control agent includes at least three L groups.
19. The composition of claim 15 wherein A is silicon.
20. The composition of claim 15 wherein the reaction control agent is tetraallyl silane.
21. The composition of claim 15 wherein the reaction control agent is capable of preventing completion of the metathesis reaction in the absence of an applied temperature greater than the mixing temperature.
22. The composition of claim 1 comprising a base paste and a catalyst paste, wherein the base paste comprises the substrate, wherein the catalyst paste comprises the metal carbene complex catalyst dissolved in a solvent that is miscible with the base paste, and wherein the catalyst is capable of initiating the metathesis reaction upon mixing the base paste with the catalyst paste at room temperature.
23. The composition of claim 22 wherein the solvent is a siloxane substituted with alkyl groups and with arylalkyl or aryl groups.
24. The composition of claim 23 wherein the solvent is a phenyl trimethicone.
25. The composition of claim 1 further comprising a solvent in which the metal carbene complex catalyst is dissolved, wherein the solvent is a siloxane substituted with alkyl groups and with arylalkyl or aryl groups.
26. The composition of claim 25 wherein the solvent is a phenyl trimethicone.
27. A composition capable of undergoing a metathesis reaction upon mixing of its components, the components comprising:
a resin having a carboxylate ester backbone functionalized with at least two cycloolefin groups capable of undergoing a metathesis reaction;
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 (PCy 3 ), and X 1 is a phosphine, phosphite, phosphinite or phosphonite having a basicity lower than that of PCy 3 ; and
a reaction control agent for preventing completion of the metathesis reaction after mixing the composition components at a mixing temperature and until exposing the composition to an elevated temperature above the mixing temperature, the reaction control agent having the structure:
wherein:
G is selected from the group consisting of: L 3 ,
L is a hydrocarbon fragment containing an allyl group, a vinyl group, an ethynyl group or a propargyl group,
L 1 –L 9 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.
28. The composition of claim 27 wherein the cycloolefin groups are selected from the group consisting of norbornenyl, norbornenylethyl, cyclopentenyl, 7-oxanorbornenyl, norbornadienyl, and 7-oxanorbornadienyl.
29. The composition of claim 27 wherein X 1 is a phosphine of the formula PR 3 R 4 R 5 wherein R 3 , R 4 , and R 5 are each an alkyl, aralkyl or aryl.
30. The composition of claim 29 wherein X 1 is a phosphine of the formula PR 3 R 4 R 5 wherein R 3 , R 4 , and R 5 are n-butyl.
31. The composition of claim 27 wherein the X has the structure:
wherein Mes is mesityl and R′ is hydrogen or phenyl.
32. The composition of claim 27 wherein the catalyst has the structure:
wherein Bu is butyl, Ph is phenyl and Mes is mesityl.
33. The composition of claim 27 wherein the reaction control agent includes at least two L groups.
34. The composition of claim 27 wherein the reaction control agent includes at least three L groups.
35. The composition of claim 27 wherein A is silicon.
36. The composition of claim 27 wherein the reaction control agent is tetraallyl silane.
37. The composition of claim 27 wherein the resin comprises a dinorbornenyl dicarboxylate ester.
38. The composition of claim 27 further comprising a solvent in which the metal carbene complex catalyst is dissolved, wherein the solvent is a siloxane substituted with alkyl groups and with arylalkyl or aryl groups.
39. The composition of claim 38 wherein the solvent is a phenyl trimethicone.
40. A two-paste composition capable of undergoing a metathesis reaction at room temperature upon mixing the two pastes together, the composition comprising:
(a) a base paste comprising a base resin having a carboxylate ester backbone functionalized with at least two cycloolefin groups capable of undergoing a metathesis reaction;
(b) a catalyst paste comprising a metal carbene complex catalyst dissolved in a catalyst solvent that is miscible with the base paste and 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 (PCy 3 ),
Z is oxygen (O) or sulfur (S)
X 2 and X 3 are either the same or different and are any anionic ligand,
R 4 is a substituent selected from the group consisting of C 1 –C 20 alkyl, C 2 –C 20 alkenyl, C 2 –C 20 alkynyl, aryl, C 1 –C 20 carboxylate, C 1 –C 20 alkoxy, C 2 –C 20 alkenyloxy, C 2 –C 20 alkynyloxy, aryloxy, C 2 –C 20 alkoxycarbonyl, C 1 –C 20 alkylthio, C 1 –C 20 alkylamino, C 1 –C 20 alkylsulfonyl and C 1 –C 20 alkylsulfinyl, wherein each of the substituents is substituted or unsubstituted, and
R 5 , a, b, c, and d are either the same or different and are each independently hydrogen or a substituent selected from the group consisting of C 1 –C 20 alkyl, C 2 –C 20 alkenyl, C 2 –C 20 alkynyl, aryl, C 1 –C 20 carboxylate, C 1 –C 20 alkoxy, C 2 –C 20 alkenyloxy, C 2 –C 20 alkynyloxy, aryloxy, C 2 –C 20 alkoxycarbonyl, C 1 –C 20 alkylthio, C 1 –C 20 alkylsulfonyl and C 1 –C 20 alkylsulfinyl, wherein each of the substituents is substituted or unsubstituted.
41. The composition of claim 40 wherein the cycloolefin groups are selected from the group consisting of norbornenyl, norbornenylethyl, cyclopentenyl, 7-oxanorbornenyl, norbornadienyl, and 7-oxanorbornadienyl.
42. The composition of claim 40 wherein M is ruthenium; X is an imidazolidene ligand with basicity higher than that of tricyclohexylphosphine; X 2 and X 3 are halogen atoms; Z is oxygen; R 4 is a C 1 to C 10 alkyl fragment; a, b, c and d are each hydrogen, a C 1 to C 10 alkyl, or a C 1 to C 10 alkoxy group; and R 5 is hydrogen.
43. The composition of claim 40 wherein M is ruthenium; X is 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene; X 2 and X 3 are chlorine atoms; Z is oxygen; R 4 is 2-propyl; a, b, c and d are each either hydrogen or methoxy; and R 5 is hydrogen.
44. The composition of claim 40 wherein the solvent is a siloxane substituted with alkyl groups and with arylalkyl or aryl groups.
45. The composition of claim 44 wherein the solvent is a phenyl trimethicone.