Polyether-based composition curable by metathesis reaction
View Patent ↗One-part and two-part compositions curable by a metathesis reaction comprising a resin containing a polyether-based 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 urethane polyester or polyether carboxylate 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 is a urethane polyether carboxylate or a urethane polyester carboxylate, functionalized with at least two cycloolefin groups, and having the formula:
wherein:
a=1-100, c=0 or 1 and d=2-100,
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,
Z is a linear, branched, cyclic or polycyclic urethane polyether or urethane polyester 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 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, and
R 4 , R 5 , a, b, c, and d 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.
2. The composition of claim 1 wherein the substrate comprises a dinorbornenyl dicarboxylate urethane polyester.
3. The composition of claim 1 wherein the substrate comprises a dinorbornenyl dicarboxylate urethane polyether.
4. The composition of claim 1 wherein D is a norbornenyl group; a=1, C=1, and Z is:
where R=hexyl and PE=polyether.
5. The composition of claim 1 wherein the substrate is a difunctional urethane polyether carboxylate and the polyether comprises one or more of butylene oxide units, ethylene oxide units or propylene oxide units, or combinations thereof.
6. The composition of claim 1 wherein D is a cycloolefinic residue selected from the group consisting of norbornenyl, norbornenylethyl, cyclopentenyl, 7-oxanorbornenyl, norbomadienyl, and 7-oxanorbomadienyl.
7. The composition of claim 1 wherein the catalyst has the structure:
wherein Bu is butyl, Ph is phenyl and Mes is mesityl.
8. 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.
9. The composition of claim 1 comprising a base part and a catalyst part, wherein the base part comprises the substrate, wherein the catalyst part comprises the metal carbene complex catalyst dissolved in a solvent that is miscible with the base part, and wherein the catalyst is capable of initiating the metathesis reaction upon mixing the base part with the catalyst part at room temperature.
10. A composition capable of undergoing a metathesis reaction upon mixing of its components, the components comprising:
a resin having an urethane polyester carboxylate backbone or an urethane polyether carboxylate 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 tricyclohexyiphosphine (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.
11. The composition of claim 10 wherein the cycloolefin groups are selected from the group consisting of norbornenyl, norbornenylethyl, cyclopentenyl, 7-oxanorbornenyl, norbomadienyl, and 7-oxanorbomadienyl.
12. The composition of claim 10 wherein the catalyst has the structure:
wherein Bu is butyl, Ph is phenyl and Mes is mesityl.
13. The composition of claim 10 wherein the reaction control agent is Tetraallyloxysilane.
14. The composition of claim 10 wherein the resin comprises a dinorbornenyl dicarboxylate urethane polyether.
15. The composition of claim 10 wherein the resin is:
where R=hexyl, PE=polyether, and
16. The composition of claim 9 , wherein the catalyst has the structure (b).
17. The composition of claim 16 wherein the cycloolefin groups are selected from the group consisting of norbornenyl, norbornenylethyl, cyclopentenyl, 7-oxanorbornenyl, norbornadienyl, and 7-oxanorbornadienyl.
18. The composition of claim 16 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.
19. The composition of claim 16 wherein the resin comprises a dinorbornenyl dicarboxylate urethane polyether.
20. The composition of claim 16 wherein the base resin is:
where R=hexyl, PE=polyether, and