Liquid molding compositions
The present invention relates to methods and compositions for olefin metathesis. More particularly, the present invention relates to methods and compositions for ring opening metathesis polymerization (ROMP) reactions and the manufacture of polymer articles and/or polymer composite articles via ROMP Polymer products produced via the metathesis reactions of the invention may be utilized in a wide range of materials and composite applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.
1. A ring opening metathesis polymerization (ROMP) composition, comprising a catalyst composition comprising at least one metal carbene olefin metathesis catalyst, and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight tricyclopentadiene, 0.01% to 4.00% by weight tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins.
2. The composition of claim 1 , wherein the one or more other cyclic olefins is selected from dicyclopentadiene.
3. The composition of claim 1 , wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight tricyclopentadiene, 0.01% to 4.00% by weight tetracyclopentadiene, and 64.99% to 26.00% by weight dicyclopentadiene.
4. The composition of claim 1 , wherein the at least one metal carbene olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I)
in which:
M is a Group 8 transition metal;
L 1 , L 2 , and L 3 are neutral electron donor ligands;
n is 0 or 1, such that L 3 may or may not be present;
m is 0, 1, or 2;
k is 0 or 1;
X 1 and X 2 are anionic ligands; and
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or functional groups,
wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 can be taken together to form one or more cyclic groups, and further wherein any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 may be attached to a support.
5. The composition of claim 4 , wherein R 1 and R 2 are taken together to form an indenylidene moiety.
6. The composition of claim 4 , wherein L 1 is carbene ligand having the structure of formula (II)
wherein,
X and Y are heteroatoms selected from N, O, S, or P;
p is zero when X is O or S, and p is 1 when X is N or P;
q is zero when Y is O or S, and q is 1 when Y is N or P;
Q 1 , Q 2 , Q 3 , and Q 4 are linkers selected from hydrocarbylene, substituted hydrocarbylene, hetero-atom containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene, and —(CO)—, and further wherein two or more substituents on adjacent atoms within Q 1 , Q 2 , Q 3 , and Q 4 may be linked to form an additional cyclic group;
w, x, y, and z are independently zero or 1; and
R 3 , R 3A , R 4 , and R 4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl,
wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , R 2 , R 3 , R 3A , R 4 , R 4A , Q 1 , Q 2 , Q 3 , and Q 4 can be taken together to form a cyclic group, and any one or more of X 1 , X 2 , L 2 , L 3 , Q 1 , Q 2 , Q 3 , Q 4 , R 1 , R 2 , R 3 , R 3A , R 4 , and R 4A may be attached to a support.
7. The composition of claim 4 , wherein L 1 is an N-heterocyclic carbene ligand.
8. A method for making a ring opening metathesis polymerization (ROMP) polymer, comprising providing a catalyst composition comprising at least one metal carbene olefin metathesis catalyst, providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight tricyclopentadiene, 0.01% to 4.00% by weight tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins, combining the catalyst composition and the resin composition to form a ROMP composition, and subjecting the ROMP composition to conditions effective to promote polymerization of the ROMP composition.
9. The method of claim 8 , wherein the one or more other cyclic olefins is selected from dicyclopentadiene.
10. The method of claim 8 , wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight tricyclopentadiene, 0.01% to 4.00% by weight tetracyclopentadiene, and 64.99% to 26.00% by weight dicyclopentadiene.
11. The method of claim 8 , wherein the at least one metal carbene olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I)
in which:
M is a Group 8 transition metal;
L 1 , L 2 , and L 3 are neutral electron donor ligands;
n is 0 or 1, such that L 3 may or may not be present;
m is 0, 1, or 2;
k is 0 or 1;
X 1 and X 2 are anionic ligands; and
R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or functional groups,
wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 can be taken together to form one or more cyclic groups, and further wherein any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 may be attached to a support.
12. The method of claim 11 , wherein R 1 and R 2 are taken together to form an indenylidene moiety.
13. The method of claim 11 , wherein L 1 is carbene ligand having the structure of formula (II)
wherein,
X and Y are heteroatoms selected from N, O, S, or P;
p is zero when X is O or S, and p is 1 when X is N or P;
q is zero when Y is O or S, and q is 1 when Y is N or P;
Q 1 , Q 2 , Q 3 , and Q 4 are linkers selected from hydrocarbylene, substituted hydrocarbylene, hetero-atom containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene, and —(CO)—, and further wherein two or more substituents on adjacent atoms within Q 1 , Q 2 , Q 3 , and Q 4 may be linked to form an additional cyclic group;
w, x, y, and z are independently zero or 1; and
R 3 , R 3A , R 4 , and R 4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl,
wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , R 2 , R 3 , R 3A , R 4 , R 4A , Q 1 , Q 2 , Q 3 , and Q 4 can be taken together to form a cyclic group, and any one or more of X 1 , X 2 , L 2 , L 3 , Q 1 , Q 2 , Q 3 , Q 4 , R 1 , R 2 , R 3 , R 3A , R 4 , and R 4A may be attached to a support.
14. The method of claim 11 , wherein L 1 is an N-heterocyclic carbene ligand.