Claims
- 1. A method of synthesizing polymers from acrylates, norbornenes and mixtures thereof, which comprises contacting under polymerization conditions and in the presence of a solvent (a) at least one monomer selected from the group consisting of acrylates, norbornenes and mixtures thereof with (b) a catalyst system consisting essentially of a Pd(II) dimer component having the formula:
- [(L)Pd(R)(X)].sub.2,
- wherein L is a monodentate phosphorus or nitrogen ligand, X is an anionic group, and R is an alkyl or aryl group.
- 2. The method of claim 1, wherein R is selected from the group consisting of ethyl, methyl, propyl, isopropyl, n-butyl, t-butyl, and X is selected from the group consisting of Cl, Br and carboxylate.
- 3. The method of claim 1, wherein said at least one monomer is selected from the group consisting of acrylate monomers.
- 4. The method of claim 1, wherein said at least one monomer is selected from the group consisting of norbornene monomers.
- 5. The method of claim 1, wherein said at least one monomer comprises a mixture of at least one acrylate monomer and at least one norbornene monomer.
- 6. The method of claim 2, wherein L is selected from the group consisting of aromatic and heterocyclic amines and compounds conforming to the formula R.sup.2.sub.3 P, where R.sup.2 is selected from alkyl groups, aryl groups and mixtures thereof.
- 7. The method of claim 6, wherein L is selected from the group consisting of triphenyl phosphine (PPh.sub.3), tricyclohexyl phosphine (PCy.sub.3), trimethyl phosphine (PMe.sub.3), triethyl phosphine (PEt.sub.3), tri-n-propyl phosphine (P(n-Pr).sub.3), tri-n-butyl phosphine (P(n-Bu).sub.3), tri-t-butyl phosphine (P(t-Bu).sub.3), tri-p-tolyl phosphine (P(p-Tol).sub.3), methyldiphenyl phosphine (P(Me)(Ph).sub.2), phenyldimethyl phosphine (PPh(Me).sub.2), ethyldiphenyl phosphine (P(Et)(Ph).sub.2), pyridine, t-butyl pyridine, aniline, trimethyl aniline and imidazole.
- 8. The method of claim 3, wherein L is selected from the group consisting of aromatic and heterocyclic amines and compounds conforming to the formula R.sup.2.sub.3 P, where R.sup.2 is selected from alkyl groups, aryl groups and mixtures thereof.
- 9. The method of claim 8, wherein L is selected from the group consisting of triphenyl phosphine (PPh.sub.3), tricyclohexyl phosphine (PCy.sub.3), trimethyl phosphine (PMe.sub.3), triethyl phosphine (PEt.sub.3), tri-n-propyl phosphine (P(n-Pr).sub.3), tri-n-butyl phosphine (P(n-Bu).sub.3), tri-t-butyl phosphine (P(t-Bu).sub.3), tri-p-tolyl phosphine (P(p-Tol).sub.3), methyldiphenyl phosphine (P(Me)(Ph).sub.2), phenyldimethyl phosphine (PPh(Me).sub.2), ethyldiphenyl phosphine (P(Et)(Ph).sub.2), pyridine, t-butyl pyridine, aniline, trimethyl aniline and imidazole.
- 10. The method of claim 4, wherein L is selected from the group consisting of aromatic and heterocyclic amines and compounds conforming to the formula R.sup.2.sub.3 P, where R.sup.2 is selected from alkyl groups, aryl groups and mixtures thereof.
- 11. The method of claim 10, wherein L is selected from the group consisting of triphenyl phosphine (PPh.sub.3), tricyclohexyl phosphine (PCy.sub.3), trimethyl phosphine (PMe.sub.3), triethyl phosphine (PEt.sub.3), tri-n-propyl phosphine (P(n-Pr).sub.3), tri-n-butyl phosphine (P(n-Bu).sub.3), tri-t-butyl phosphine (P(t-Bu).sub.3), tri-p-tolyl phosphine (P(p-Tol).sub.3), methyldiphenyl phosphine (P(Me)(Ph).sub.2), phenyldimethyl phosphine (PPh (Me).sub.2), ethyldiphenyl phosphine (P(Et)(Ph).sub.2), pyridine, t-butyl pyridine, aniline, trimethyl aniline and imidazole.
- 12. The method of claim 5, wherein L is selected from the group consisting of aromatic and heterocyclic amines and compounds conforming to the formula R.sup.2.sub.3 P, where R.sup.2 is selected from alkyl groups, aryl groups and mixtures thereof.
- 13. The method of claim 12, wherein L is selected from the group consisting of triphenyl phosphine (PPh.sub.3), tricyclohexyl phosphine (PCy.sub.3), trimethyl phosphine (PMe.sub.3), triethyl phosphine (PEt.sub.3), tri-n-propyl phosphine (P(n-Pr).sub.3), tri-n-butyl phosphine (P(n-Bu).sub.3), tri-t-butyl phosphine (P(t-Bu).sub.3), tri-p-tolyl phosphine (P(p-Tol).sub.3), methyldiphenyl phosphine (P(Me)(Ph).sub.2), phenyldimethyl phosphine (PPh (Me).sub.2), ethyldiphenyl phosphine (P(Et)(Ph).sub.2), pyridine, t-butyl pyridine, aniline, trimethyl aniline and imidazole.
- 14. The method of claim 2, wherein L is selected from the group consisting of compounds conforming to the formula R.sup.3.sub.3 N, where R.sup.3 is selected from the group consisting of alkyl groups, aryl groups and mixtures thereof.
- 15. The method of claim 14, wherein R.sup.3 is selected from the group consisting of methyl (CH.sub.3), ethyl (CH.sub.2 CH.sub.3), propyl (CH.sub.2 CH.sub.2 CH.sub.3), n-butyl (CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), t-butyl (C--(CH.sub.3).sub.3), phenyl (C.sub.6 H.sub.6) and p-tolyl (C.sub.7 H.sub.8) and mixtures thereof.
- 16. The method of claim 3, wherein L is selected from the group consisting of compounds conforming to the formula R.sup.3.sub.3 N, where R.sub.3 is selected from the group consisting of alkyl groups, aryl groups and mixtures thereof.
- 17. The method of claim 16, wherein R.sup.3 is selected from the group consisting of methyl (CH.sub.3), ethyl (CH.sub.2 CH.sub.3), propyl (CH.sub.2 CH.sub.2 CH.sub.3), n-butyl (CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), t-butyl (C--(CH.sub.3).sub.3), phenyl (C.sub.6 H.sub.6) and p-tolyl (C.sub.7 H.sub.8) and mixtures thereof.
- 18. The method of claim 4, wherein L is selected from the group consisting of compounds conforming to the formula R.sup.3.sub.3 N, where R.sup.3 is selected from the group consisting of alkyl groups, aryl groups and mixtures thereof.
- 19. The method of claim 18, wherein R.sup.3 is selected from the group consisting of methyl (CH.sub.3), ethyl (CH.sub.2 CH.sub.3), propyl (CH.sub.2 CH.sub.2 CH.sub.3), n-butyl (CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), t-butyl (C--(CH.sub.3).sub.3), phenyl (C.sub.6 H.sub.6) and p-tolyl (C.sub.7 H.sub.8) and mixtures thereof.
- 20. The method of claim 5, wherein L is selected from the group consisting of compounds conforming to the formula R.sup.3.sub.3 N, where R.sup.3 is selected from the group consisting of alkyl groups, aryl groups and mixtures thereof.
- 21. The method of claim 20, wherein R.sup.3 is selected from the group consisting of methyl (CH.sub.3), ethyl (CH.sub.2 CH.sub.3), propyl (CH.sub.2 CH.sub.2 CH.sub.3), n-butyl (CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), t-butyl (C--(CH.sub.3).sub.3), phenyl (C.sub.6 H.sub.6) and p-tolyl (C.sub.7 H.sub.8) and mixtures thereof.
- 22. The method of claim 3, wherein said acrylate monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate and compounds of the formula H.sub.2 C.dbd.CHCOOR, where R is an alkyl group or an aryl group.
- 23. The method of claim 3, wherein R is selected from the group consisting of methyl (CH.sub.3), ethyl (CH.sub.2 CH.sub.3), propyl (CH.sub.2 CH.sub.2 CH.sub.3), n-butyl (CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3), t-butyl (C--(CH.sub.3).sub.3), phenyl (C.sub.6 H.sub.6) and p-tolyl (C.sub.7 H.sub.8).
- 24. The method of claim 4, wherein said norbornene monomer is selected from the group consisting of norbornene, norbornadiene and compounds conforming to the formulas 5-norbornene-2-R.sup.1a, 5-norbornene-2,2-R.sup.1a, 5-norbornene-3-R.sup.1a, 5-norbornene-3,3-R.sup.1a, 5-norbornene-2,3-R.sup.1a , or 5-norbornene-2-R.sup.1a -3-R.sup.1b , where R.sup.1a and R.sup.1b , independently, represent an alkyl or aryl group, or a residue of an alcohol or carboxylic acid.
- 25. The method of claim 4, wherein said norbornene monomer is selected from the group consisting of norbornene, 5-norbornene-2-methanol, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, 5-norbornene-2,2-dimethanol, 5-norbornen-2-ol, norbornadiene, 5-norbornene-2,3-diphenyl, cis-5-norbornene-endo-2,3-dicarboxylic acid dimethyl ester, 5-norbornen-2-yl-acetate and 5-norbornene-2-carboxyaldehyde.
- 26. The method of claim 5, wherein at least one acrylate monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, acrylamide, acrolein, acryloyl chloride, and compounds of the formula H.sub.2 C.dbd.CHCOOR, where R is an alkyl group or an aryl group; and wherein at least one norbornene monomer is selected from the group consisting of norbornene, norbornadiene and compounds conforming to the formulas 5-norbornene-2-R.sup.1a, 5-norbornene-2,2- R.sup.1a, 5-norbornene-3- R.sup.1a, 5-norbornene-3,3-R.sup.1a, 5-norbornene-2,3-R.sup.1a, or 5-norbornene-2-R.sup.1a -3-R.sup.1b , where R.sup.1a R.sup.1b , independently, represent an alkyl or aryl group, or a residue of an alcohol or carboxylic acid.
- 27. The method of claim 5, wherein the ratio of acrylate monomer to norbornene monomer added to the polymerization reaction is from about 100:1 to about 1:100.
- 28. The method of claim 5, wherein the ratio of acrylate monomer to norbornene monomer added to the polymerization reaction is from about 10:1 to about 1:10.
- 29. The method of claim 26, wherein the ratio of acrylate monomer to norbornene monomer added to the polymerization reaction is from about 100:1 to about 1:100.
- 30. The method of claim 26, wherein the ratio of acrylate monomer to norbornene monomer added to the polymerization reaction is from about 10:1 to about 1:10.
Parent Case Info
This application claims the benefit of U.S. Provisional No. 60/050,107 filed Jun. 18, 1997.
US Referenced Citations (1)
Number |
Name |
Date |
Kind |
6034259 |
Brookhart et al. |
Mar 2000 |
|
Foreign Referenced Citations (1)
Number |
Date |
Country |
837079 A2 |
Apr 1998 |
EPX |