Claims
- 1. A method for extending the pot life of a bulk polymerizable reaction solution comprising adding an effective amount of a pot life adjusting agent of the formula: ##STR3## wherein R, R.sub.1, and R.sub.2 independently represent hydrogen, C.sub.1 to C.sub.6 alkyl and the monomethyl, monochloro and dichloro substituents thereof, C.sub.2 to C.sub.6 alkenyl and the monomethyl, monochloro and dichloro substituents thereof; R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 independently represent hydrogen, a methyl group or a halogen atom; R.sub.9 and R.sub.10 independently represent hydrogen or C.sub.1 to C.sub.6 alkyl; n is 0 to 4; and "a" represents a single or double bond with the proviso that when "a" is a double bond, R and R.sub.1 are not present; to a reactive solution comprising at least one norbornene monomer having 3 or more rings in its backbone, tricylcopentadiene, a molybdenum metathesis catalyst and a cocatalyst.
- 2. The method of claim 1 wherein the tricyclopentadiene is selected from the group consisting of symmetrical trimers, unsymmetrical trimers and mixtures thereof.
- 3. The method of claim 1 wherein the norbornene monomer is selected from the group consisting of dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene/methylcyclopentadiene codimer, 1,4-methano-1,1,4a,5,6,7,8,8a-octahydronaphthalene, tetracyclododecene, methyltetracyclododecene, ethyltetracyclododecene, dimethyltetracyclododecene, ethylidenetetracyclododecene, vinyltetracyclododecene, phenyltetracyclododecene and mixtures thereof.
- 4. The method of claim 1 wherein the reactive solution further comprises monomers selected from the group consisting of 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenyl-2-norbornene, cyclobutene, 5-phenyl-2-norbornene, cyclobutene, cyclopentene, cyclopentadiene, cyclooctane, cyclododecene, and mixtures thereof.
- 5. The method of claim 1 wherein the pot life adjusting agent is selected from the group consisting of 5-vinylbicyclo[2,2,1]hepto-2-ene, 5-isopropenylbicylo[2,2,1]hepto-2-ene, 5-vinyl-4-vinylbicyclo[2,2,1]hepto-2-ene, 5-propenylbicyclo[2,2,1]hepto-2-ene, 5-butenyl-bicyclo[2,2,1]hepto-2-ene, 5-pentenyl-bicyclo[2,2,1]hepto-2-ene; monomethyl substitutes of the above; monochloro substitutes of the above; dichloro substitutes of the above; 5-alpha-chlorovinylbicyclo[2,2,1]hepto-2-ene; 5-vinylbicyclo[2,2,1]hepto-1,4-diene; and mixtures thereof.
- 6. The method of claim 1 wherein the pot life adjusting agent is added in the amount of at least 0.5 weight parts per 100 weight parts of monomer.
- 7. The method of claim 6 wherein the pot life adjusting agent is added in an amount of about 1 to 60 weight parts per 100 weight parts of monomer.
- 8. The method of claim 1 wherein the tricyclopentadiene is present in the amount from about 5 to about 60 weight percent of the total monomer in the reaction solution.
- 9. The method of claim 1 wherein the norbornene monomer is present in the amount from about 40 to 95 weight percent of the total monomer in the reactive soltuion.
- 10. The method of claim 1 wherein the reactive solution comprises 5 to 40 weight percent of tricyclopentadiene, 50 to 90 weight percent of at least one norbornene monomer, and 5 to 45 weight percent of the pot life adjusting agent wherein all weight percents are based on the total amount of monomer present in the reactive solution.
- 11. The method of claim 1 wherein the reactive solution further comprises a hydrocarbon based elastomer with a solubility parameter of less than 8.2.
- 12. The method of claim 11 wherein the reactive solution comprises a) about 10 to 50 weight percent of a norbornene monomer selected from the group consisting of tricyclic monomers, tetracyclic monomers, and mixtures thereof; b) 10 to 50 weight percent of the tricyclopentadiene; and c) 40 to 80 weight percent of the pot life adjusting agent wherein all weights are based upon the total monomer contained in the reactive solution.
- 13. The method of claim 12 wherein the pot life adjusting agent is present in the amount from about 45 to 70 weight percent.
- 14. The method of claim 11 wherein said elastomer is selected from the group consisting of natural rubber, ethylene-propylene rubber, butyl rubber, polyisoprene, and mixtures thereof.
- 15. A method for making a ring-opened polynorbornene molded article comprising: feeding a bulk polymerizable reactive solution into a mold, said solution comprising at least one norbornene monomer having 3 or more rings in its backbone, tricyclopentadiene, a pot life extending agent of the formula: ##STR4## wherein R, R.sub.1, and R.sub.2 independently represent hydrogen, C.sub.1 to C.sub.6 alkyl and the monomethyl, monochloro and dichloro substituents thereof, C.sub.2 to C.sub.6 alkenyl and the monomethyl, monochloro and dichloro substituents thereof: R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 independently represent hydrogen, a methyl group or a halogen atom; R.sub.9 and R.sub.10 independently represent hydrogen or C.sub.1 to C.sub.6 alkyl; n is 0 to 4; and "a" represents a single or double bond with the proviso that when "a" is a double bond, R and R.sub.1 are not present, a molybdenum metathesis catalyst and a cocatalyst and; polymerizing said reactive solution in said mold producing a solid article.
- 16. The method of claim 15 wherein reinforcing material is placed in the mold before introducing the reactive solution.
- 17. The method of claim 16 wherein the reinforcing material does not shift during the mold fill step.
- 18. The method of claim 15 wherein the tricyclopentadiene is selected from the group consisting of symmetrical trimers, unsymmetrical trimers and mixtures thereof.
- 19. The method of claim 15 wherein the norbornene monomer is selected from the group consisting of dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene/methylcyclopentadiene codimer, 1,4-methano-1,1,4a,5,6,7,8,8a-octahydronaphthalene, tetracyclododecene, methyltetracyclododecene, ethyltetracyclododecene, dimethyltetracyclododecene, ethylidenetetracyclododecene, vinyltetracyclododecene, phenyltetracyclododecene and mixtures thereof.
- 20. The method of claim 15 wherein the reactive solution further comprises monomers selected from the group consisting of 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenyl-2-norbornene, cyclobutene, cyclopentene, cyclopentadiene, cyclooctane, cyclododecene, and mixtures thereof.
- 21. The method of claim 15 wherein the pot life extending agent is selected from the group consisting of 5-vinylbicyclo[2,2,1]hepto-2-ene, 5-isopropenylbicyclo[2,2,1]hepto-2-ene, 5-vinyl-4-vinylbicyclo[2,2,1]hepto-2-ene, 5-pentenyl-bicyclo[2,2,1]hepto-2-ene; monomethyl substitutes of the above; monochloro substitutes of the above; dichloro substitutes of the above; 5-alpha-chlorovinylbicyclo[2,2,1]hepto-2-ene; 5-vinylbicyclo[2,2,1]hepto-1,4-diene; and mixtures thereof.
- 22. The method of claim 15 wherein the pot life extending agent is added in the amount of at least 0.5 weight parts per 100 weight parts of monomer.
- 23. The method of claim 22 wherein the VNB pot life adjusting agent is added in an amount of about 1 to 60 weight parts per 100 weight parts of monomer.
- 24. The method of claim 16 wherein said reinforcing material is present in the amount of at least 20 weight percent based on the total weight of the molded article.
- 25. The method of claim 15 wherein the tricyclopentadiene is present in the amount from about 5 to about 60 weight percent of the total monomer in the reaction solution.
- 26. The method of claim 15 wherein the norbornene monomer is present in the amount from about 40 to 95 weight percent of the total monomer in the reactive solution.
- 27. The method of claim 15 wherein the reaction solution comprises 5 to 40 weight percent of tricyclopentadiene, 50 to 90 weight percent of at least one norbornene monomer, and 5 to 45 weight percent of the pot life adjusting agent wherein all weight percents are based on the total amount of monomer present in the reactive solution.
- 28. The method of claim 15 wherein the reactive solution further comprises a hydrocarbon based elastomer with a solubility parameter of less than 8.2.
- 29. The method of claim 28 wherein the reactive solution comprises a) about 10 to 50 weight percent of a norbornene monomer selected from the group consisting of tricyclic monomers, tetracyclic monomers, and mixtures thereof; b) 10 to 50 weight percent of the tricyclopentadiene; and c) 40 to 80 weight percent of the pot life adjusting agent wherein all weights are based upon the total monomer contained in the reactive solution.
- 30. The method of claim 29 wherein the pot life adjusting agent is present in the amount from about 45 to 70 weight percent.
- 31. The method of claim 28 wherein said elastomer is selected from the group consisting of natural rubber, ethylene-propylene rubber, butyl rubber, polyisoprene, and mixtures thereof.
- 32. A reactive feed composition having a prolonged pot life comprising: a) at least one norbornene monomer having 3 or more rings in its backbone; b) tricyclopentadiene, c) a molybdenum metathesis catalyst and cocatalyst; and d) a pot life extending agent of the formula: ##STR5## wherein R, R.sub.1, and R.sub.2 independently represent hydrogen, C.sub.1 to C.sub.6 alkyl and the monomethyl, monochloro and dichloro substituents thereof C.sub.2 to C.sub.6 alkenyl and the monomethyl, monochloro and dichloro substituents thereof; R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 independently represent hydrogen, a methyl group or a halogen atom; R.sub.9 and R.sub.10 independently represent hydrogen or C.sub.1 to C.sub.6 alkyl; n is 0 to 4; and "a" represents a single or double bond with the proviso that when "a" is a double bond, R and R.sub.1 are not present.
- 33. The composition of claim 32 wherein the tricyclopentadiene is selected from the group consisting of symmetrical trimers, unsymmetrical trimers and mixtures thereof.
- 34. The composition of claim 32 wherein the norbornene monomer is selected from the group consisting of dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene/methylcyclopentadiene codimer, 1,4-methano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, tetracyclododecene, methyltetracyclododecene, ethyltetracyclododecene, dimethyltetracyclododecene, ethylidenetetracyclododecene, vinyltetracyclododecene, phenyltetracyclododecene; and mixtures thereof.
- 35. The composition of claim 32 wherein the reaction solution further comprises monomers selected from the group consisting of 2-norbornene, 5-methyl-2norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenyl-2-norbornene, cyclobutene, cyclopentene, cyclopentadiene, cyclooctane, cyclododecene, and mixtures thereof.
- 36. The composition of claim 2 wherein the pot life adjusting agent is selected from the group consisting of 5-vinylbicyclo[2,2,1]hepto-2-ene, 5-isopropenylbicyclo [2,2,1]hepto-2-ene, 5-vinyl-4-vinylbicyclo[2,2,1]hepto-2-ene, 5-propenyl-bicyclo[2,2,1]hepto-2-ene, 5-butenyl-bicyclo[2,2,1]hepto-2-ene, 5-pentenyl-bicyclo[2,2,1]hepto-2-ene; monomethyl substitutes of the above; monochloro substitutes of the above; dichloro substitutes of the above; 5-alpha-chlorovinylbicyclo[2,2,1]hepto-2-ene; 5-vinylbicyclo [2,2,1]hepto-1,4-diene; and mixtures thereof.
- 37. The composition of claim 32 wherein the pot life adjusting agent is added in the amount of at least 0.5 weight parts per 100 weight parts of monomer.
- 38. The composition of claim 32 wherein the pot life adjusting agent is added in an amount of about 1 to 60 weight parts per 100 weight parts of monomer.
- 39. The composition of claim 32 wherein the tricyclopentadiene is present in the amount from about 5 to about 60 weight percent of the total monomer in the reaction solution.
- 40. The composition of claim 32 wherein the norbornene monomer is present in the amount from about 40 to 95 weight percent of the total monomer in the reactive solution.
- 41. The composition of claim 32 wherein the reaction solution comprises 5 to 40 weight percent of tricyclopentadiene, 50 to 90 weight percent of at least one norbornene monomer, and 5 to 45 weight percent of the pot life adjusting agent wherein all weight percents are based on the total amount of monomer present in the reactive solution.
- 42. The composition of claim 32 wherein the reactive solution further comprises a hydrocarbon based elastomer with a solubility parameter of less than 8.2.
- 43. The composition of claim 42 wherein the reactive solution comprises a) about 10 to 50 weight percent of a norbornene monomer selected from the group consisting of tricyclic monomers, tetracyclic monomers, and mixtures thereof; b) 10 to 50 weight percent of the tricyclopentadiene; and c) 40 to 80 weight percent of the pot life adjusting agent wherein all weights are based upon the total monomer contained in the reactive solution.
- 44. The composition of claim 43 wherein the pot life adjusting agent is present in the amount from about 45 to 70 weight percent.
- 45. The composition of claim 42 wherein said elastomer is selected from the group consisting of natural rubber, ethylene-propylene rubber, butyl rubber, polyisoprene, and mixtures thereof.
Priority Claims (2)
Number |
Date |
Country |
Kind |
1-285555 |
Nov 1989 |
JPX |
|
1-285556 |
Nov 1989 |
JPX |
|
Parent Case Info
This application is a continuation-in-part of copending application Ser. No. 07/606,810 filed Oct. 31, 1990, now abandoned.
US Referenced Citations (1)
Number |
Name |
Date |
Kind |
4943621 |
Janda et al. |
Jul 1990 |
|
Foreign Referenced Citations (3)
Number |
Date |
Country |
0264260 |
Apr 1988 |
EPX |
63-12612 |
Jan 1988 |
JPX |
3012612 |
Jan 1988 |
JPX |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
606810 |
Oct 1990 |
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