Claims
- 1. A method for preparing a triblock copolymer of the formula:
- 2. The method of claim 1 wherein the metathesis catalyst is of the formula:
- 3. The method of claim 2 wherein the substituent group is substituted with one or more substituted or unsubstituted moieties selected from the group consisting of C1-C1 alkyl, C1-C10 alkoxy, and aryl.
- 4. The method of claim 3 wherein the moiety is substituted with one or more groups selected from the group consisting of halogen, C1-C5 alkyl, C1-C5 alkoxy.
- 5. The method of claim 2 wherein the substituent is functionalized with a moiety selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
- 6. The method of claim 2 wherein R is hydrogen and R1 is selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, aryl, unsubstituted phenyl, substituted phenyl, unsubstituted vinyl, and substituted vinyl; and wherein the substituted phenyl and substituted vinyl are each independently substituted with one or more groups selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, phenyl, hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
- 7. The method of claim 2 wherein L and L1 are each independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether.
- 8. The method of claim 2 wherein L and L1 are each a phosphine of the formula PR3R4R5 wherein R3, R4, and R5 are each independently selected from the group consisting of aryl and C1-C10 alkyl.
- 9. The method of claim 8 wherein R3, R4, and R5 are each independently selected from the group consisting of primary alkyl, secondary alkyl, and cycloalkyl.
- 10. The method of claim 8 wherein L and L1 are each independently selected from the group consisting of P(cyclohexyl)3, P(cyclopentyl)3, P(isopropyl)3, and P(phenyl)3.
- 11. The method of claim 2 wherein X and X1 are each independently selected from the group consisting of hydrogen, halogen, substituted moiety and unsubstituted moiety, wherein the moiety is selected from the group consisting of C1-C20 alkyl, aryl, C1-C20 alkoxide, aryloxide, C3-C20 alkyldiketonate, aryidiketonate, C1-C20 carboxylate, arylsulfonate, C1-C20 alkylsulfonate, C1-C20 alkylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, and wherein the moiety substitution is selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, and aryl.
- 12. The method of claim 2 wherein X and X1 are each independently selected from the group consisting of halide, benzoate, C1-C5 carboxylate, C1-C5 alkyl, phenoxy, C1-C5 alkoxy, C1-C5 alkylthio, aryl, and C1-C5 alkyl sulfonate.
- 13. The method of claim 2 wherein X and X1 are each independently selected from the group consisting of halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate.
- 14. The method of claim 1 wherein the cycloalkene is selected from the group consisting of norbornene, norbornadiene, cyclopentene, dicyclopentadiene, cyclo-octene, 7-oxanorbornene, 7-oxanorbornadiene, cyclodocene, 1,3-cyclooctadiene, 1,5-cyclooctadiene, and 1,3-cycloheptadiene, wherein the cycloalkene is substituted or unsubstituted.
- 15. The method of claim 1 wherein the cycloalkene is 1,5-cyclo-octadiene.
- 16. The method of claim 1 wherein Z is selected from the group consisting of chloride, bromide, allyl chloride, allyl bromide, 2-chloro isobutyrate, 2-bromo isobutyrate, 2-chloro proprionate, 2-bromo proprionate, 2-chloro acetate, 2-bromo acetate, benzyl chloride, benzyl bromide, C1-C20 alkyl benzyl chloride, C1-C20 alkyl benzyl bromide, toluenesulfonyl chloride, toluenesulfonyl bromide, trichloromethyl, tribromomethyl, dichloromethyl, and dibromomethyl, wherein Z is substituted or unsubstituted.
- 17. The method of claim 16 wherein Z is substituted with a moiety selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, and aryl, wherein the moiety is substituted or unsubstituted.
- 18. The method of claim 17 wherein the moiety is substituted with one or more groups selected from the group consisting of halogen, C1-C5 alkyl, C1-C5 alkoxy, and phenyl.
- 19. The method of claim 1 wherein R′ is substituted with a substituent selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, and aryl, wherein the substituent is substituted or unsubstituted.
- 20. The method of claim 19 wherein the substituent substitution is selected from the group consisting of halogen, C1-C5 alkyl, and C1-C5 alkoxy.
- 21. The method of claim 1 wherein the alkene is functionalized with a group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
- 22. The method of claim 1 wherein the alkene is selected from the group consisting of styrene, methyl methacrylate, n-butyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, 4-vinylpyridine and glycidyl acrylate.
- 23. The method of claim 1 wherein the ATRP catalyst is of the formula MXpLq wherein M is selected from the group consisting of iron, ruthenium, nickel, and copper; X is bromide or chloride; and L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether; and wherein p and q are integers.
- 24. The method of claim 1 wherein the ATRP catalyst is selected from the group consisting of CuCl/2,2′-bipyridine, CuBr/2,2′-bipyridine, CuCl/4-4′-di-n-heptyl-2,2′-bipyridine and CuBr/4-4′-di-n-heptyl-2,2′-bipyridine.
- 25. The method of claim 1 wherein the formation of the triblock copolymers occurs in one pot.
- 26. A method for preparing a triblock copolymer of the formula
- 27. The method of claim 26 wherein the cycloalkene is 1,5-cyclooctadiene, Z is allyl chloride or 2-bromoisobutyrate and the alkene is styrene or methyl methacrylate.
- 28. A triblock copolymer of the formula:
- 29. The copolymer of claim 28 wherein the cycloalkene is 1,5-cyclooctadiene, Z is allyl chloride or 2-bromoisobutyrate, the alkene is styrene or methyl methacrylate and the ATRP organometallic catalyst is CuCl/2,2′-bipyridine or CuBr/2,2′-bipyridine.
- 30. A method for preparing a copolymer of the formula:
- 31. A method for preparing a triblock copolymer of the formula:
- 32. A method for preparing an SBS triblock copolymer of the formula:
- 33. A triblock copolymer having no 1,2 PBD structure in the PBD portion of the copolymer.
Parent Case Info
[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 60/124,915, filed Mar. 18, 1999, the contents of which are herein incorporated by reference in its entirety.
Government Interests
[0002] The U.S. Government has certain rights in this invention pursuant to Grant No. 9509745 awarded by the National Science Foundation.
Provisional Applications (1)
|
Number |
Date |
Country |
|
60124915 |
Mar 1999 |
US |
Divisions (1)
|
Number |
Date |
Country |
Parent |
09527757 |
Mar 2000 |
US |
Child |
10151543 |
May 2002 |
US |