Polymerization catalysts, methods and products
The invention provides novel polymer compositions and methods for preparing such compositions. The invention also provides methods for polymerizing various unsaturated monomers, including naturally occurring or plant biomass-derived renewable acrylic monomers. The monomers can be rapidly polymerized using various organic catalysts or organometallic catalysts, as described herein. In one embodiment, nearly perfectly isotactic polymers (mmmm>99%) can be prepared using a C 2 -symmetric zirconocenium catalyst.
1. A highly isotactic polymer of Formula (I):
wherein
n is about 10 to about 45,000;
R 1 is (C 1 -C 6 )alkyl, phenyl, or benzyl; and
each of the carbons having substituent R 1 has an (R) stereochemical configuration, or each of the carbons having substituent R 1 has an (S) stereochemical configuration; wherein the polymer of Formula (I) comprises at least 90% isotactic triads with respect to the quaternary carbons of the polymer chain.
2. The polymer of claim 1 wherein the polymer comprises at least 99% isotactic triads with respect to the quaternary carbons of the polymer chain.
3. The polymer of claim 2 wherein the polymer comprises at least 99% isotactic pentads with respect to the quaternary carbons of the polymer chain.
4. The polymer of claim 1 wherein the polymer is insoluble in water, methanol, toluene, methylene chloride, 1,2-dichlorobenzene, acetonitrile, THF, DMSO, and DMF at room temperature.
5. The polymer of claim 1 wherein the polymer is insoluble in 1,2-dichlorobenzene at 180° C., THF at 60° C., DMSO at 100° C., and DMF at 100° C.
6. The polymer of claim 1 wherein the polymer has a glass transition temperature (T g ) of at least about 250° C.
7. The polymer of claim 1 wherein the polymer has a glass transition temperature (T g ) of at least about 280° C.
8. A composition comprising highly isotactic polymers of claim 1 , wherein the composition comprises a first set of polymers wherein each of the carbons having substituent R 1 have an (R) stereochemical configuration and a second set of polymers wherein each of the carbons having substituent R 1 have an (S) stereochemical configuration.
9. The composition of claim 8 wherein the polymers comprise at least 99% isotactic pentads with respect to the quaternary carbons of the polymer chains.
10. A method for preparing a polymer of Formula (II):
wherein
n is about 10 to about 45,000; R 1 is H, (C 1 -C 6 )alkyl, phenyl, or benzyl; R 2 is H, (C 1 -C 6 )alkyl, phenyl, or benzyl; and one or both of R 1 and R 2 is H;
the method comprising polymerizing a monomer of Formula (III):
wherein R 1 is H, (C 1 -C 6 )alkyl, phenyl, or benzyl; R 2 is H, (C 1 -C 6 )alkyl, phenyl, or benzyl; and one or both of R 1 and R 2 is H;
in the presence of an effective amount of a catalyst, wherein the catalyst is the C 2 -symmetric zirconocenium catalyst (1) or (2):
wherein the polymer of Formula (II) is formed by coordination polymerization with the catalyst and the glass transition temperature (T g ) of the product polymer is greater than about 190° C.
11. The method of claim 10 wherein the monomer of Formula (III) is β-methyl-α-methylene-γ-butyrolactone ( β MMBL), and the polymer of Formula (II) is highly isotactic at the main chain quaternary carbons, comprising at least 90% isotactic triads.
12. The method of claim 11 wherein the C 2 -symmetric zirconocenium catalyst is (1):
13. The method of claim 12 wherein the polymer of Formula (II) comprises at least 99% isotactic pentads.
14. The method of claim 13 wherein the polymer of Formula (II) is insoluble in water, methanol, toluene, methylene chloride, 1,2-dichlorobenzene, acetonitrile, THF, DMSO, and DMF at room temperature, and insoluble in 1,2-dichlorobenzene at 180° C., THF at 60° C., DMSO at 100° C., and DMF at 100° C.
15. The method of claim 10 wherein the monomer of Formula (III) is α-methylene-γ-butyrolactone (MBL), γ-methyl-α-methylene-γ-butyrolactone ( γ MMBL), or β-methyl-α-methylene-γ-butyrolactone ( β MMBL).
16. The method of claim 10 wherein the polymer product has a molecular weight polymer of at least 10 kDa.
17. The method of claim 13 wherein the polymer of Formula (II) has a glass transition temperature (T g ) of greater than about 290° C.
18. The polymer of claim 1 wherein R 1 is methyl.
19. The polymer of claim 3 wherein R 1 is methyl.
20. The polymer of claim 7 wherein R 1 is methyl.
21. The method of claim 13 wherein the monomer of Formula (III) is β-methyl-α-methylene-γ-butyrolactone ( β MMBL).