Polyethers, methods of making same, and uses thereof
Isotactic polyethers, methods of making polyethers, and uses of polyethers. The polyethers have a chain transfer group formed from a chain transfer agent. The methods of making the polyethers use monoalcohol chain transfer agents or multifunctional chain transfer agents. The polyethers can be used in materials, such as polyurethanes, elastomers, thermoset plastics, and thermoplastics, and as non-ionic surfactants.
1. A polymer having the following structure:
wherein CTG is a chain transfer group and PE is an isotactic polyether group, and i is from 1 to 10, and
wherein the mm-triad content of the polymer is greater than 75% and the M n of the polymer is from 1,000 to 40,000 g/mol.
2. The polymer of claim 1 , wherein the polymer has the following structure:
where R 1 is
R 2 is H or C 1 to C 20 aliphatic group, R 3 is H or C 1 to C 20 aliphatic group, R 4 is H or a C 1 to C 20 aliphatic group, R 5 is H or a C 1 to C 20 aliphatic group, R 6 is C 2 to C 20 aliphatic group, C 3 to C 20 carbocyclic group, C 6 to C 24 aryl group,
R 7 is H,
or C 1 to C 20 aliphatic group, R 8 is absent or C 1 to C 20 aliphatic group, n is from 5 to 500, m is from 1 to 500, and x is from 5 to 500,
wherein, optionally, any two of R 4 , R 5 , and R 2 taken together can form with their intervening atoms can form one or more rings selected from the group consisting of: C 3 to C 14 carbocyclic group, C 3 to C 14 heterocyclic group, C 6 to C 10 aryl group, and C 5 to C 10 heteroaryl group.
3. The polymer of claim 1 , wherein the chain transfer group is a diol chain transfer group, a diacid chain transfer group, or a hydroxyacid chain transfer group.
4. The polymer of claim 1 , wherein the M n of the polymer is from 1,000 to 30,000 g/mol, 1,000 to 15,000 g/mol, or 1,000 to 12,000 g/mol.
5. The polymer of claim 1 , wherein the polymer has a mm-triad content is greater than 80%, 85%, 90%, 91%, 92%, 95%, 96%, 97%, 98%, or 99%.
6. The polymer of claim 1 , wherein the PDI of the polymer is less than 2.
7. The polymer of claim 1 , wherein the polymer is polypropylene oxide.
8. A method for making a polymer having the structure of claim 1 comprising the steps of: polymerizing an epoxide in the presence of a catalyst, an ionic co-catalyst, and a monoalcohol chain transfer agent or multifunctional chain transfer agent.
9. The method of claim 8 , wherein the monoalcohol chain transfer agent is methanol, ethanol, i-propanol, benzyl alcohol, p-methoxybenzyl alcohol, or has the following structure:
wherein * denotes a chiral carbon center.
10. The method of claim 8 , wherein the multifunctional chain transfer agent is R 16 —(COOH/OH) z , wherein R 16 is C 1 to C 20 aliphatic group, or C 1 to C 20 carbocyclic group, and z is from 1 to 10.
11. The method of claim 8 , wherein the multifunctional chain transfer agent is
sugars, polysaccharides, glycerols, or hydroxyl or carboxyl functional polymers.
12. The method of claim 8 , wherein the epoxide is chiral or racemic.
13. The method of claim 8 , wherein the epoxide, catalyst, ionic co-catalyst, and monoalcohol chain transfer agent or multifunctional chain transfer agent are contacted in a solvent.
14. The method of claim 8 , wherein the catalyst is:
M is a metal, X is a nucleophile or counterion, t is an integer from 0 to 2, Q is C 1 to C 20 aliphatic group, C 5 to C 20 cycloalkyl group, and each R 9 through R 17 independently are selected from the group consisting of hydrogen, C 1 to C 20 aliphatic group, halide, C 1 to C 20 alkoxide group, and C 6 to C 20 aryl group,
wherein, optionally, adjacent R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , or R 17 groups taken together with their intervening atoms to form a saturated, partially unsaturated, or aromatic 5 to 12 membered ring containing 0 to 4 heteroatoms, 5 to 6 membered carbocyclic group, aryl group, or 5 to 7-membered heteroaryl group, wherein the rings or groups are substituted, and the catalyst is racemic or chiral.
15. The method of claim 14 , wherein the catalyst is selected from the group consisting of:
16. The method of claim 8 , wherein the ionic co-catalyst is PPNOPiv.
17. A material comprising the polymer of claim 1 .
18. The material of claim 17 , wherein the material is a polyurethane, elastomer, thermoset plastic, or thermoplastic.
19. The polymer of claim 1 , wherein the M n of the polymer is from 1,000 to 8,000 g/mol and the melting point of the polymer is 58° C. or greater.
20. The polymer of claim 1 , wherein the M n of the polymer is from 1,000 to 8,000 g/mol and the melting point of the polymer is 58° C. to 71° C.