Isotactic polyethers and bimetallic catalysts, methods of making same, and uses thereof
Provided are compositions comprising isotactic polyethers. Methods of making isotactic polyethers, and uses thereof are also disclosed. Also provided are bimetallic complexes that can be used as catalyst. Methods of making isotactic polyethers and bimetallic complexes and uses thereof are also disclosed. For example, a racemic bimetallic (salalen)CrCl polymerization catalyst was prepared and used alkyl diol, PO-oligomer triols, and aPPO and PCL diols as CSAs in order to produce α,ω-hydroxy telechelic iPPO. These telechelic polymers have controlled molecular weights and are semicrystalline. Amorphous α,ω-hydroxy telechelic PPO can also be produced by increasing the reaction temperature in conjunction with the use of CSAs.
1. A polymer comprising the structure:
wherein CSG is a chain shuttling group and PE is an isotactic polyether group, and i is from 1 to 10,
the isotactic polyether group comprises at least 2 stereoregular blocks having the following structure:
wherein R 1 is H or C 1 to C 20 aliphatic group, R 4 is H or C 1 to C 20 aliphatic group,
R 2 is H or a C 1 to C 20 aliphatic group, R 3 is H or a C 1 to C 20 aliphatic group, n is independently at each occurrence in the polyether group 5 to 500, x and y are independently at each occurrence in the polyether group 5 to 500, and z is greater than or equal to 1, and
the mr-triad+rm-triad is greater than or equal to 2 times the rr-triad, and the M n of the polymer is from 500 to 500,000 g/mol.
2. The polymer of claim 1 , wherein the chain shuttling group has one of the following structures:
wherein A is O or S, R 5 is a C 1 to C 20 carbon-containing selected from the group consisting of a C 1 to C 20 aliphatic group, C 1 to C 20 heteroaliphatic group, C 3 to C 12 carbocyclic group, a C 5 to C 20 aliphatic carbocyclic group, C 3 to C 12 heterocyclic group, and a C 5 to C 20 aliphatic heterocyclic group.
3. The polymer of claim 1 , wherein the M n of the polymer is from 500 to 30,000 g/mol.
4. The polymer of claim 1 , wherein the PDI of the polymer is less than 2.
5. The polymer of claim 1 , wherein the isotactic polyether group is polypropylene oxide.
6. A method of making a polymer of claim 1 comprising:
polymerizing an epoxide in the presence of a catalyst having the following structure:
wherein 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 aliphatic carbocyclic group, and each R 6 through R 18 independently are selected from the group consisting of hydrogen, C 1 to C 20 aliphatic group, halide, C 1 to C 20 alkoxide group, C 6 to C 20 aryl group,
wherein, optionally, adjacent R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , or R 18 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
an ionic co-catalyst and/or a chain shuttling agent.
7. The method of claim 6 , wherein the chain shuttling agent is a multifunctional chain shuttling agent is R 19 —(COOH/OH) z , wherein R 19 is C 1 to C 20 aliphatic group, or C 1 to C 20 carbocyclic group, and z is from 1 to 10.
8. The method of claim 7 , wherein the multifunctional chain shuttling group is selected from
sugars, polysaccharides, glycerols, or hydroxyl or carboxyl functional polymers, wherein y is 1-100.
9. The method of claim 6 , wherein the epoxide, catalyst, ionic co-catalyst, and multifunctional chain shuttling group are contacted in a solvent.
10. The method of claim 6 , wherein the epoxide is a racemic epoxide or an enantiopure epoxide.
11. The method of claim 6 , wherein the catalyst is a racemic catalyst or an enantiopure catalyst.
12. The method of claim 6 , wherein the epoxide is a racemic epoxide and the catalyst is a racemic catalyst.
13. The method of claim 6 , wherein the ionic co-catalyst is PPNCl, PPNBr, PPNI, PPNN 3 , PPNOAc, or PPNOPiv.
14. A material comprising the polymer of claim 1 and a polyurethane, elastomer, thermoset plastic, or thermoplastic.
15. The method of claim 6 , wherein the catalyst is selected from the following:
16. The method of claim 6 , wherein the metal is Cr.
17. The method of claim 6 , wherein Q is
18. The method of claim 6 , wherein X is Cl, Br, I, N 3 , OAc, or OPiv.
19. The method of claim 6 , wherein R 10 , R 11 , and/or R 12 is a C 1 -C 4 alkyl group.
20. The method of claim 6 , wherein R 10 , R 11 , and/or R 12 is a methyl group or an isopropyl group.
21. The method of claim 6 , wherein the chain shuttling agent is a monoalcohol, a diol, a diacid, or a hydroxyacid.
22. The method of claim 1 , wherein the mm-triad content of the isotactic polyether group is less than or equal to 94%.