Catalytic polymerization of polymers containing electrophilic linkages using nucleophilic reagents
The disclosure relates to methods and materials useful for polymerizing a monomer. In one embodiment, for example, the disclosure provides a method for polymerizing a monomer containing a plurality of electrophilic groups, wherein the method comprises contacting the monomer with a nucleophilic reagent in the presence of a guanidine-containing catalyst. The methods and materials of the disclosure find utility, for example, in the field of materials science.
1. A method for forming a polymer, the method comprising: contacting a monomer with a nucleophilic reagent in the presence of a guanidine-containing compound to form a prepolymer and polymerizing the prepolymer to form a polymer, wherein the monomer comprises two electrophilic moieties, wherein the guanidine-containing compound has the structure of formula (Ib)
wherein
n3 is selected from 0 and 1;
X 1 and X 2 are independently selected from the group consisting of —NR 10 — and —C(R 11 )(R 12 )—, wherein R 10 , R 11 , and R 12 are independently selected from H and alkyl;
R 2 and R 5 are independently selected from the group consisting of substituted and unsubstituted C 1 -C 30 alkyl; and
R 8a , R 8b , R 9a , and R 9b are independently selected from the group consisting of H and substituted and unsubstituted alkyl, aryl, aralkyl, and alkaryl, any of which may be heteroatom-containing, provided that any two of R 8a , R 8b , R 9a , R 9b , R 10 , R 11 , and R 12 may be taken together to form a cycle.
2. The method of claim 1 , wherein the guanidine-containing compound has the structure
3. The method of claim 1 , wherein the prepolymer is bis(hydroxyl ethylene)terephthalate.
4. The method of claim 1 , wherein the guanidine-containing compound is present in an amount less than about 1 mol % relative to the amount of monomer.
5. The method of claim 1 , wherein the monomer has the structure X 1 -L-X 2 , wherein X 1 and X 2 are electrophilic moieties independently selected from esters, carbonates, urethanes, substituted urethanes, phosphates, amido groups, substituted amido groups, thioesters, and sulfonate esters, and L is a linker moiety selected from C 1 -C 30 hydrocarbylene and functional linker groups.
6. The method of claim 5 , wherein X 1 and X 2 are ester moieties.
7. The method of claim 5 , wherein L is selected from substituted and unsubstituted C 1 -C 24 alkylene, substituted and unsubstituted C 5 -C 24 arylene, substituted and unsubstituted C 5 -C 24 alkarylene, and substituted and unsubstituted C 5 -C 24 aralkylene.
8. The method of claim 6 , wherein the nucleophilic reagent comprises at least one hydroxyl group.
9. The method of claim 1 , wherein the polymerizing provides polymerization products substantially free of metal contaminants.
10. The method of claim 1 , wherein the polymerizing involves a condensation reaction and is carried out under reduced pressure.
11. The method of claim 1 , wherein the polymer is selected from the group consisting of poly(alkylene terephthalates), poly(alkylene adipates), poly(alkylene suberates), poly(alkylene sebacates), poly(alkylene isophthalates), poly(alkylene sulfonyl-4,4′-dibenzoates), poly(alkylene 2,6-naphthalene-dicarboxylates), poly(p-phenylene alkylene dicarboxylates), poly(trans-1,4-cyclohexanediyl alkylene dicarboxylates), poly(1,4-cyclohexane-dimethylene alkylene dicarboxylates), poly([2.2.2]-bicyclooctane-1,4-dimethylene alkylene dicarboxylates), polycarbonates of bisphenol A, polyamides, poly(alkylene carbonates), lactic acid polymers and copolymers, polyurethanes and polyurethane/polyester copolymers, poly(ε-caprolactone), and poly(β-propiolactone).
12. The method of claim 1 , wherein the polymer comprises poly(ethylene terephthalate) (PET).
13. The method of claim 1 , wherein the polymer comprises poly(butylene terephthalate) (PBT).
14. The method of claim 1 , wherein the polymer comprises poly(hexamethylene terephthalate).
15. The method of claim 1 , wherein the polymer is selected from the group consisting of poly(ethylene adipate), poly(1,4-butylene adipate), and poly(hexamethylene adipate).
16. The method of claim 1 , wherein the polymer is selected from the group consisting of poly(ethylene suberate), poly(ethylene sebacate), poly(ethylene isophthalate), and poly(ethylene sulfonyl-4,4′-dibenzoate).
17. The method of claim 1 , wherein the polymer is selected from the group consisting of poly(ethylene 2,6-naphthalene-dicarboxylate), poly(p-phenylene ethylene dicarboxylates), poly(trans-1,4-cyclohexanediyl ethylene dicarboxylate), poly(1,4-cyclohexane-dimethylene ethylene dicarboxylate), and poly([2.2.2]-bicyclooctane-1,4-dimethylene ethylene dicarboxylate).
18. The method of claim 1 , wherein the polymer is selected from the group consisting of 3,3′-dimethylbisphenol A; 3,3′,5,5′-tetrachlorobisphenol A; and 3,3′,5,5′-tetramethylbisphenol A.
19. The method of claim 1 , wherein the polymer comprises poly(p-phenylene terephthalamide).
20. The method of claim 1 , wherein the polymer comprises polypropylene carbonate).
21. The method of claim 1 , wherein the polymer is selected from the group consisting of (S)-polylactide, (R,S)-polylactide, poly(tetramethylglycolide), and poly(lactide-co-glycolide).