Polymers and methods of producing thereof
Provided herein are methods of producing polymers from furan and optionally diol compounds, using an organocatalyst. A polymer composition comprising a polymer prepared by the method is contemplated. Provided herein are also polymer compositions, such as poly(alkylene-2,5-furandicarboxylate). In some embodiments, polymer compositions have any one of the characteristics discussed herein, or any combinations thereof.
1. A polymer composition having reduced color content, comprising:
a polymer with a polymer backbone, wherein the polymer backbone comprises one of a substituted or unsubstituted f urandicarboxylate moiety and a substituted or unsubstituted tetrahydrof urandicarboxylate moiety, and
an organocatalyst comprising carbene, or a fragment of the organocatalyst thereof,
wherein the composition is free from metal catalysts or metal catalyst fragments, wherein the metal catalysts are at least one of a transesterification catalyst, a polycondensation catalyst, or polymerization catalysts used to produce the polymer or precursors thereof, and
wherein the polymer composition having a reduced color content has a number average molecular weight of at least 10,000 Da, and
wherein a solution of 5 mg/mL of the composition in (i) hexafluoroisopropanol or (ii) hexafluoroisopropanol/dichloromethane has an absorbance of less than 0.5 at 400 nm.
2. The polymer composition of claim 1 , wherein the solution of 5 mg/mL of the polymer composition in (i) hexafluoroisopropanol or (ii) hexafluoroisopropanol/dichloromethane has an absorbance of less than 0.08 to 400 nm.
3. The polymer composition of claim 1 , wherein the solution of 5 mg/mL of the polymer composition in (i) hexafluoroisopropanol or (ii) hexafluoroisopropanol/dichloromethane has an absorbance of less than 0.05 to 400 nm.
4. The polymer composition of claim 1 , wherein the organocatalyst is an N-heterocyclic carbene.
5. The polymer composition of claim 1 , wherein the substituted or unsubstituted furandicarboxylate moiety is the substituted or unsubstituted 2,5-furandicarboxylate moiety, and the substituted or unsubstituted tetrahydrofurandicarboxylate moiety is the substituted or unsubstituted 2,5-tetrahydrofurandicarboxylate moiety.
6. The polymer composition of claim 1 , wherein the substituted or unsubstituted furandicarboxylate moiety is:
7. The polymer composition of claim 1 , wherein the polymer is poly(alkylene-2,5-furandicarboxylate) or poly(alkylene-2,5-tetrahydrofurandicarboxylate).
8. The polymer composition of claim 1 , wherein the polymer is poly-ethylene-2,5-furandicarboxylate) or poly(ethylene-2,5-tetrahydrofurandicarboxylate).
9. The polymer composition of claim 1 , wherein the polymer is poly-ethylene-2,5-furandicarboxylate) (PEF), and wherein the organocatalyst is a N-heterocyclic carbene.
10. The polymer composition of claim 1 , further comprising an antioxidant or fragment thereof.
11. The polymer composition of claim 1 , wherein the composition has a total metal content of less than 0.003 wt %.
12. The polymer composition of claim 1 , wherein the composition has less than 0.005 wt % of antimony.
13. The polymer composition of claim 1 , wherein the composition has a total content of aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, zinc, geranium, zirconium, cadmium, tin, antimony, hafnium, tungsten, lead, and bismuth, if present, less than 0.02 wt % combined.
14. The polymer composition of claim 1 , wherein the total metal content includes the content of transition metals, post-transition metals, metalloids, or lanthanoid metals, or any combinations thereof.
15. A method of preparing a polymer composition having reduced color content, comprising:
a) polymerizing one of a substituted or unsubstituted furan-2,5-dicarboxylic acid dialkyl ester, and a substituted or unsubstituted tetrahydrofuran-2,5-dicarboxylic acid dialkyl ester in the presence of an organocatalyst and an antioxidant at a temperature of less than 250° C.; and
b) annealing the polymer composition, followed by performing solid state polymerization to provide a polymer composition having reduced color content,
wherein the polymer composition comprises one of the substituted or unsubstituted furandicarboxylate moiety and the substituted or unsubstituted tetrahydrofurandicarbwrylate moiety, and
an organocatalyst comprising carbene, or a fragment of the organocatalyst thereof,
wherein the polymer composition is free from metal catalysts or metal catalyst fragments, wherein the metal catalysts are at least one of a transesterification catalyst, a polycondensation catalyst, or polymerization catalysts used to produce the polymer or precursors thereof, and
wherein a solution of 5 mg/mL of the polymer composition in (i) hexafluoroisopropanol or (ii) hexafluoroisopropanol/dichloromethane has an absorbance of less than 0.5 at 400 nm; and
wherein the polymer composition having reduced color content has a number average molecular weight of at least 10,000 Da.
16. The method of claim 15 , wherein in step a), the temperature is less than 230° C.
17. The method of claim 15 , wherein in step a), the temperature is less than 200° C.
18. The method of claim 15 , wherein in step a), the temperature is less than 170° C.
19. The method of claim 15 , wherein the solution of 5 mg/mL of the polymer composition in (i) hexafluoroisopropanol or (ii) hexafluoroisopropanol/dichloromethane has an absorbance of less than 0.08 to 400 nm.
20. The method of claim 15 , wherein the solution of 5 mg/mL of the polymer composition in (i) hexafluoroisopropanol or (ii) hexafluoroisopropanol/dichloromethane has an absorbance of less than 0.05 at 400 nm.
21. The method of claim 15 , wherein the organocatalyst is an N-heterocyclic carbene.
22. A polymer composition having reduced color content produced by the method according to claim 15 .