PATENTSCOPE will be unavailable a few hours for maintenance reason on Tuesday 19.11.2019 at 4:00 PM CET
Search International and National Patent Collections
Some content of this application is unavailable at the moment.
If this situation persists, please contact us atFeedback&Contact
1. (WO2010077133) A PROCESS FOR PREPARING A POLYMER HAVING A 2,5-FURANDICARBOXYLATE MOIETY WITHIN THE POLYMER BACKBONE AND SUCH (CO)POLYMERS
Note: Text based on automatic Optical Character Recognition processes. Please use the PDF version for legal matters

Claims

1. A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone, and having a number average molecular weight of at least 10,000 (as determined by GPC based on polystyrene standards), wherein the process comprises a first step wherein a prepolymer is made having the 2,5- furandicarboxylate moiety within the polymer backbone, followed in a second step by a polycondensation reaction, characterized in that:

- in the first step a 2,5-furandicarboxylate ester is transesterified with a compound or mixture of compounds containing two or more hydroxyl groups, preferably a diol or polyol, and in the presence of a tin(IV) based transesterification catalyst, and - in the second step at reduced pressure, preferably below 1 mbar, and under melt conditions the prepolymer prepared in the first step is polycondensed in the presence of a tin(ll) based polycondensation catalyst until the polymer is obtained.

2. The process of claim 1 , wherein the transesterification catalyst is or comprises an organotin(IV) based catalyst, preferably a monoalkyltin(IV) salt, a dialkyltin(VI) or trialkyltin(IV) salt.

3. The process of claim 1 or 2 wherein the 2,5-furandicarboxylate ester is an ester of a volatile alcohol or phenol, preferably having a boiling point of less than 150 °C, more preferably having a boiling point of less than 100 0C, still more preferably an ester of methanol or ethanol, most preferably of methanol. 4. The process of any one of claims 1 to 3, wherein in the first step the temperature is in the range of from about 150 to about 200 0C, preferably in the range of from about 180 to about 200 0C.

5. The process of any one of claims 1 to 4, wherein the transesterification step is carried out for a time sufficient to reduce the content of the starting 2,5- furandicarboxylate ester until it reaches the range of about 3 mol % to about 1 mol

%.

6. The process of any one of claims 1 to 5, where in the second step the temperature is in the range of from about the melting point, but not less than about 180 to 30 0C above melting point of the polymer. 7. The process of any one of claims 1 to 6, wherein the polycondensation catalyst is selected from: alkyltin(ll) salts, preferably obtained by the reduction of an alkyltin(IV) salt with a reducing compound, more obtained by the reduction of the tin(IV) based transesterification catalyst with a reducing compound.

8. The process of claim 7, wherein the reducing compound is an organophosphorus compound of trivalent phosphorus, preferably a monoalkyl or dialkyl phosphinate, a phosphonite, a phosphinate, or a phosphite, more preferably a phosphite, most preferably a triarylphosphite. 9. The process of any one of claims 1 to 8, wherein the prepolymer is made by reacting the 2,5-furandicarboxylate ester or a mixture of the 2,5-furandicarboxylate ester with another acid ester on the one hand, and a diol, a polyol or a mixture thereof on the other hand.

10. The process of claim 9, wherein the diol or polyol is selected from aromatic, aliphatic or cycloaliphatic diols or polyols, or a combination thereof.

11. The process of claim 9, wherein the diol or polyol is selected from ethylene glycol, diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,4-cyclohexanedimethanol, 1 ,4-benzenedimethanol, 2,2-dimethyl- 1 ,3-propanediol, poly(ethylene glycol), poly(tetrahydofuran), 2,5- di(hydroxymethyl)glycerol, glycerol, pentaerythritol, sorbitol, mannitol, erythritol, threitol, or a combination thereof.

12. The process of claim 9, wherein a mixture of the 2,5-furandicarboxylate ester with another acid ester or lactone is used.

13. The process of claim 9, wherein a mixture of the 2,5-furandicarboxylate ester with another acid ester or lactone is used, selected from dimethyl terephthalate, dimethyl isophthalate, dimethyl adipate, dimethyl azelate, dimethyl sebacate, dimethyl dodecanoate, dimethyl 1 ,4-cyclohexane dicarboxylate, dimethyl maleate, dimethyl succinate, trimethyl 1 ,3,5-benzenetricarboxylate or selected from pivalolactone ε- caprolactone or lactides (L1L; D1D; D1L). 14. The process of any one of claims 1 to 13, wherein a polymer is made having an absorbance as a 5 mg/mL solution in a dichloromethane:hexafluoroisopropanol 8:2 at 400 nm of below 0.05, without intermediate or subsequent purification and/or washing step.

15. The process of any one of claims 1 to 14, wherein the polymer is subjected to a subsequent Solid State Polycondensation (SSP) step.

16. The process of claim 15, wherein the polymer is subjected to an SSP step for a sufficient amount of time at an elevated temperature below the melting temperature of the polymer to increase the number average molecular weight to at least 20,000 (as determined by GPC based on styrene standards).

17. A polymer having a 2,5-furandicarboxylate moiety within the polymer backbone, and having a number average molecular weight of at least 20,000 (as determined by GPC based on styrene standards), and an absorbance as a 5 mg/mL solution in a dichloromethaneihexafluoroisopropanol 8:2 at 400 nm of below 0.05. 18. The polymer of claim 17, further having a 1 ,4-bis(hydroxymethyl)cyclohexane (cis, trans or both) moiety within the polymer backbone.

19. The polymer of claim 17, further having a 2,2-dimethyl-1,3-propanediol moiety within the polymer backbone.

20. The polymer of claim 17, further having a poly(ethylene glycol) moiety within the polymer backbone.

21. The polymer of claim 17, further having a poly(tetrahydofuran) moiety within the polymer backbone.

22. The polymer of claim 17, further having a glycerol moiety within the polymer backbone. 23. The polymer of claim 17, further having a pentaerythritol moiety within the polymer backbone.

24. The polymer of claim 17, further having a lactic acid moiety within the polymer backbone.

25. The polymer of claim 17, further having a 6-hydroxyhexanoic acid moiety within the polymer backbone.