Pet polymer with an anti-crystallization comonomer that can be bio-sourced

Abstract

A polyethylene terephthalate (PET) polymer having diacid units derived from diacid compounds, said diacid units comprising: a) from 92.50 mol % to 97.75 mol % of terephthalic units derived from terephthalic acid (TA) or an ester thereof, and b) from 2.25 mol % to 7.50 mol % of 2,5-FDCA units derived from 2,5-furandicarboxylic acid (2,5-FDCA) or an ester thereof, and—diol units derived from diol compound(s), the diol units having monoethylene glycol units derived from monoethylene glycol (MEG), as well as to a method to prepare such a PET polymer. The use of a 2,5-FDCA compound selected from 2,5-furandicarboxylic acid (2,5-FDCA) and esters thereof as an anti-crystallization comonomer in a PET polymer and a bio-based PET polymer in which the anti-crystallisation comonomer is bio-based.

1 . A polyethylene terephthalate (PET) polymer comprising:
 diacid units derived from diacid compounds, said diacid units comprising:
 a) from 92.50 mol % to 97.75 mol % of terephthalic units derived from terephthalic acid (TA) or an ester thereof, and 
 b) from 2.25 mol % to 7.50 mol % of 2,5-FDCA units derived from 2,5-furandicarboxylic acid (2,5-FDCA) or an ester thereof, and 
 diol units derived from diol compound(s), said diol units comprising monoethylene glycol units derived from monoethylene glycol (MEG). 
   
     
     
         2 . The PET polymer according to  claim 1 , wherein the diacid units comprise:
 a) from 95.00 mol % to 97.50 mol % of terephthalic units derived from terephthalic acid (TA) or an ester thereof, and   b) from 2.50 mol % to 5.00 mol % of 2,5-FDCA units derived from 2,5-furandicarboxylic acid (2,5-FDCA) or an ester thereof.   
     
     
         3 . The PET polymer according to  claim 1 , wherein the diol units comprise at least 95.00 mol % of monoethylene glycol units. 
     
     
         4 . The PET polymer according to  claim 1 , wherein the diol units further comprise diethylene glycol units in an amount of less than 5.00 mol % of the diol units. 
     
     
         5 . The PET polymer according to  claim 1 , wherein:
 the diacid compounds comprise terephthalic acid or dimethyl therephthalate; and 2,5-furandicarboxylic acid or dimethyl 2,5-furandicarboxylate, and   the diol compound(s) comprise monoethylene glycol.   
     
     
         6 . The PET polymer according to  claim 1 , wherein at least one of the diacid and diol compounds is obtained from at least one bio-material. 
     
     
         7 . The PET polymer according to  claim 1 , wherein the PET polymer is in the form of a packaging element. 
     
     
         8 . The PET polymer according to  claim 7 , wherein the PET polymer is in the form of a container. 
     
     
         9 . A method to prepare a PET polymer according to  claim 1  comprising a copolymerization of a mixture of:
 the diacid compounds comprising terephthalic acid (TA) or an ester thereof, and 2,5-furandicarboxylic acid (2,5-FDCA) or an ester thereof, and 
 the diol compound(s) comprising monoethylene glycol. 
 
     
     
         10 . The method according to  claim 9 , wherein the copolymerization comprising a first step of melt polymerization and a second step of solid state polymerization. 
     
     
         11 . (canceled) 
     
     
         12 . (canceled) 
     
     
         13 . A bio-based PET polymer comprising:
 bio-based terephthalic units,   bio-based monoethylene glycol units, and   from 0.50 mol % to 7.50 mol %, of anti-crystallization units based on the total amount of the diol units of the bio-based PET polymer if the anti-crystallization units correspond to diol units or based on the total amount of the diacid units of the bio-based PET polymer if the anti-crystallization units correspond to diacid units,   wherein the anti-crystallization units are derived from bio-based anti-crystallization comonomers.   
     
     
         14 . The bio-based PET polymer according to  claim 13 , wherein the bio-based anti-crystallization comonomers are selected from bio-based 1,3-propanediol (PDO), 1,4-butanediol (BDO), 2,5-FDCA, esters of 2,5-FDCA and mixtures thereof. 
     
     
         15 . The bio-based PET polymer according to  claim 13 , comprising from 2.25 mol % to 7.50 mol % of anti-crystallization units based on the total amount of the diol units of the bio-based PET polymer if the anti-crystallization units correspond to diol units or based on the total amount of the diacid units of the bio-based PET polymer if the anti-crystallization units correspond to diacid units. 
     
     
         16 . The bio-based PET polymer according to  claim 13 , comprising from 2.50 mol % to 5.00 mol % of anti-crystallization units based on the total amount of the diol units of the bio-based PET polymer if the anti-crystallization units correspond to diol units or based on the total amount of the diacid units of the bio-based PET polymer if the anti-crystallization units correspond to diacid units. 
     
     
         17 . The PET polymer according to  claim 7 , wherein the packaging element is a container or a film. 
     
     
         18 . The PET polymer according to  claim 8 , wherein the container is a bottle or a cup. 
     
     
         19 . A method to avoid spherulitic crystallization during the manufacturing of a PET polymer comprising the addition of a 2,5-FDCA compound selected from 2,5-furandicarboxylic acid (2,5-FDCA) and esters thereof during the manufacturing of the PET polymer. 
     
     
         20 . The method according to  claim 19 , wherein the 2,5-FDCA compound is selected from 2,5-furandicarboxylic acid (2,5-FDCA) and dimethyl furandicarboxylate. 
     
     
         21 . The method according to  claim 19 , wherein the 2,5-FDCA compound is 2,5-furandicarboxylic acid (2,5-FDCA).