Bio-Based Terephthalate Polyesters

Abstract

Bio-based terephthalic acid (bio-TPA), bio-based dimethyl terephthalate (bio-DMT), and bio-based polyesters, which are produced from a biomass containing a terpene or terpenoid, such as limonene are described, as well as the process of making these products. The bio-based polyesters include poly(alkylene terephthalate)s such as bio-based poly(ethylene terephthalate) (bio-PET), bio-based poly(trimethylene terephthalate) (bio-PTT), bio-based poly(butylene terephthalate) (bio-PBT), and bio-based poly(cyclohexylene dimethyl terephthalate) (bio-PCT).

1 . A compound comprising bio-based 1,4-cyclohexane dimethanol of Formula VII: 
       
         
           
           
               
               
           
         
         wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 5%. 
       
     
     
         2 . The compound of  claim 1  wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 80%. 
     
     
         3 . The compound of  claim 1  wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 90%. 
     
     
         4 . The compound of  claim 1  wherein the compound is made by a process comprising converting bio-based dimethyl terephthalate to 1,4-cyclohexane dimethanol by hydrogenation of the bio-based dimethyl terephthalate. 
     
     
         5 . The compound of  claim 1  wherein the compound is made by a process comprising converting bio-based terephthalic acid to 1,4-cyclohexane dimethanol by hydrogenation of the bio-based terephthalic acid. 
     
     
         6 . A process of making a compound comprising bio-based 1,4-cyclohexane dimethanol of Formula VII: 
       
         
           
           
               
               
           
         
       
       the process comprising:
 (a) providing a biomass comprising a terpene, terpenoid or a mixture thereof; 
 (b) converting the terpene, terpenoid, or mixture thereof to para-cymene; 
 (c) converting the para-cymene to terephthalic acid by oxidation, the oxidation being performed in the absence of chromium oxide; and 
 (d) converting the terephthalic acid to the bio-based 1,4-cyclohexane dimethanol, 
 wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 5%; and 
 wherein the biomass is a biological material which excludes organic material that has been transformed by geological processes into a member selected from the group consisting of petroleum, petrochemicals, and combinations thereof. 
 
     
     
         7 . A polymer compound comprising bio-based poly(cyclohexylene dimethylene terephthalate) of Formula VIII: 
       
         
           
           
               
               
           
         
         wherein n is an integer between about 50 and about 130; and 
         wherein the bio-based poly(cyclohexylene dimethylene terephthalate) has a mean bio-based content of at least 5%. 
       
     
     
         8 . A polymer compound according to  claim 7  wherein the bio-based poly(cyclohexylene dimethylene terephthalate) has a mean bio-based content of at least 80%. 
     
     
         9 . A polymer compound according to  claim 7  wherein the bio-based poly(cyclohexylene dimethylene terephthalate) has a mean bio-based content of at least 90%. 
     
     
         10 . The polymer compound of  claim 7 , wherein polymer compound is a copolymer and the polymer compound of  claim 6  further comprises a monomer selected from the group consisting of petrochemically derived ethylene glycol, and bio-based ethylene glycol. 
     
     
         11 . A polymer compound according to  claim 7  wherein the compound is made by a process comprising reacting bio-based dimethyl terephthalate a 1,4-cyclohexane dimethanol selected from the group consisting of petroleum based 1,4-cyclohexane dimethanol, bio-based 1,4-cyclohexane dimethanol, and combinations thereof. 
     
     
         12 . A polymer compound according to  claim 7  wherein the composition is made by a process comprising reacting bio-based dimethyl terephthalate with bio-based 1,4-cyclohexane dimethanol,
 wherein the bio-based dimethyl terephthalate has a mean bio-based content of at least 5%; and   wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 5%.   
     
     
         13 . A polymer compound according to  claim 7  wherein the composition is made by a process comprising reacting bio-based dimethyl terephthalate with bio-based 1,4-cyclohexane dimethanol,
 wherein the bio-based dimethyl terephthalate has a mean bio-based content of at least 80%; and   wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 80%.   
     
     
         14 . A polymer compound according to  claim 7  wherein the composition is made by a process comprising reacting bio-based dimethyl terephthalate with bio-based 1,4-cyclohexane dimethanol,
 wherein the bio-based dimethyl terephthalate has a mean bio-based content of at least 90%; and   wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 90%.   
     
     
         15 . A polymer compound according to  claim 7  wherein the compound is made by a process comprising:
 (a) providing a biomass;   (b) converting the biomass to bio-based terephthalic acid; and   (c) converting the bio-based terephthalic acid to bio-based poly(cyclohexylene dimethylene terephthalate) of Formula VIII,   wherein the biomass is a biological material which excludes organic material that has been transformed by geological processes into a member selected from the group consisting of petroleum, petrochemicals, and combinations thereof.   
     
     
         16 . A polymer compound according to  claim 15  wherein in process step (b), the biomass is a terpene, terpenoid or a mixture thereof. 
     
     
         17 . A polymer compound according to  claim 15  wherein in process step (b), the biomass is converted to bio-based terephthalic acid substantially in the absence of chromium oxide. 
     
     
         18 . A polymer compound according to  claim 15  wherein in process step (c) the step of converting the bio-based terephthalic acid to bio-based poly(cyclohexylene dimethylene terephthalate) of Formula VIII is performed by first converting the bio-based terephthalic acid to bio-based dimethyl terephthalate. 
     
     
         19 . A polymer compound according to  claim 15  wherein in process step (c), the step of converting the bio-based terephthalic acid to bio-based poly(cyclohexylene dimethylene terephthalate) of Formula VIII is performed by reacting the bio-based terephthalic acid with bio-based 1,4-cyclohexane dimethanol,
 wherein the bio-based terephthalic acid has a mean bio-based content of at least 5%; and   wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 5%.   
     
     
         20 . A polymer compound according to  claim 15  wherein in step (c) the process of converting the bio-based terephthalic acid to bio-based poly(cyclohexylene dimethylene terephthalate) of Formula VIII is performed by reacting the bio-based dimethyl terephthalate with bio-based 1,4-cyclohexane dimethanol,
 wherein the bio-based dimethyl terephthalatehas a mean bio-based content of at least 5%; and   wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 5%.