Methods for preparation of macrocyclic polyester oligomer via heterogeneous catalysis

Abstract

The invention relates to methods and systems for preparing macrocyclic polyester oligomer (MPO) directly from monomer via heterogeneous catalysis, rather than by depolymerizing a polyester. For example, in an exemplary embodiment, cyclic poly(butylene terephthalate) (cPBT) is produced by reacting butanediol (BDO) and dimethylterephthalate (DMT) in an organic solvent—for example, ortho-dichlorobenzene (oDCB). The mixture flows over (or otherwise contacts) the catalyst-coated fiberglass or silica gel, e.g., which is packed in a column or bed. MPO is produced in the reaction mixture, while residual linears and catalyst residue remain in the column/bed.

What is claimed is: 
     
         1 . A method for preparing a macrocyclic polyester oligomer (MPO), the method comprising:
 (a) heating a mixture, the mixture comprising:
 (i) a diol; 
 (ii) dimethylterephthalate (DMT) or, alternatively or additionally, a DMT precursor; and 
 (iii) an organic solvent; and 
   (b) contacting the mixture with a solid comprising a catalyst, thereby producing MPO.   
     
     
         2 . The method of  claim 1 , further comprising removing alcohol produced. 
     
     
         3 . The method of  claim 2 , wherein the alcohol is methanol. 
     
     
         4 . The method of any one of the preceding claims, wherein the heating and contacting steps are performed at the same time. 
     
     
         5 . The method of any one of the preceding claims, wherein the MPO is cyclic poly(butylene terephthalate) (cPBT). 
     
     
         6 . The method of any one of the preceding claims, wherein the mixture in step (a) comprises a DMT precursor, wherein the DMT precursor is terephthalic acid (TPA). 
     
     
         7 . The method of any one of the preceding claims, wherein the organic solvent is ortho-dichlorobenzene (oDCB). 
     
     
         8 . The method of any one of the preceding claims, wherein the solid comprising the catalyst is a member selected from the group comprising titanium catalyst-coated fiberglass, titanium catalyst-coated silica gel, and titanium catalyst-adhered magnetic iron oxide. 
     
     
         9 . The method of any one of the preceding claims, wherein the solid comprising the catalyst is packed in a column. 
     
     
         10 . The method of any one of  claims 1 - 8 , wherein the solid comprising the catalyst is packed in a bed. 
     
     
         11 . The method of any one of  claims 1 - 8 , wherein the solid comprising the catalyst is loose in a reactor vessel. 
     
     
         12 . The method of any one of the preceding claims, wherein the contacting step is performed in the presence of heat. 
     
     
         13 . The method of any one of the preceding claims, wherein the MPO is a member selected from the group consisting of cPBT, cPPT, cPCT, cPET, and cPEN. 
     
     
         14 . The method of any one of the preceding claims, wherein the MPO is a copolymer oligomer. 
     
     
         15 . The method of any one of the preceding claims, further comprising collecting the MPO. 
     
     
         16 . The method of  claim 15 , wherein the collected MPO is at least 80 wt. % dimer, trimer, tetramer, and/or pentamer species. 
     
     
         17 . The method of any one of the preceding claims, wherein the yield of MPO is at least 35%. 
     
     
         18 . The method of  claim 17 , wherein the yield of MPO is at least 50%.