manufacture of certain cyclic ester oligomers
View Patent ↗Enzymes which are capable of catalyzing esterifications and/or transesterifications such as selected lipases and esterases can, under specified conditions, convert certain lower linear oligomers of polyesters to their cyclic ester oligomers in quantities greater than would be predicted by thermodynamic calculation or prior art methods. The cyclic ester oligomers are useful for the production of higher molecular weight linear polyesters.
1. A process for the production of certain cyclic ester oligomers, comprising the step of:
reacting, in a preselected solvent, components comprising:
(1) a first component which is a linear ester oligomer derived from reactants comprising an aromatic dicarboxylic acid and a diol of the general formula HOCH 2 (CR 1 R 2 ) n CH 2 OH, wherein R 1 and R 2 are each independently hydrogen or an alkyl group and n is 0, 1 or 2, which first component has an average degree of polymerization of about 1.5 to about 10; in the presence of
(2) a second component which is an enzyme capable of catalyzing transesterification of esters, with the proviso that if said first component has more than 5 mole percent carboxylic acid ends, said second component is also capable of catalyzing esterification of carboxylic acids;
wherein said reacting step is carried out at a predetermined temperature at which said first component has a solubility of at least one w/v percent in said preselected solvent.
2. A process in accordance with claim 1 wherein said first component has a solubility of at least three w/v percent in said preselected solvent.
3. A process in accordance with claim 1 wherein said first component has a solubility of at least five w/v percent in said preselected solvent.
4. A process in accordance with claim 1 wherein n is 1 or 2.
5. A process in accordance with claim 1 wherein said first component has an average degree of polymerization of about 2.0 to 5.0.
6. A process in accordance with claim 1 wherein said first component the linear ester oligomer, is derived from an aromatic dicarboxylic acid selected from the group consisting of diesters, half-acid esters, compounds of the formula HO 2 C(CH) m CO 2 H wherein m is an integer of 5 to 12, isophthalic acid, substituted isophthalic acids, terephthalic acid, substituted terephthalic acids, and 2,6-naphthalenedicarboxylic acid, and combinations thereof.
7. A process in accordance with claim 1 wherein said second component, said enzyme, is selected from the group consisting of lipases, proteases and esterases.
8. A process in accordance with claim 1 wherein said second component, said enzyme, is unsupported.
9. A process in accordance with claim 1 wherein said second component, said enzyme, is supported.
10. A process in accordance with claim 10 wherein said second component, said enzyme, is supported by materials selected from the group consisting of diatomaceous earth, polysaccharides including chitosan, alginate or carrageenan, titania, silica, alumina, polyacrylates and polymethacrylates.
11. A process in accordance with claim 1 wherein said preselected solvent is selected from the group consisting of o-dichlorobenzene, phenyl ether, chlorobenzene, methyl t-butyl ether, di-isopropyl ether, tetrahydrofuran, acetone, acetonitrile, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide, 1,1,1-trichloroethane, dichloromethane, toluene, xylene, cyclohexane, heptane, iso-octane and halocarbons such as perchloroethylene.
12. A process in accordance with claim 1 wherein said predetermined reaction temperature ranges from 0° C. to 130° C.
13. A process in accordance with claim 1 wherein said predetermined reaction temperature is about 80° C.