Catalytic lactide and glycolide (co)polymerization system
View Patent ↗A catalytic lactide and glycolide copolymerization system comprising a trifluoromethane sulfonate as a catalyst and copolymerization additive and a copolymerization process.
1. A method for (co)polymerizing lactide and/or glycolide monomers via a ring-opening (co)polymerization process comprising:
contacting said lactide and/or glycolide monomers with a catalytic system comprising
(a) a trifluoromethanesulfonate of the formula
in which
R 1 is hydrogen, deuterium atom, or
-E 14 (R 14 )(R′ 14 )(R″ 14 );
E 14 is an element of group 14;
R 14 , R′ 14 and R″ 14 are independently hydrogen, deuterium atom, substituted or non-substituted alkyl, cycloalkyl or aryl, and in which said substituent or substituents are halo, alkyl, cycloalkyl or aryl,
as catalyst, and
(b) a (co)polymerization additive of the formula
R 2 -E-R 3 (2)
in which
E is an element of group 16;
R 2 is a hydrogen or deuterium atom;
R 3 is hydrogen, deuterium atom, or
-E′ 14 (T 14 )(T′ 14 )(T″ 14 );
E′ 14 is an element of group 14;
T 14 , T′ 14 and T″ 14 are, independently, hydrogen; deuterium atom; or substituted or non-substituted alkyl, cycloalkyl or aryl, wherein said substituent or substituents are halo, hydroxy, alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy, carboxy, alkoxycarbonyl, cycloalkoxycarbonyl or aryloxycarbonyl,
thereby (co)polymerizing said lactide and/or glycolide monomers.
2. The method of claim 1 , wherein the quantity of (co)polymerization additive with respect to the catalyst is between 0.05 and 5 molar equivalents.
3. The method of claim 1 , wherein the compound of formula (1) is such that R 1 is hydrogen or -E 14 (R 14 )(R′ 14 )(R″ 14 ).
4. The method of claim 1 , wherein the compound of formula (1) is such that R 1 is hydrogen.
5. The method of claim 1 , wherein the compound of formula (1) is such that R 1 is -E 14 (R 14 )(R′ 14 )(R″ 14 ) and E 14 is a carbon or silicon atom.
6. The method of claim 5 , wherein E 14 is a carbon atom and R 14 , R′ 14 and R″ 14 are, independently, hydrogen or alkyl.
7. The method of claim 5 , wherein the compound of formula (2) is such that
E is oxygen or sulfur;
R 2 is hydrogen;
R 3 is hydrogen or -E′ 14 (T 14 )(T′ 14 )(T″ 14 );
E′ 14 is carbon or silicon;
T 14 , T′ 14 and T″ 14 are, independently, hydrogen or substituted or non-substituted alkyl, cycloalkyl or aryl, wherein said substituent or substituents are halo, alkyl, cycloalkyl, phenyl, naphthyl, carboxy or alkoxycarbonyl.
8. The method of claim 5 , wherein:
E is oxygen;
R 2 is hydrogen;
R 3 is hydrogen or -E′ 14 (T 14 )(T′ 14 )(T″ 14 ) in which E′ 14 is carbon and T 14 , T′ 14 and T″ 14 are, independently, hydrogen or alkyl.
9. The method of claim 1 , wherein the compound of formula (2) is water or an aliphatic alcohol.
10. The method of claim 1 , wherein the compound of formula (2) is isopropanol or pentan-1-ol.
11. The method of claim 1 , wherein the molar ratio of (co)polymerization additive with respect to catalyst is from 0.5:1 to 2:1.
12. The method of claim 1 , wherein the molar ratio of (co)polymerization additive with respect to catalyst is from 0.5:1 to 5:1.
13. The method of claim 11 , wherein said contacting occurs at a temperature between −20° C. and approximately 150° C.
14. The method of claim 13 , wherein said contacting occurs in solution at a temperature between 0° C. and 30° C.
15. The method of claim 11 , wherein said contacting occurs between a few minutes and 48 hours.