Method for stabilizing a condensed phase composition including a cyclic ester in a process of manufacturing a polyester or of lactide

Patent metadata

Field	Value
Publication number	US-10059799-B2
Application number	US-201515510917-A
Country	US
Kind code	B2
Filing date	Aug 19, 2015
Priority date	Sep 17, 2014
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

A method for stabilizing a condensed phase composition in a process of manufacturing a polyester from cyclic ester monomer comprising the steps of devolatilizing a reaction mixture, which contains i) at least one polymerizable cyclic ester, ii) at least one catalyst and optionally at least one initiator, to produce a vapor stream and a molten residue, wherein the vapor stream includes mainly i) the at least one polymerizable cyclic ester and ii) the at least one catalyst and/or the at least one initiator and/or a reaction product or a residue of the at least one catalyst and/or the at least one initiator and condensing the vapor stream to form the condensed phase composition, wherein at least one polymerization inhibitor is added as stabilizer to the reaction mixture and/or to the condensed phase composition in an amount so that the degree of conversion of the polymerizable cyclic ester in the condensed phase composition is not more than 15%, wherein the degree of conversion is 100▪(c0−C F )/c 0 , wherein c 0 is the initial concentration of the cyclic ester in the condensed phase composition obtained by the condensation of the vapor stream and C F is the concentration of the cyclic ester in the condensed phase composition after addition of 150 ppm of tin octoate as catalyst and of 100 mmol/kg of ethyl-hexanol as initiator to the condensed phase composition and a subsequent heat treatment of condensed phase composition under inert atmosphere conditions for 12 hours at 160° C.

First claim

The invention claimed is:

1. A method for stabilizing a condensed phase composition, which contains i) at least one polymerizable cyclic ester and ii) at least one catalyst capable of catalyzing a polymerization of the cyclic ester and/or at least one initiator capable of initiating a polymerization of the cyclic ester and/or a reaction product or a residue of the at least one catalyst and/or of the at least one initiator,
i) wherein the method is used in a process of manufacturing a polyester from cyclic ester monomer and comprises the steps of:
a) providing a cyclic ester,
b) polymerizing the cyclic ester in the presence of the catalyst and/or the initiator in a reactor to form a reaction mixture comprising polyester and unreacted cyclic ester,
c) subjecting the reaction mixture to a devolatilization to obtain a purified polyester as molten residue and a vapor, which includes mainly i) the at least one polymerizable cyclic ester and ii) the at least one catalyst and/or the at least one initiator and/or a reaction product or a residue of the at least one catalyst and/or the at least one initiator, and
d) subjecting the vapor stream to a condensation to obtain the condensed phase composition,
wherein at least one polymerization inhibitor is added as stabilizer to the reaction mixture and/or to the condensed phase composition in an amount so that the degree of conversion of the polymerizable cyclic ester in the condensed phase composition is not more than 15%, wherein the degree of conversion is 100·(c 0 −c F )/c 0 , wherein c 0 is the initial concentration of the cyclic ester in the condensed phase composition obtained by the condensation of the vapor stream and c F is the concentration of the cyclic ester in the condensed phase composition after addition of 150 ppm of tin octoate as catalyst and of 100 mmol/kg of ethyl-hexanol as initiator to the condensed phase composition and a subsequent heat treatment of the condensed phase under inert atmosphere conditions for 12 hours at 160° C.,
wherein
i a ) either at least a part of the polymerization inhibitor is added to the vapor stream drawn off from the devolatilization and/or to the condensed composition, and/or
i b ) at least a part of the polymerization inhibitor is added to the reaction mixture before step c), and wherein the devolatilization is performed at a temperature above 203° C. and at a pressure below 4 mbar or, alternatively, at a temperature above 220° C. and at a pressure below 5 mbar, or

ii) wherein the method is used in a process of manufacturing lactide from lactic acid and comprises the steps of:
a) providing lactic acid,
b) polycondensation of the lactic acid in a reactor to form a reaction mixture comprising a polylactic acid prepolymer,
c) adding a catalyst to the reaction mixture and depolymerizing the reaction mixture,
d) devolatilizing the reaction mixture to obtain a crude lactide stream,
e) subjecting the vapor stream to a condensation to obtain the condensed phase composition,
wherein at least one polymerization inhibitor is added as stabilizer to the reaction mixture and/or to the condensed phase composition in an amount so that the degree of conversion of the polymerizable cyclic ester in the condensed phase composition is not more than 15%, wherein the degree of conversion is 100·(c 0 −c F )/c 0 , wherein c 0 is the initial concentration of the cyclic ester in the condensed phase composition obtained by the condensation of the vapor stream and c F is the concentration of the cyclic ester in the condensed phase composition after addition of 150 ppm of tin octoate as catalyst and of 100 mmol/kg of ethyl-hexanol as initiator to the condensed phase composition and a subsequent heat treatment of the condensed phase under inert atmosphere conditions for 12 hours at 160° C.,
wherein at least a part of the polymerization inhibitor is added to the vapor stream drawn off from the devolatilization and/or to the condensed composition.

2. The method in accordance with claim 1 , wherein the degree of conversion of the polymerizable cyclic ester in the condensed phase composition is not more than 10%.

3. The method in accordance with claim 1 , wherein the at least one cyclic ester is selected from the group consisting of lactide, L-lactide, D-lactide, meso-lactide, ε-caprolactone, glycolide and mixtures of one or more of the aforementioned substances.

4. The method in accordance with claim 1 , wherein the reaction mixture and the condensed phase composition each contain as catalyst at least one organometallic compound comprising a metal selected from the group consisting of magnesium, titanium, zinc, aluminum, indium, yttrium, tin, lead, antimony, bismuth and any combination of two or more of the aforementioned metals.

5. The method in accordance with claim 1 , wherein the reaction mixture and the condensed phase composition each contain as initiator at least one compound comprising at least one carboxyl group and/or hydroxyl group.

6. The method in accordance with claim 1 , wherein the at least one polymerization inhibitor is an imine or a diimine.

7. The method in accordance with claim 1 , wherein the condensed phase composition comprising the polymerization inhibitor is subjected to a purification step to obtain a purified condensed phase composition.

8. The method in accordance with claim 7 , wherein the purified cyclic ester is recycled into the reactor.

9. The method in accordance with claim 1 , wherein the condensed phase composition is mixed in order to homogenously distribute the polymerization inhibitor.

10. A condensed phase composition produced in accordance with the method of claim 1 , the condensed phase composition comprising:
i) at least 95% by weight of cyclic ester,
ii) at least 0.5 ppm of at least one catalyst capable of catalyzing a polymerization of the cyclic ester and/or at least 0.01 mmol per kg of at least one initiator capable of initiating a polymerization of the cyclic ester and
iii) 0.001 to 0.5% by weight of polymerization inhibitor.

11. A method for use of a condensed phase composition in accordance with claim 10 for the production of a polyester, comprising polymerizing the condensed phase composition, wherein before the start of the polymerization, polymerization catalyst and/or polymerization initiator are added to the condensed phase composition, so that the total amount of polymerization catalyst is 1 ppm to 1% by weight and/or the total amount of polymerization initiator is 0.1 to 50 mmol/kg based on the total amount of condensed phase composition.

12. A method for use of a condensed phase composition in accordance with claim 10 for the production of a polyester, comprising the steps of: (I) mixing the condensed phase composition with a melt comprising a cyclic ester and/or a polyester; and so that the total amount of polymerization catalyst is 1 ppm to 1% by weight and/or the total amount of polymerization initiator is 0.1 to 50 mmol/kg based on the total amount (II) polymerizing the condensed phase composition.

13. The method of claim 12 , wherein the condensed phase composition is further mixed with polymerization catalyst and/or polymerization initiator, so that the total amount of polymerization catalyst is 1 ppm to 1% by weight and/or the total amount of polymerization initiator is 0.1 to 50 mmol/kg based on the total amount of final composition, wherein the so obtained mixture is then further polymerized.

14. The method of claim 1 , wherein the cyclic ester is polymerized in step i(b) in the presence of both the catalyst and the initiator.

Assignees

• Sulzer Chemtech Ag

Inventors

• Costa Liborio Ivano
• Brack Hans-Peter
• Tancini Francesca
• Yu Yingchuan

Classifications

• C08F2/42

  using short-stopping agents · CPC title

• C08G63/78 Primary

  Preparation processes · CPC title

• C08G63/08 Primary

  Lactones or lactides · CPC title

• C08G63/85 Primary

  Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof {(C08G63/823 takes precedence)} · CPC title

• C08G63/90

  Purification; Drying · CPC title