Continuous method for manufacturing a polyester from cyclic ester monomer

Patent metadata

Field	Value
Publication number	US-10066054-B2
Application number	US-201515510859-A
Country	US
Kind code	B2
Filing date	Sep 3, 2015
Priority date	Sep 17, 2014
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

A process of manufacturing a polyester from cyclic ester monomer comprises the steps of: a) providing a cyclic ester, b) polymerizing the cyclic ester in the presence of a catalyst and optionally an initiator in a reactor to form a reaction mixture comprising polyester and unreacted cyclic ester, wherein after the polymerization at least one polymerization inhibitor is added to the reaction mixture, wherein the polymerization inhibitor is selected from the group consisting of monoimines, diimines, mono alkyl phosphates according to the formula RPO4H2, wherein R is a C6-16 linear, branched or cyclic alkyl group, di alkyl phosphates according to the formula R2PO4H, wherein each R is independently a C6-16 linear, branched or cyclic alkyl group or a combination thereof, and phosphate esters according to the general formula (I) wherein at least one of R′, R″ and R″′ has the general structure as in general formula (II) wherein n>0 and Q is independently a C1-16 linear, branched or substituted alkyl group, and R is independently an H or linear, branched, cyclic or substituted alkyl group or a phenyl group derivative, and wherein any of R′, R″ and R″′ not having the general structure as in general formula (II) is independently an H or a linear, branched, cyclic or substituted alkyl group or a phenyl group derivative.

First claim

The invention claimed is:

1. A process of manufacturing a polyester from cyclic ester monomer, wherein the method comprises the steps of:
a) providing a cyclic ester,
b) polymerizing the cyclic ester in the presence of a catalyst in a reactor to form a reaction mixture comprising polyester and unreacted cyclic ester,
wherein after the polymerization at least one polymerization inhibitor is added to the reaction mixture, wherein the polymerization inhibitor is selected from the group consisting of monoimines, diimines, mono alkyl phosphates according to the formula RPO 4 H 2 , wherein R is a C 6-16 linear, branched or cyclic alkyl group, di alkyl phosphates according to the formula R 2 PO 4 H, wherein each R is independently a C 6-16 linear, branched or cyclic alkyl group or a combination thereof, and phosphate esters according to the general formula (I)

wherein at least one of R′, R″ and R′″ has the general structure as in general formula (II)

wherein n>0 and Q is independently a C 1-16 linear, branched or substituted alkyl group, and R is independently an H or linear, branched, cyclic or substituted alkyl group or a phenyl group derivative, and wherein any of R′, R″ and R″ not having the general structure as in general formula (II) is independently an H or a linear, branched, cyclic or substituted alkyl group or a phenyl group derivative.

2. The process in accordance with claim 1 , wherein as polymerization inhibitor a phosphate ester according to the general formula (I) is used, in which either i) R′ is an H and R″ and R′″ are according to the general formula (II) or ii) R′ and R″ are an H and R′″ is according to the general formula (II).

3. The process in accordance with claim 1 , wherein as polymerization inhibitor a phosphate ester according to the general formula (I) is used, in which n of the at least one of R′, R″ and R′″ having the general structure as in general formula (II) is 2 to 20, and in which Q of the at least one of R′, R″ and R″ having the general structure as in general formula (II) is a C 1-15 linear, branched or substituted alkyl group.

4. The process in accordance with claim 1 , wherein as polymerization inhibitor a poly(oxy-1,2-ethanediyl), alpha-isotridecyl-omega-hydroxy-phosphate, a poly(oxy-1,2-ethanediyl), alpha-hydro-omega-hydroxy-mono-C 12-15 -alkyl ether phosphate, or combination thereof is used.

5. The process in accordance with claim 1 , wherein as polymerization inhibitor a diimine is used.

6. The process in accordance with claim 5 , wherein as polymerization inhibitor N,N′-bis(salicylidene)-1,3-propanediamine is used.

7. The process in accordance with claim 1 , which further comprises the following steps:
c) subjecting the reaction mixture to a devolatilization to obtain a purified polyester as molten residue and vapor, wherein the vapor includes mainly i) cyclic ester and ii) catalyst and/or initiator and/or a reaction product or a residue of catalyst and/or of initiator, and
d) subjecting the vapor stream to a condensation to obtain a condensed phase composition,
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, and/or wherein at least a part of the polymerization inhibitor is added to the reaction mixture before step c).

8. The process in accordance with claim 1 , wherein an amount of the cyclic ester devolatilized to an overhead system comprising a gas removal line ( 20 ) and/or vapor removal lines ( 16 , 44 ) is decreased relative to the amount of the cyclic ester devolatilized when no polymerization inhibitor is added to the reaction mixture.

9. The process in accordance with claim 1 , wherein the polyester has a yellowness index measured after pelletization in accordance with YI-D1925 that is reduced relative to a yellowness index after pelletization of a polyester in which no polymerization inhibitor has been added to the reaction mixture.

10. The process 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 thereof.

11. A polyester produced in accordance with the process of claim 1 .

12. A condensed phase composition produced in accordance with the process of claim 7 , 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.

13. A method for the production of a polyester, comprising the steps of obtaining and performing a polymerization of the condensed phase composition of claim 12 , wherein before the start of the 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.

14. A method for the production of a polyester, comprising the steps of obtaining the condensed phase composition of claim 12 , wherein the condensed phase composition is mixed with a melt comprising a cyclic ester and/or a polyester, with the optional addition of a polymerization catalyst and or polymerization initiator, so that the total amount of polymerization initiator is 0.1 to 50 mmol/kg by weight based on the total amount of final composition, wherein the so obtained mixture is then further polymerized.

15. The method of claim 14 , wherein the condensed phase composition is purified before mixing with the melt.

16. The method of claim 13 , wherein the condensed phase composition is purified before the addition of catalyst, before the addition of polymerization initiator, or both.

17. The process of claim 1 , wherein (b) the cyclic ester is further polymerized in the presence of an initiator in the reactor to form the reaction mixture.

18. The process of claim 3 , wherein as polymerization inhibitor a phosphate ester according to the general formula (I) is used, in which n of the at least one of R′, R″ and R′″ having the general structure as in general formula (II) is 2 to 11.

19. The process of claim 1 , wherein Q of the at least one of R′, R″ and R′″ is a 1,2-ethanediyl group.

Assignees

• Sulzer Chemtech Ag

Inventors

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

Classifications

• C08F2/42

  using short-stopping agents · CPC title

• C08G63/08 Primary

  Lactones or lactides · CPC title

• C08G63/78 Primary

  Preparation processes · CPC title

• C08G63/85

  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