Process for controlling the structure of a block copolymer by selective copolymerization, by ring opening, of cyclic carbonate and lactone monomers

Patent metadata

Field	Value
Publication number	US-2018346643-A1
Application number	US-201615780897-A
Country	US
Kind code	A1
Filing date	Nov 29, 2016
Priority date	Dec 4, 2015
Publication date	Dec 6, 2018
Grant date	—

Abstract

The invention relates to a process for controlling the structure of a block copolymer by selective copolymerization, by ring opening, of cyclic carbonate and lactone monomers in the presence of a catalyst based on methanesulfonic acid, the said process comprising a sequence of stages carried out strictly in the following order:
a) dissolving the cyclic carbonate monomer in a nonchlorinated aromatic solvent, b) adding, to the monomer solution, a bifunctional initiator chosen from diols or water, c) adding methanesulfonic acid (MSA) as catalyst of the polymerization reaction, d) when all the cyclic carbonate has been consumed, a telechelic polycarbonate capable of acting as macroinitiator of polymerization of the lactone is obtained, e) adding the lactone to the reaction medium in order to selectively obtain a block copolymer.

First claim

1 - 7 . (canceled)

8 . A process for controlling the structure of a block copolymer by selective copolymerization, by ring opening, of cyclic carbonate and lactone monomers in the presence of a catalyst based on methanesulfonic acid, comprising in succession:
(a) dissolving a cyclic carbonate monomer in a nonchlorinated aromatic solvent to produce a monomer solution, followed by (b) adding a bifunctional initiator chosen from diols or water to the monomer solution from (a), followed by (c) adding methanesulfonic acid (MSA) to the solution from (b), followed by (d) polymerizing the cyclic carbonate monomer in the solution from (c), wherein when all the cyclic carbonate has been consumed, a telechelic polycarbonate capable of acting as macroinitiator of polymerization of the lactone is obtained, and followed by (e) adding the lactone to the reaction medium from (d) in order to selectively obtain a block copolymer.

9 . The process of claim 8 , wherein the cyclic carbonate is trimethylene carbonate (TMC), the lactone is s-caprolactone (s-CL), and the block copolymer is a P(CL-b-TMC-b-CL) triblock copolymer.

10 . The process of claim 9 , wherein the molar ratio of monomers to bifunctional initiator, TMC/s-CL/bifunctional initiator, is between 60/60/1 and 120/240/1.

11 . The process of claim 8 , wherein the bifunctional initiator/methanesulfonic acid (MSA) molar ratio is between 1/1 and 1/3.

12 . The process of claim 8 , which is conducted at a temperature of between 20 and 120° C.

13 . The process of claim 8 , which is conducted at a temperature of between 30° C. and 60° C.

14 . The process of claim 8 , wherein the nonchlorinated aromatic solvent is toluene, ethylbenzene or xylene.

15 . The process of claim 8 , wherein the cyclic carbonate is trimethylene carbonate (TMC).

16 . The process of claim 8 , wherein the lactone is s-caprolactone (s-CL).

17 . The process of claim 8 , wherein the nonchlorinated aromatic solvent is toluene.

18 . The process of claim 8 , wherein the block copolymer obtained is a P(CL-b-TMC-b-CL) triblock copolymer.

19 . The process of claim 8 , wherein the bifunctional initiator comprises water.

20 . The process of claim 8 , wherein the bifunctional initiator comprises a diol.

21 . The process of claim 8 , which is conducted continuously or batchwise.

22 . The process of claim 8 , wherein the block copolymer exhibits a linear morphology.

23 . The process of claim 8 , wherein the block copolymer is obtained free from contamination by other copolymers or homopolymers.

24 . The process of claim 8 , wherein the block copolymer is a triblock copolymer.

25 . The process of claim 8 , wherein the block copolymer contains nanodomains.

26 . A PCL-b-PTMC-b-PCL block copolymer obtained by the process of claim 8 , wherein
each of the PCL blocks exhibits a degree of polymerization of between 30 and 120 and a number-average molecular weight Mn of between 3400 and 13680 g/mol, and the PTMC block exhibits a degree of polymerization of between 60 and 120 and a number-average molecular weight Mn of between 6100 and 12200 g/mol.

Assignees

• Arkema France
• Centre Nat Rech Scient
• Univ Toulouse 3 Paul Sabatier

Inventors

• Navarro Christophe
• Bourissou Didier
• Martin-Vaca Blanca
• Couffin Aline
• Kayser Franck

Classifications

• C08G63/823 Primary

  for the preparation of polylactones or polylactides · CPC title

• C08G64/302

  and cyclic ethers · CPC title

• C08G81/027

  containing polyester or polycarbonate sequences · CPC title

• C08K5/42

  Sulfonic acids; Derivatives thereof · CPC title

• C08G63/64

  Polyesters containing both carboxylic ester groups and carbonate groups · CPC title