Isocyantate-free method for preparing poly(carbonate-urethane) or poly(ester-urethane)

Patent metadata

Field	Value
Publication number	US-9365675-B2
Application number	US-201514729499-A
Country	US
Kind code	B2
Filing date	Jun 3, 2015
Priority date	Jul 15, 2010
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

Poly(carbonate-urethane) or poly(ester-urethane) may be characterized in that of carbonate soft segments have molecular weights Mn ranging between 10,000 and 250,000 g/mol. The segments' length may be monitored by the ring-opening polymerization condition. The process of preparing the poly(carbonate-urethane) or poly(ester-urethane) may include immortal ring-opening polymerization of a cyclic carbonate or of a cyclic ester or diester monomers in the presence of a first catalyst system and diols or polyols. The process may include chemical modification of the hydroxyl chain-end groups into carboxylic groups in the presence of a second catalyst system. The process may include a coupling reaction with at least 2 equivalents of a second cyclic carbonate, enabling coupling with the carboxylic moiety in the presence of a third catalyst system. The process may include polyaddition of a diamine or a polyamine via ring-opening of the second cyclic carbonate, and obtention of poly(carbonate-urethane) or poly(ester-urethane).

First claim

The invention claimed is:

1. Poly(carbonate-urethane) or poly(ester-urethane) obtained by a process and characterised in that the poly(carbonate-urethane) has polycarbonate soft segments or the poly(ester-urethane) has polycarbonate soft segments, wherein the polycarbonate soft segments have molecular weights Mn ranging between 10,000 and 250,000 g/mol, wherein the process comprises the steps of:
a) immortal ring-opening polymerisation of a first 5-, 6-, or 7-membered cyclic carbonate or of a cyclic ester or diester monomers, bearing or not bearing functional groups, in the presence of a first catalyst system and in the presence of one or more diols or polyols acting both as co-initiators and chain transfer agents;
b) chemical modification of the hydroxyl chain-end groups into carboxylic groups in the presence of a second catalyst system;
c) coupling reaction with at least 2 equivalents of a second 5-, 6-, or 7-membered cyclic carbonates, bearing at least one functional group enabling coupling with the carboxylic moiety, in the presence of a third catalyst system;
d) polyaddition of a diamine or a polyamine via ring-opening of the second terminal 5-, 6-, or 7-membered cyclic carbonate of step c); and
e) obtention of poly(carbonate-urethane) or poly(ester-urethane);
wherein the poly(carbonate-urethane) or the poly(ester-urethane) is prepared without use of isocyanates.

2. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the first catalyst system is selected from an organometallic compound, or from (LO)ZnR where LO is a multidentate phenolate ligand and R is Et or N(SiMe 3 ) 2 , or from a Lewis acidic metal salt, or from an organocatalyst wherein the organocatalyst precursors are selected from 4-dimethylaminopyridine (DMAP) or 1,5,7-triazobicyclo-[4,4,0]dec-5-ene (TBD) or tert-butylimino-1,3-dimethylperhydro-1,3,2diazaphosphine (BEMP).

3. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the first catalyst system is selected from amido-zinc β-diiminate (BDI)ZnN(SiMe 3 ) 2 , or from a triflate compound M(OSO 2 CF 3 ) n , with M=Al or Bi.

4. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the diol or polyol is of general formula R(OH)n where n is equal to 2 or more and R is a linear or branched, aliphatic or aromatic hydrocarbyl having up to 20 carbon atoms, or any combination thereof.

5. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the ratio monomer/catalyst ranges between 1,000,000:1 and 100:1.

6. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the ratio monomer/diol or polyol ranges between 10,000:1 and 10:1.

7. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the chemical modification of step b) is carried out by reacting the polycarbonate or polyester obtained in step a) with an anhydride, optionally in the presence of an inert solvent.

8. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the second catalyst system is a catalyst suitable for opening of an anhydride with an alcohol, selected from pyridine or from a mixture of triethylamine and 4-dimethylaminopyridine (DMAP).

9. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the coupling reaction of step c) is carried out in the presence of a third catalyst system selected from pyridine or DMAP, optionally in the presence of a coupling agent.

10. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the third catalyst system is loaded in an amount of 0.1 to 5% with respect to the second 5-, 6-, or 7-membered cyclic carbonates, bearing at least one functional group.

11. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the polyaddition of step d) is carried out with a diamine or a polyamine of general formula R(NH 2 ) n where n is equal to 2 or more and R is a linear or branched, aliphatic or aromatic hydrocarbyl having up to 12 carbon atoms, or a combination thereof.

12. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 11 , wherein the ratio NH 2 /cyclic carbonate ranges between 0.5 and 5.

13. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 12 , wherein the length of the polymer chain is determined by the ratio NH 2 /cyclic carbonate.

14. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , wherein the length of the polymer chain increases with increasing temperature of the polyaddition reaction.

15. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 1 , characterised in that polycarbonate soft segments have molecular weights Mn ranging between 50,000 and 100,000 g/mol.

16. Poly(carbonate-urethane) having polycarbonate soft segments or poly(ester-urethane) having polycarbonate soft segments, wherein the poly(carbonate-urethane) or the poly(ester-urethane) is characterised in that the polycarbonate soft segments have molecular weights Mn ranging between 10,000 and 250,000 g/mol, wherein the poly(carbonate-urethane) or the poly(ester-urethane) is prepared without use of isocyanates.

17. Poly(carbonate-urethane) or poly(ester-urethane) according to claim 16 , characterised in that polycarbonate soft segments have molecular weights Mn ranging between 50,000 and 100,000 g/mol.

Assignees

• Total Res & Technology Feluy
• Centre Nat Rech Scient
• Centre Nat Recherche

Inventors

• Guillaume Sophie
• Helou Marion
• Carpentier Jean-François
• Slawinski Martine

Classifications

• C08G71/04 Primary

  Polyurethanes · CPC title

• C08G64/0225

  containing atoms other than carbon, hydrogen or oxygen · CPC title

• C08G64/0216

  containing a chain-terminating or -crosslinking agent · CPC title

• C08G64/305

  and alcohols · CPC title

• C08G64/0208

  saturated · CPC title