Oligocarbonate polyols obtained from dianhydrohexitol dialkylcarbonate or a dimer of dianhydrohexitol carbonate, method for the production thereof and uses thereof

Patent metadata

Field	Value
Publication number	US-11299585-B2
Application number	US-201816756346-A
Country	US
Kind code	B2
Filing date	Oct 15, 2018
Priority date	Oct 16, 2017
Publication date	Apr 12, 2022
Grant date	Apr 12, 2022

Abstract

Provided is a method for producing an oligocarbonate polyol devoid of aromatic groups and phenolic functions, comprising a step of polycondensation by transesterification of monomers (A1) and/or dimers (A2) and of diol monomers (B1) and/or of triol monomers (B2), in a particular molar ratio, in order to obtain an oligocarbonate polyol having a molar mass of less than 5000 g/mol and at least two hydroxyl-type chain ends, the monomer (A1) corresponding to the following formula: (A1) and the dimer (A2) corresponding to the following formula: (A2) as well as the oligocarbonate polyol that can be obtained by this method and the polycarbonate that can be obtained by reacting this oligocarbonate with a polyisocyanate.

First claim

The invention claimed is:

1. A process for the preparation of a polycarbonate-urethane, wherein an oligocarbonate polyol is reacted with a polyisocyanate, wherein the oligocarbonate polyol is obtained by a second process comprising the steps of:
a stage (1) of introduction, into a reactor:
of a monomer of formula (A1):

in which R 1 and R 2 are identical or different alkyl groups, or of a dimer of formula (A2):

in which R 3 and R 4 are identical or different alkyl groups, or of a mixture of (A1) and (A2);

a stage (2) of introduction, into the reactor, of a diol monomer (B1) or of a triol monomer (B2) or of a mixture of (B1) and (B2), (B1) and (B2) both being different from (A1) and (A2);
the molar ratio in the reactor of (A1) and (A2) with respect to (B1) and (B2) corresponding to the following formula:

[

(

A
⁢
1

)

2

+

(

A
⁢
2

)

2

]

[

(

B
⁢
1

)

2

+

(

B
⁢
2

)

3

]

<
1

,

a subsequent stage (3) of polycondensation by transesterification of the monomers and dimers (A1), (A2), (B1) and (B2) in order to obtain an oligocarbonate polyol having a molar mass of less than 5000 g/mol and two or more hydroxyl chain end groups, and
a stage (4) of recovery of the oligocarbonate polyol;

wherein the diol monomer (B1) is chosen from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol or 1,10-decanediol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,4-hexanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol or 2-methyl-1,3-propanediol or from the following cyclic diols:
cyclohexanedimethanols;
tricyclodecanedimethanols;
pentacyclopentanedimethanols;
decalindimethanols;
norbornanedimethanols;
adamantanedimethanols,
cyclohexanediols,
tricyclodecanediols,
pentacyclopentadecanediols,
decalindiols,
norbornanediols,
adamantanediols,
spiroglycol,
2,2,4,4-tetramethyl-1,3-cyclobutanediol;
di-O-methylene-D-glucitol and dimethyl di-O-methylene-D-glucarate.

2. The process as claimed in claim 1 , wherein the monomer (A1) is introduced into the reactor in stage (1) alone or as a mixture with the dimer (A2).

3. The process as claimed in claim 1 , wherein the molar ratio in the reactor of (A1) and (A2) with respect to (B1) and (B2), corresponding to the following formula:

[

(

A
⁢
1

)

2

+

(

A
⁢
2

)

2

]

[

(

B
⁢
1

)

2

+

(

B
⁢
2

)

3

]

is strictly less than 1 and greater than 0.5.

4. The process as claimed in claim 1 , wherein R 1 , R 2 , R 3 and R 4 are independently chosen from alkyl groups comprising from 1 to 10 carbon atoms.

5. The process as claimed in claim 2 , wherein the monomer (A1) is an isosorbide bis(alkyl carbonate).

6. The process as claimed in claim 1 , wherein the triol monomer (B2) is chosen from aliphatic diols and triols, branched aliphatic diols and triols and cyclic aliphatic diols and triols.

7. The process as claimed in claim 1 , wherein stage (3) takes place in the presence of a catalyst of polycondensation by transesterification.

8. The process as claimed in claim 7 , wherein the molar amount of catalyst with respect to the amount of the monomer (A1) and of the dimer (A2) advantageously ranges from 10 −7 % to 1% by weight.

9. The process as claimed in claim 1 , wherein stage (3) is carried out under an inert atmosphere.

10. The process as claimed in claim 1 , wherein a part of stage (3) is carried out at a temperature ranging from 100° C. to 250° C.

11. The process as claimed in claim 1 , wherein the oligocarbonate polyol comprises a phenol content of less than 50 ppb.

12. The process as claimed in claim 1 , wherein the polyisocyanate is a diisocyanate.

13. The process as claimed in claim 12 , wherein the diisocyanate is a linear or cyclic aliphatic diisocyanate.

14. A polycarbonate-urethane obtained by the process as claimed in claim 1 , having a molar mass greater than 5000 g/mol.

15. The polycarbonate-urethane as claimed in claim 14 , exhibiting a maximum flexural stress of greater than 1800 MPa, as measured according to Standard ISO 178:2010.

16. The po

Assignees

• Roquette Freres

Inventors

• Corpart Jean-Marc
• Saint-Loup René

Classifications

• C08G64/403

  Recovery of the polymer · CPC title

• C08G64/305 Primary

  and alcohols · CPC title

• C08G64/02 Primary

  Aliphatic polycarbonates · CPC title

• C08G64/0208

  saturated · CPC title

• C08G18/44

  Polycarbonates · CPC title