SPECIFIC METHOD FOR PREPARING BIOBASED POLYESTERS

• US 20170306087A1
• Filed: 09/10/2015
• Published: 10/26/2017
• Est. Priority Date: 09/12/2014
• Status: Active Grant

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Cogordan, Frank, Ozeray, Herve W., Riondel, Alain F.
• Granted Patent: US 9,969,840 B2
• Time in Patent Office: Days
• CPC Class Codes: C08G 63/668 derived from polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 63/672 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/85 Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof C08G63/823 takes precedence
• CPC Class Codes: C08G 63/916 Dicarboxylic acids and dihydroxy compounds

Abstract

The present invention relates to a method for preparing a linear or branched hydroxylated and/or carboxylated polyester resin that is free of unsaturated fatty acids, comprising reacting an acid component with an alcohol component, said acid component comprising at least one C4 to C6 polycarboxylic acid or anhydride, and at least one C8 to C54 polycarboxylic acid or anhydride, and said alcohol component comprising at least one biobased polyol having a functionality of at least 2 bearing a 1,4:3,6-dianhydrohexitol unit, and at least one of two polyols b2) and b3).

Claims

1. A process for preparing a hydroxylated or carboxylated, optionally hydroxylated and carboxylated, linear or branched polyester resin free of unsaturated fatty acid, wherein said process comprises reaction between an acid component a) and an alcohol component b), with said acid component a) comprising:

a1) at least one C₄ to C₆ polycarboxylic acid or anhydride,

a2) at least one C₅ to C₅₄ polycarboxylic acid or anhydride, and

a3) optionally, at least one C₂ to C₂₂ saturated monoacid, and

with said alcohol component b) comprising;

b1) at least one biobased polyol having a functionality f_b1 of at least 2, bearing a 1,4;

3,6-dianhydrohexitol unit,

and at least one of the-fallow two polyols b2) or b3);

b2) at least one polyol different than b1) having a functionality f_b2 of at least 2

b3) at least one polyol different than b1) and b2) having a functionality f_b3 of at least 3,

with said reaction being carried out according to the following successive steps;

i) reaction of all of the acid component a) with said component b1) of said alcohol component b) until a conversion of at least 85%, of said component b1) is obtained, followed by

ii) reaction of the product resulting from step i) with the rest of said alcohol component b), comprising at least one of said polyols b2) or b3),

the reactions of said steps i) and ii) taking place in solution in at least one organic solvent which can form an azeotrope with water.

2. The process as claimed in claim 1, wherein said step i) is carried out in the presence of a catalyst chosen from:

tin derivatives from tin oxalate, butylstannoic acid or tin(II) oxide,

titanium derivatives from alkyl titanates.

3. The process as claimed in claim 2, wherein the amount by weight of said catalyst relative to the weight of all of the reactants of step i) (a)+b1)) ranges from 0.01% to 0.5%.

4. The process as claimed in claim 1 wherein said step i) is carried out at a temperature ranging from 150 to 220°

C.

5. The process as claimed in claim 1 wherein said step ii) is carried out at a temperature ranging from 180 to 250°

C.

6. The process as claimed in claim 1 wherein said organic solvent is selected from the group consisting of ketones, aromatic solvents, cycloaliphatic solvents, and alkanes which are at least C₇ alkanes.

7. The process as claimed in claim 1 wherein a fraction by weight of at least 50% of said polyol b) is biobased.

8. The process as claimed in claim 1 wherein said component b1) is chosen from the group consisting of isosorbide (1,4:

3,6-dianhydro-D-sorbitol), isomannide (1,4;

3,6-dianhydro-D-mannitol) and isoidide (1,4;

3,6-dianhydro-L-iditol).

9. The process as claimed in claim 1 wherein at least 50%, by weight relative to the overall weight of said components a)+b) is biobased.

10. The process as claimed in claim 1 wherein the components a) and b) are 100% biobased.

11. The process as claimed in claim 1 wherein said polyol b2) is biobased and chosen from the prowsonsistinq of, 1,3-propylenediol, 1,2-propylenediol, 1,4-butanediol, and diols based on saturated fatty acids.

12. The process as claimed in that claim 1 wherein said polyol b3) is biobased and chosen from the group consisting glycerol and ether-polyol derivatives thereof.

13. The process as claimed in claim 1 wherein said polyacid a1) is a biobased aliphatic diacid chosen from the group consisting of succinic acid, tartaric acid, citric acid, malic acid, itaconic acid, glutaric acid, glutamic acid, fumaric acid, furandicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid and tetrahydrafuran-3,5-dicarboxylic acid.

14. The process as claimed in claim 1 wherein said polyacid a2) is biobased and chosen from the group consisting of azelaic acid (C₉), sebacic acid (C₁₀), undecanedioic acid, dodecanedioic acid OF and respectively C₃₆ and C₅₄ fatty acid dimers and trimers.

15. The process as claimed in claim 1 wherein said monoacid a3) is selected from the group consisting of acetic acid, pyruvic acid, lactic acid, rosin (which meansa abietic acid and C₂₀ isomers) and a C₁₂ to C₂₂ saturated fatty acid.

16. The process as claimed in claim 1 wherein said polyol b1) represents at least 40 mol/mol % relative to the component b).

17. The process as claimed in claim 1 wherein during the first step i), the molar ratio of the carboxy groups of said component a) relative to the OH groups of said polyol b1) ranges from 1.1 to 2.1.

18. The process of claim 1, wherein said at least one C₄ to Ce polycarboxylic acid or anhydride has a functionality f_a, ranging from 2 to 4 and the at least one C₉ to C₅₄ polycarboxylic acid or anhydride has a functionality f_a2 ranging from 2 to 4.

19. The process of claim 1, wherein the said polyol b2) is a polyol in C₃-C₃₆.

20. The process of claim 1, wherein f_a1=2, f_a2=2, f_b1=2, f_b2=2 and f_b3=3.

21. The process of claim 1, wherein the reaction of all of the acid component a) with said component b1) of said alcohol component b) proceeds until a conversion of 100% of said component b1) is obtained.

22. The process of claim 2, wherein said alkyl titanates are selected from the group consisting of ethyl titanate, isopropyl titanate, butyl titanate, and 2-ethylhexyl titanate.

23. The process of claim 22, wherein said alkyl titanates are selected from the group consisting of isopropyl titanate and butyl titanate.