(Meth)acrylated compounds based on recycled PET

Patent metadata

Field	Value
Publication number	US-11267949-B2
Application number	US-202117160771-A
Country	US
Kind code	B2
Filing date	Jan 28, 2021
Priority date	Jul 12, 2016
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

The present invention relates to a process for preparing a polyester (meth)acrylate resin (I), said process comprising the steps of: (a) Reacting a thermoplastic polyester with (a1) at least one polyhydric alcohol and, optionally, with (a2) at least one triglyceride, wherein the molar ratio of triglyceride to thermoplastic polyester is between 0 and 0.3, and the molar ratio of polyhydric alcohol to thermoplastic polyester is at most 1.9 to obtain a depolymerization product A that has a hydroxyl number within the range of from 200 to 800 mg KOH/g; (b) Reacting the depolymerization product A with (b1) at least one fatty acid and/or (b2) at least one polybasic carboxylic acid and, optionally, with (b3) at least one polyhydric alcohol to provide a polyester polyol B; (c) Reacting the polyester polyol B with (c) at least one (meth)acrylating compound to provide a (meth)acrylated compound (I), wherein the weight ratio of fatty acid (b1) to the depolymerization product A is between 0 and 0.6, wherein the weight ratio of polybasic carboxylic acid (b2) to the depolymerization product A is less than 0.3, wherein the weight ratio of (meth)acrylating compounds (c) to the depolymerization product A is between 0.1 and 0.8, and wherein the (meth)acrylated compound (I) that is obtained has a number average molecular weight (Mn) of between 500 and 5,000 Dalton. Typically PET is used as starting material. Typically compounds (I) of the invention have a PET content of at least 15 wt %, preferably at least 25 wt %. The present invention also relates to (meth)acrylated compounds (I) thus obtained and to coating compositions and inks based upon these materials. Materials of the invention allow the use of a high amount of PET waste. Inks and coatings prepared from these materials exhibit an excellent pigment wetting and/or ink-water balance.

First claim

The invention claimed is:

1. A process for preparing a (meth)acrylated compound (I) comprising the steps of:
(a) reacting a thermoplastic polyester with (a1) at least one polyhydric alcohol and, optionally, with (a2) at least one triglyceride, wherein, when present, the molar ratio of triglyceride to thermoplastic polyester is between 0 and 0.3, and the molar ratio of polyhydric alcohol to thermoplastic polyester is at most 1.9 to obtain a depolymerization product A with a hydroxyl number within the range of from 200 to 800 mg KOH/g;
(b) reacting the depolymerization product A with (b1) at least one fatty acid and/or (b2) at least one polybasic carboxylic acid and, optionally, with (b3) at least one polyhydric alcohol to provide a polyester polyol B;
(c) reacting the polyester polyol B with (c1) at least one (meth)acrylating compound to provide a (meth)acrylated compound (I),
wherein the weight ratio of fatty acid (b1), when present, to the depolymerization product A is between 0 and 0.6,
wherein the weight ratio of polybasic carboxylic acid (b2), when present, to the depolymerization product A is less than 0.3,
wherein the weight ratio of (meth)acrylating agent to the depolymerization product A is between 0.1 and 0.8,
wherein the (meth)acrylated compound (I) has a number average molecular weight (Mn) between 500 and 5000 Da, and
wherein steps b) and c) are carried out at the same time.

2. The process of claim 1 , wherein the molar ratio of polyhydric alcohol (a1) to thermoplastic polyester is lower than 1.8.

3. The process of claim 1 , wherein the molar ratio of triglyceride (a2) to thermoplastic polyester is between 0.01 and 0.25.

4. The process of claim 1 , wherein the thermoplastic polyester in step (a) is selected from one or more of the group consisting of: polyethylene naphthalate (PEN); polyethylene terephthalate (PET); polypropylene terephthalate (PPT); polybutylene terephthalate (PBT); polytrimethylene terephthalate; glycol-modified polyethylene terephthalate; copolymers of terephthalic acid and 1,4-cyclohexanedimethanol; isophthalic acid-modified copolymers of terephthalic acid and 1,4-cyclohexanedimethanol; polyhydroxy alkanoates; copolymers of diols with 2,5-furandicarboxylic acid or dialkyl 2,5-furandicarboxylates; copolymers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol with isophthalic acid, terephthalic acid or orthophthalic derivatives; and dihydroferulic acid polymers.

5. The process of claim 4 , wherein the thermoplastic polyester is derived from waste material generated in the production of PET or in the production of PET molded articles.

6. The process of claim 1 , wherein the depolymerization product A that is formed in step (a) has a hydroxyl number of from 200 to 700 mg KOH/g.

7. The process of claim 1 , wherein the (b1) at least one fatty acid is/are dimer fatty acids (b1), the dimer fatty acids (b1) being added in step (b) in an amount of less than 70 wt %, based upon the total weight of the depolymerization product A.

8. The process of claim 7 , the dimer fatty acids (b1) being added in step (b) in an amount is from 1 to 60 wt %.

9. The process of claim 1 , wherein polybasic carboxylic acids (b2) are added in step (b) in an amount of less than 40 wt %, based upon the total weight of the depolymerization product A.

10. The process of claim 1 , wherein at least one polyhydric alcohol (b3) is added to the reaction mixture in step (b).

11. The process of claim 1 , wherein at least one monofunctional acid (b4) is added to the reaction mixture in step (b).

12. The process of claim 1 , wherein the weight ratio of (meth)acrylating compounds to the depolymerization product A is between 0.1 and 0.8.

13. The process of claim 1 , wherein the hydroxyl number is measured by titration of acetic acid after acetylation of hydroxyl groups and hydrolysis of acetic anhydride excess.

14. A (meth)acrylated compound (I) prepared by a process of claim 1 , wherein the (meth)acrylated compound (I) has a PET content of at least 15 wt %.

15. A radiation curable composition that is an ink, a varnish, a lacquer, a coating composition or an adhesive prepared from a (meth)acrylated compound (I) according to claim 14 .

16. An article, coated or printed, entirely or in part, with a radiation curable composition according to claim 15 .

17. A (meth)acrylated compound (I) prepared by a process of claim 1 , wherein the (meth)acrylated compound (I) has a PET content of at least 25 wt %.

Assignees

• ALLNEX Belgium SA

Inventors

• Van Den Bergen Hugues
• Gevaert Paul
• Peeters Stephan

Classifications

• C09J167/07

  having terminal carbon-to-carbon unsaturated bonds · CPC title

• C08G63/183

  Terephthalic acids · CPC title

• C08G63/91

  Polymers modified by chemical after-treatment · CPC title

• C07C67/03

  by reacting an ester group with a hydroxy group · CPC title

• C09D11/104

  Polyesters · CPC title