Bio-based plasticiser for resins and blends containing said plasticiser

Abstract

The present invention relates to a family of preferably bio-based plasticisers and resins containing said plasticisers. The disclosed plasticisers belong to the poly (ester ether) family. Resins containing the plasticisers exhibit a broad range of applicability in terms of suitable processing techniques and utilisation for final products.

Claims

1. A plasticiser having a number average molecular weight of at least 1500 g/mol, the plasticiser comprising the following: a. dicarboxylic acids and dialcohols, b. one of a multifunctional alcohol or a carboxylic acid in a concentration below 20% by weight, c. a molecule with at least one ether moiety and reactive groups towards one of alcohols or carboxylic acids or a molecule capable of forming an ether upon reaction with the dialcohols, where the number average molecular weight of the molecule with at least one ether moiety and reactive groups towards one of alcohols or carboxylic acids is at least 140 g/mol and where the amount of cycloaliphatic molecules is below 50% by weight.

2. The plasticiser according to claim 1, where the molar mass is at least 2000 g/mol, preferably at least 5000 g/mol, even more preferably at least 8000 g/mol and most preferably at least 10000 g/mol.

3. The plasticiser according to claim 1 or 2, where the one of the multifunctional alcohol or the carboxylic acid is present in a concentration below 15% by weight, preferably below 10% by weight, and more preferably below 5% by weight.

4. The plasticiser according to any of claims 1-3, where the multifunctional alcohol or carboxylic acid in addition to comprising one of a an alcohol or a carboxylic acid group also comprises an anhydride or amine group, preferably one or more of the following: molecules including malic acid, citric acid, tartaric acid, glucose, fructose, sucrose, glycerol, xylitol, sorbitol, glyceric acid, and suitable amino acids such as arginine, lysine, asparagine, and serine.

5. The plasticiser according to any of claims 1-4, where the molecule with at least one ether moiety and reactive groups towards one of alcohol and carboxylic acids or a molecule capable of forming an ether upon reaction with the dialcohols is present in a concentration of 10-50% by weight, preferably 15-40% by weight, more preferably 20-35% by weight, and most preferably 21-33% by weight.

6. The plasticiser according to any of claims 1-5, where the amount of aromatic molecules is below 20% by weight, preferably below 10% by weight, more preferably below 5% by weight, and most preferably the plasticiser is free of aromatic moieties.

7. The plasticiser according to any of claims 1-6, where the amount of cycloaliphatic molecules is below 20% by weight, preferably below 10% by weight, and more preferably below 5% by weight.

8. The plasticiser according to any of claims 1-7, where a percentage of the alcohol groups in the monomers is substituted for amino groups and where the percentage is below 10% by weight, preferably below 7% by weight, and more preferably below 5% by weight.

9. The plasticiser according to any of claims 1-8, where part of the dialcohol is replaced by a diamine or a molecule containing one primary amine group and one of a carboxylic acid or an alcohol group to introduce amide bonds into the plasticiser, and where molecules for substitution of dialcohol comprise alanine, isoleucinemethionine, phenylalanine, glycine, valine, isophoronediamine, 1,3-propanediamin, 1,4-butanediamiane, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, aminomethanol, ethanolamine, propanolamine, aminomethyl propanol, and valinol.

10. The plasticiser according to any of claims 1-9, where the molecules used to produce said plasticiser is derived from at least 40% by weight of renewable materials, preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, and most preferably 100% by weight of renewable materials.

11. A resin comprising a plasticiser of any of claims 1-10, where said plasticiser has a number average molecular weight of at least 1500 g/mol and where the plasticiser comprises the following: dicarboxylic acids and dialcohols; at least one of a multifunctional alcohol or a carboxylic acid in a concentration below 20% by weight; one of a molecule with at least one ether moiety and reactive groups towards alcohol and carboxylic acids or a molecule capable of forming an ether upon reaction with the dialcohols and where said molecule with at least one ether moiety and reactive groups towards alcohol and carboxylic acids has a number average molecular weight of at least 140 g/mol and the amount of cycloaliphatic molecules in the plasticiser is below 50% by weight.

12. A resin according to claim 11, where the plasticiser is miscible in a concentration up to 5% by weight, preferably up to 10% by weight, and more preferably up to 15% by weight.

13. A resin according to claim 11 or 12, where the resin comprises poly lactic acid (PLA).

14. A resin according to any of claims 11-13, where at least one of the resin or the plasticiser contains a dye.

15. A resin synthesised from a plasticiser of any of claims 1-10, where said plasticiser has a number average molecular weight of at least 1500 g/mol and where the plasticiser comprises the following: dicarboxylic acids and dialcohols; at least one of a multifunctional alcohol or a carboxylic acid in a concentration below 20% by weight; one of a molecule with at least one ether moiety and reactive groups towards alcohol and carboxylic acids or a molecule capable of forming an ether upon reaction with the dialcohols and where the ending groups of the plasticiser is used to ring open a cyclic monomer to create a polymer with the plasticiser as the core of the polymer.

Description

EXAMPLE 1

[0056] A round bottomed flask equipped with a stirrer, a reflux condenser, and a pressure gauge is placed in an oil bath at 150? C. 0.2 mol succinic acid, 0.12 mol butanediol, 0.02 mol citric acid, 0.1 mol PEG-200, and 0.03 mol hydrochloric acid are allowed to react for 3 h under conditions of reduced pressure below 5000 Pa.

EXAMPLE 2

[0057] A round bottomed flask equipped with a stirrer is placed in an oil bath at 140? C. and 0.12 mol malonic acid, 0.12 mol glutaric acid, 0.2 mol butanediol, 0.15 mol 1,3-propanediol, 0.02 mol malic acid, 0.1 mol O,O-oxydiethylene-diglycolic acid, and 0.03 mol sulphuric acid are allowed to react for 4 h under conditions of reduced pressure below 15.000 Pa.

EXAMPLE 3

[0058] A round bottomed flask equipped with a stirrer, a reflux condenser, and a pressure gauge is placed in an oil bath at 130? C. 0.2 mol adipic acid, 0.1 mol ethanediol, 0.15 mol lysine, 0.1 mol citric acid, 0.1 mol O,O-oxydiethylene-diglycolic acid, 0.05 mol Jeffamine D-230 (polyoxypropylene diamine) and 0.03 mol phosphoric acid are allowed to react for 3 h under conditions of reduced pressure below 10.000 Pa.

EXAMPLE 4

[0059] 10 g of the plasticiser of example 1 is in an extruder mixed with 40 g of PLA and extruded into pellets.

EXAMPLE 5

[0060] A round bottomed flask is placed in an oil bath at 170? C. and 10 g of the plasticiser of example 3, 90 g lactide and 0.1 mg stannous octoate are added to the flask. The mixture is allowed to react for 2 h.

EXAMPLE 6

[0061] A round bottomed flask equipped with a magnetic stirrer is placed in a silicone oil bath at 170? C. and 15.6 g (0.1 mol) 2,5-furandicarboxylic acid, 5.9 g (0.05 mol) succinic acid and 11.4 g (0.15 mol) 1,3-propanediol are added. When the chemicals have melted, 50 mg 8 mol/L sulphuric acid is added. The mixture is allowed to react for 3 h under atmospheric pressure. Subsequently, 30 g of the plasticizer of example 3 is added to the flask and the pressure is reduced to a value not higher than 10.000 Pa.