WO2022008051A1

WO2022008051A1 - Plasticizer compositions

Info

Publication number: WO2022008051A1
Application number: PCT/EP2020/069303
Authority: WO
Inventors: Peter Daute; Martin Schaefer; Thomas Schweichler
Original assignee: Emery Oleochemicals GmbH
Current assignee: Emery Oleochemicals GmbH
Priority date: 2020-07-08
Filing date: 2020-07-08
Publication date: 2022-01-13
Anticipated expiration: 2023-01-08

Abstract

The present invention relates to plasticizer compositions comprising at least one polyester plasticizer obtainable from a monomer composition comprising at least one aliphatic linear or branched, saturated or unsaturated C2-C22 monocarboxylic acid; at least one aliphatic linear or branched saturated C2-C12 dialcohol; and at least one dicarboxylic acid selected from aliphatic linear or branched saturated C2-C12 dicarboxylic acids and heterocyclic saturated, unsaturated or aromatic C6-C10 dicarboxylic acids. The present invention also relates to a use of a plasticizer composition as claimed as plasticizer; a plasticized composition comprising a plasticizer composition as claimed; as well as a use thereof.

Description

P L A S T I C I Z E R C O M P O S I T I O N S

The present invention relates to plasticizer compositions comprising at least one polyester plasticizer obtainable from a monomer composition comprising at least one aliphatic linear or branched, saturated or unsaturated C₂-C₂2 monocarboxylic acid; at least one aliphatic linear or branched saturated C₂-Ci₂ dialcohol; and at least one dicarboxylic acid selected from aliphatic linear or branched saturated C₂-Ci₂ dicarboxylic acids and heterocyclic saturated, unsaturated or aromatic C₆-Cio dicarboxylic acids.

The present invention also relates to a use of a plasticizer composition as claimed as plasticizer; a plasticized composition comprising a plasticizer composition as claimed; as well as a use thereof.

BACKGROUND

The present invention relates to compounds and compositions, which at least partially are derived from renewable resources and/or renewable origin.

If not stated otherwise, renewable resources and/or renewable origin in the context of the present invention is understood as organic raw materials that originate from agricultural and forestry production. For example, the products that can be considered of renewable resources and/or renewable origin are those obtained from sources that, by their very nature, are regenerable and inexhaustible on the time scale of human life and the use of which consequently does not negatively affect the availability of natural resources for future generations. A typical example of a renewable resource consists of vegetable crops. Renewable additives are ideal for use in bioplastics so that the whole composition comprising of main polymer/resin and plasticizer can still be regarded as 100% biobased.

Many polymer materials can be improved. In particular polyesters are brittle and have poor mechanical properties and thus require plasticizers. So far, there is a trend towards polyesters on renewable raw material but at the same time, there are very few plasticizers available that fulfil the present needs. In particular, plasticizers and plasticizer compositions that are available do not satisfy the present requirements sufficiently. Major drawbacks are inter alia the resources of the available systems are not adequately renewable; the mechanical properties of the available systems are not satisfying; plasticizers like AMG type, ATBC, soft-n-safe are not 100% biobased/renewable; some plasticizers show undesired high migration into other media.

The objective of the present invention therefore is to provide a plasticizer composition that fulfils the following requirements:

The plasticizer composition should be obtainable from monomers derived from renewable resources and/or renewable origin.

The plasticizer composition should provide advantageous mechanical properties, in particular regarding elongation at break.

The plasticizer composition should have advantageous physicochemical properties. Plasticizer migration should be minimized, in particular into other media.

These and other objectives are solved by the invention disclosed herein.

SUMMARY OF THE INVENTION

The present invention provides plasticizer compositions comprising at least one polyester plasticizer obtainable from a monomer composition comprising

- at least one aliphatic linear or branched, saturated or unsaturated C₂-C₂2 monocarboxylic acid,

- at least one aliphatic linear or branched saturated C₂-Ci₂ dialcohol, and

- at least one dicarboxylic acid selected from aliphatic linear or branched saturated C₂-Ci₂ dicarboxylic acids and heterocyclic saturated, unsaturated or aromatic C₆-Ci₀ dicarboxylic acids.

The compositions of the disclosed invention have several advantages. A particular advantage is that the compositions is obtainable from monomers derived from renewable resources and/or renewable origin. This allows a plasticized composition that entirely bases on renewable resources and/or renewable origin. A further particular advantage is that the compositions provide advantageous mechanical properties as plasticizers, in particular for polyesters. In addition, plasticizer migration is minimized.

Further embodiments of present invention are the use of a plasticizer composition as claimed as plasticizer; a plasticized composition comprising a plasticizer composition as claimed; as well as the use thereof.

The invention disclosed herein allows providing plasticizer compositions as well as plasticized polymer compositions based on renewable resources and/or renewable origin.

DETAILLED DESCRIPTION

Definitions

If not stated otherwise "aliphatic linear or branched, saturated or unsaturated C₂-C₂₂ monocarboxylic acid" comprise e.g. monocarboxylic acids having 2 to 22 C atoms. The monocarboxylic acids can be linear or branched. The monocarboxylic acids can be saturated or unsaturated, where the unsaturated monocarboxylic acids have at least one unsaturated C-C bond. Preferred compounds include C₁₂ fatty acids such as lauric acid and C_M fatty acids such as myristic acid and myristoleic acid.

If not stated otherwise "aliphatic linear or branched saturated C₂-Ci₂ dialcohol" comprise e.g. aliphatic dialcohol compounds having 2 to 12 C atoms. The dialcohol compounds can be linear or branched. The dialcohol compounds can be saturated or unsaturated, where the unsaturated dialcohol compounds have at least one unsaturated C-C bond. Preferred compounds include 1,2-ethandiol, 1,2-propandiol, 1,3-propandiol, 1,2-butandiol, 1,3-butandiol, und 1,4-butandiol.

If not stated otherwise "aliphatic linear or branched saturated C₂-Ci₂ dicarboxylic acids" comprise e.g. dicarboxylic acids having 2 to 12 C atoms. The dicarboxylic acids can be linear or branched. Preferred compounds include succinic acid, azelaic acid, and sebacic acid.

If not stated otherwise "heterocyclic saturated, unsaturated or aromatic C₆-Ci₀ dicarboxylic acids" comprise e.g. dicarboxylic acids having 6 to 10 C atoms. The dicarboxylic acids are heterocyclic, i.e. having as ring members atoms of at least two different elements. The compounds can be saturated, unsaturated or aromatic. Preferred compounds include 2,5-furandicarboxylic acid. Polyester plasticizer compositions

According to the invention, the plasticizer comprises at least one polyester plasticizer obtainable from a monomer composition comprising

- at least one aliphatic linear or branched saturated C₂-Ci₂ dialcohol, and

In a preferred embodiment, the monomer composition comprises at least 50 wt-% of the monomer composition, based on the total weight of the monomer composition, of monomers derived from renewable resources and/or renewable origin.

In a more preferred embodiment, the monomer composition comprises at least 70 wt.-%, preferably at least 90 wt.-%, more preferably at least 95 wt.-%, even more preferably at least 99 wt.-% of the monomer composition, based on the total weight of the monomer composition, of monomers derived from renewable resources and/or renewable origin.

In an even more preferred embodiment, the monomer composition essentially consists of monomers that are derived from renewable resources and/or renewable origin. More preferably, the monomer composition only consists of monomers that are derived from renewable resources and/or renewable origin.

In a preferred embodiment, the monomer composition comprises

- at least one aliphatic linear or branched, saturated or unsaturated C₂-C₂₂ monocarboxylic acid,

- at least one aliphatic linear or branched saturated C₂-Ci₂ dialcohol, and

- at least one dicarboxylic acid selected from aliphatic linear or branched saturated C₂-Ci₂ dicarboxylic.

However, more general, the at least one dicarboxylic acid is usually selected from aliphatic linear or branched saturated C₂-Ci₂ dicarboxylic acids and heterocyclic saturated, unsaturated or aromatic C₆-Cio dicarboxylic acids. Suitable heterocyclic saturated, unsaturated or aromatic C₆-Ci₀ dicarboxylic acids are commonly known and include for example 2,5-furandicarboxylic acid.

In a preferred embodiment, the at least one monocarboxylic acid is selected from C₈-Ci₈ fatty acids and mixtures thereof, that include linear and branched, saturated and unsaturated carboxylic acids.

In a more preferred embodiment, the at least one monocarboxylic acid is selected Ci₂-Ci₆ fatty acids such as Ci2 fatty acids, C_M atty acids, Ci₆ fatty acids, where a mixture of C₁₂ fatty acids and C_M fatty acids is particularly preferred.

In an even more preferred embodiment, the monocarboxylic acid is a combination of lauric acid and myristic acid.

In a preferred embodiment, the at least one dialcohol is selected from C₂-C₆-dialcohols including mixtures thereof. The at least one dialcohol is preferably selected from 1,2-ethandiol,

1,2-propandiol, 1,3-propandiol, 1,2-butandiol, 1,3-butandiol, and 1,4 butandiol.

In an even more preferred embodiment, the dialcohol is 1,2-propandiol. In a preferred embodiment, the at least one dicarboxylic acid is selected from linear and branched C2-C12 dicarboxylic acids. In a first embodiment, the decarboxylic acid is selected from C₂-C₆ dicarboxylic acids, preferably C₄ dicarboxylic acid, more preferably succinic acid. In a second embodiment, the dicarboxylic acid is selected from C₈-Ci₂ dicarboxylic acids, preferably from C₉ and C10 dicarboxyclic acid, more preferably from azelaic acid and sebacic acid.

In an even more preferred embodiment, the at least one dicarboxylic acid is succinic acid.

Particular preferred plasticizer compositions comprise a plasticizer compound obtainable from a monomer composition comprising lauric acid, myristic acid, 1,2-propandiol and succinic acid. Preferably, the monomer composition comprises at least 50 wt.-%, more preferably 70, more preferably 90 wt.-% and even more 95 wt.-%, based on the total weight of monomers, of said monomers lauric acid, myristic acid, 1,2-propandiol and succinic acid.

The at least one polyester plasticizer has, in a preferred embodiment, the following structure of formula (I)

R¹-C(=0)- {0-R²-0-C(=0)-R³-C(=0)}_n -0-R²-0-C(=0)-R¹ (I) where

R¹ is independently C₇-Ci₇ alkyl;

R² is independently C₂-Ci₂ alkylene;

R³ is independently C₀-Ci₀ alkylene; n is an integer from 1 to 100;

In a preferred embodiment, the polyester plasticizer has a structure of formula (I) where R¹ is independently Cn-Ci₅ alkyl, R² is independently C₃ alkylene, R³ is independently C₂ alkylene, n is an integer from 2 to 40; and more preferably, where R¹ is independently Cn-Ci₅ alkyl, R² is independently C₃ alkylene, R³ is independently C₂ alkylene, n is an integer from 5 to 30.

Preferred polyester plasticizers of formula (I) have the following structure (l.x):

R¹-C(=0)- {O-CH(CH₃)-CH2-O-C(=O)-C₂H4-C(=O)-}₁₀0-CH(CH₃)-CH₂-0-C(=0)-R¹ (l.x) where R¹ is independently CnH₂₃ or CI₃H₂₇.

Particular preferred polyester plasticizers of formula (I) are selected from the following structures (l.a) to (l.f):

CIIH₂₃-C(=0)- {0-CH(CH₃)-CH₂-0-C(=0)-C₂H₄-C(=0)-}₁₀0-CH(CH₃)-CH₂-0-C(=0)-C₁₁H₂₃ (l.a)

CIIH₂₃-C(=0)- {O-CH(CH₃)-CH₂-O-C(=O)-C₂H₄-C(=O)-}₁₀0-CH(CH₃)-CH₂-0-C(=0)-C₁₃H₂₇ (l.b)

CI₃H₂₇-C(=0)- {O-CH(CH₃)-CH₂-O-C(=O)-C₂H₄-C(=O)-}₁₀0-CH(CH₃)-CH₂-0-C(=0)-C₁₃H₂₇ (l.c))

CIIH₂₃-C(=0)- {O-CH(CH₃)-CH₂-O-C(=O)-C₂H₄-C(=O)-}₁₀0-CH(CH₃)-CH₂-0-C(=0)-C₁₅H₃₁ (l.d)

CI₃H₂₇-C(=0)- {O-CH(CH₃)-CH₂-O-C(=O)-C₂H₄-C(=O)-}₁₀0-CH(CH₃)-CH₂-0-C(=0)-C₁₅H₃₁ (l.e)

CI₅H₃I-C(=0)- {O-CH(CH₃)-CH₂-O-C(=O)-C₂H₄-C(=O)-}₁₀0-CH(CH₃)-CH₂-0-C(=0)-C₁₅H₃₁ (l.f)

Even more particularly preferred polyester plasticizers are of structure (l.a). The plasticizer composition may also comprise at least one polyester plasticizer as defined above having the structure of formula (I) and at least one polyester plasticizer of the following structure of formula (II)

H- {0-R²-0-C(=0)-R³-C(=0)}_n -0-R²-0-C(=0)-R¹ (II) where

R¹ is independently C₇-Ci₇ alkyl;

R² is independently C₂-Ci₂ alkylene;

R³ is independently C₀-Ci₀ alkylene; n is an integer from 1 to 100.

The preferred definitions of R¹, R², R³, and n given in the context of the structure(s) of formula (I) also apply for the structure(s) of formula (II). In a preferred embodiment, the polyester plasticizer composition comprises a structure of formula (II) where R¹ is independently Cn-Ci₅ alkyl, R² is independently C₃ alkylene, R³ is independently C₂ alkylene, n is an integer from 2 to 40; and more preferably, where R¹ is independently Cn-Ci₅ alkyl, R² is independently C₃ alkylene, R³ is independently C₂ alkylene, n is an integer from 5 to 30.

Particular preferred polyester plasticizers of formula (II) are selected from the following structures (II. a) to (II. c):

Preferably, the polyester plasticizer and/or the polyester plasticizer composition has a weight average molecular weight M_w, measured by gel permeation chromatography (GPC), in the range of 500 to 5000 g/mol, more preferably in the range of 1000 to 4000 g/mol. The molecular weight is typically measured by measured by gel permeation chromatography (GPC), preferably using polyethylenglycol (PEG) standard and tetrahydrofuran (THF) solvent.

Preferably, the polyester plasticizer and/or the polyester plasticizer composition has a viscosity, measured according to DIN ISO 53019 in the range of 600 to 15000 mPas, more preferably in the range of 700 to 6000 mPas. The viscosity is typically measured according to DIN ISO 53019, preferably Brookfield.

Preferably, the polyester plasticizer and/or the polyester plasticizer composition has an acid number, measured according to DIN EN ISO 2114, of at most 3 mg KOH/g, more preferably in the range of 0.1 to 2 mg KOH/g. The acid number is typically measured according to according to DIN EN ISO 2114.

Preferably, the polyester plasticizer and/or the polyester plasticizer composition has an OH number, measured according to DIN 53240, of at most 120 mg KOH/g, more preferably of at most 50 mg KOH/g more preferably of at most 40 mg KOH/g more preferably of at most 30 mg KOH/g. The OH number is typically measured according to according to DIN 53240.

The disclosed polyester plasticizers obtainable from a monomer composition can be obtained by conventional methods that are known to skilled persons. In general, the polyester plasticizer may be obtained via polymerization such as a polycondensation reaction. In a preferred embodiment, the polyester plasticizer is obtained via a polycondensation reaction.

In general, the polyester plasticizer may be obtained using a catalyst as commonly used for those reactions. In a preferred embodiment, the catalyst is selected from acid catalysts, tin catalysts, titanium catalysts, and more preferably selected from titanium complexes, more preferably tetra- n-butyl titanate.

In general, the polyester plasticizer may be obtained by at elevated temperatures in the range of 100 to 290 °C, preferably in the range of 160 to 240 °C. Likewise, the polyester plasticizer may be obtained at normal or reduced pressure. In a preferred embodiment, the polyester plasticizer is obtained at reduced pressure and elevated temperatures in the range of 100 to 290 °C, preferable of 160 to 240 °C.

The plasticizer composition disclosed herein may, in a preferred embodiment, comprise at least 50 wt.-%, preferably at least 70 wt.-%, more preferably at least 90 wt.-%, and even more preferably at least 95 wt.-%, based on the total weight of the composition, of the at least one polyester plasticizer obtainable from the monomer composition disclosed herein.

In another embodiment, the plasticizer composition may comprise further components and ingredients such as polymers, fillers, pigments, additives and the like. Suitable polymers are for example the polyhydroxyalkanoate-based polyesters specified below. Usually, the amount of these further components and ingredients does not exceed 50 wt.%, preferably 30 wt.-%, preferably 10 wt.-%, based on the total weight of the composition.

The use of the polyester plasticizer compositions

The plasticizer composition disclosed herein are suitable for many applications.

A preferred use of the plasticizer compositions is as plasticizer for polyhydroxyalkanoate-based polyesters, preferably derived from renewable resources and/or renewable origin. This includes homopolymers and copolymers. Polyhydroxyalkanoate-based polyesters include polylactide (PLA), poly(3-hydroxybutyrate) (PHB), poly(3-hydroxyvalerate) (PHV), poly(3-hydroxybutyrate-co- 3-hydroxyvalerate) (PHBV) and the like. Preferred polyhydroxyalkanoates are selected from polylactide homopolymers, polyhydroxybutyrate homopolymers, and co-polymer polyesters based on polylactide and/or polyhydroxybutyrate. In a specific preferred embodiment polylactide polymers, in particular homopolymers are used. In another specific preferred embodiment polyhydroxybutyrate polymers, in particular homopolymers are used.

Another preferred use of the plasticizer compositions is as plasticizer for polybutylene adipate terephthalate (PBAT). PBAT is a biodegradable random copolymer, specifically a copolyester of adipic acid, 1,4-butanediol and terephthalic acid. It is well known and commercially available.

A preferred use of the plasticizer compositions is as plasticizer for improving mechanical properties, in particular improving the elongation at break. In a particular preferred embodiment, the mechanical properties of polyhydroxyalkanoate-based polyesters, in particular of homo- and/or co polymer polyesters based on polyhydroxyalkanoates such as polylactide (PLA) and/or polyhydroxybutyrate (PHB). Plasticized compositions

A further embodiment of the present invention are plasticized compositions comprising the plasticizer composition disclosed herein and at least one polyhydroxyalkanoate-based polyester. Preferred plasticizer compositions and preferred polyhydroxyalkanoate-based polyesters were described above. Preffered embodiments include polylactide (PLA) homopolymers and polyhydroxybutyrate (PHB) homopolymers and co-polymers of polylactide and/or polyhydroxybutyrate.

Preferably, the plasticized compositions comprise 5 to 30 wt.-% of the plasticizer composition, and 70 to 95 wt.-% of the least one polyhydroxyalkanoate-based polyester.

The plasticized compositions may comprise further components and ingredients such as fillers, pigments, additives and the like. Usually, the amount of these further components and ingredients does not exceed 20 wt.%, preferably 10 wt.-%, based on the total weight of the composition.

In a particular embodiment, the plasticized composition may comprise polybutylene adipate terephthalate (PBAT), a biodegradable random copolymer, specifically a copolyester of adipic acid, 1,4-butanediol and terephthalic acid. Likewise, the plasticized composition may comprise polybutylene succinate (PBS).

Use of plasticized compositions

Preferably, the plasticized compositions are used for processes selected from 3D printing, additive manufacturing, selective laser sintering (SLS), fused deposition modeling (FDM), fused filament fabrication (FFF), extrusion, film extrusion, injection molding, blow molding.

Preferably, the Preferably, the plasticized compositions are used for applications selected from packaging materials, 3D printing materials, construction materials, materials for toys.

EXAMPLES

The following examples further substantiate the present invention without being limiting.

Materials and methods

Fuller's earth - product "Tonsil Standard 310 FF" provided by "Clariant"

Succinic acid, based on renewable resources - provided by "Myriant"

Adipic acid, petrochemical - provided by "BASF"

1,2-propandiol, based on renewable resources - provided by "Oleon"

1,2-propandiol, petrochemical - provided by "BOfa"

C₁₂/C₁₄ monocarboxylic fatty acids, based on renewable resources - C12:C14 = 70:30; provided by "KLK" tetra-n-butyl titanate - provided by "Synthochem"

Examples 1 - 5

The ingredients, i.e. dicarboxylic acid, dialcohol, and monocarboxylic acid were added and 0.1 % tetra-n-butyl titanate was added before heating to approx. 170 °C under N₂ atmosphere. After approx. 3 hours, vacuum was applied to remove water and the vacuum was decreased within 4 hours to approx. 15 mbar, were the temperature was further increased to an end temperature of 230 °C. The acid number is monitored and an acid number of < 2 indicates the end of the reaction.

The mixture is cooled to approx. 90 °C and filtered after addition of 2 g Fuller's earth.

The following phycisochemical properties were determined:

Examples 6 - 11

The plasticized compositions were produced from polylactic acid (PLA Ingeo 3001D from NatureWorks) that was compounded with 20% by weight of the corresponding plasticizers by extrusion (using Leistritz ZSK 18; L/D=45) and subsequent granulation.

Test specimens for mechanical testing were produced by injection molding. The standard tension rods had 150 mm length, 4 mm thickness and 10 mm width in the middle. They have been prepared by an injection molding machine from Engel named E-mac 100.

The mechanical testing and measurements were carried out with an Instron 4282 tensile testing machine (with Bluhill 3 software; tensile rate 5 mm/min).

The examples 8, 9 and 10 have improved elongation at break, where at the same time the tensile strength is still sufficiently good.

Claims

CLAIMS:

1. A plasticizer composition comprising at least one polyester plasticizer obtainable from a monomer composition comprising

- at least one aliphatic linear or branched saturated C₂-Ci₂ dialcohol, and

2. The plasticizer composition according to claim 1, where at least 50 wt.-% of the monomer composition, based on the total weight of the monomer composition is derived from renewable resources and/or renewable origin; and where preferably at least 70 wt.-%, more preferably at least 90 wt.-%, more preferably at least 95 wt.-%, even more preferably at least 99 wt.-% of the monomer composition, based on the total weight of the monomer composition, is derived from renewable resources and/or renewable origin.

3. The plasticizer composition according to any one of the preceding claims, where the at least one monocarboxylic acid is selected from C₈-Ci₈ fatty acids and mixtures thereof; and where the at least one monocarboxylic acid is preferably selected from Ci₂-Ci₆ fatty acids; and more preferably the at least one monocarboxylic acid is a mixture of C₁₂ fatty acids and Ci4 fatty acids.

4. The plasticizer composition according to any one of the preceding claims, where the at least one dialcohol is selected from C₂-C₆-dialcohols and mixtures thereof; and where the at least one dialcohol is preferably selected from 1,2-ethandiol, 1,2-propandiol, 1,3-propandiol, 1,2-butandiol, 1,3-butandiol, and 1,4-butandiol; and more preferably the least one dialcohol is 1,2-propandiol.

5. The plasticizer composition according to any one of the preceding claims, where the at least one dicarboxylic acid is selected from linear and branched C₂-C₁₂ dicarboxylic acids; and where preferably the at least one dicarboxylic acid is selected from succinic acid (HOOC-C₂H₄-COOH), azelaic acid (HOOC-C₇H₁₄-COOH), and sebacic acid (HOOC-C₈H₁₆-COOH); and more preferably the at least one dicarboxylic acid is succinic acid (HOOC-C₂H₄-COOH).

6. The plasticizer composition according to any one of the preceding claims, where the plasticizer compound has the following structure (I)

R¹-C(=0)- {0-R²-0-C(=0)-R³-C(=0)}_n -0-R²-0-C(=0)-R¹ (I) where

R¹ is independently C₇-Ci₇ alkyl;

R² is independently C₂-Ci₂ alkylene; R³ is independently C₀-Ci₀ alkylene; n is an integer from 1 to 100.

7. The plasticizer composition according to claim 6, which comprises at least one polyester plasticizer having the structure of formula (I) and at least one polyester plasticizer of the following structure of formula (II)

H- {0-R²-0-C(=0)-R³-C(=0)}_n -0-R²-0-C(=0)-R¹ (II) where

R¹ is independently C₇-Ci₇ alkyl;

R² is independently C₂-Ci₂ alkylene;

R³ is independently C₀-Ci₀ alkylene; n is an integer from 1 to 100.

8. The plasticizer composition according to any one of the preceding claims,

- where the polyester plasticizer has a weight average molecular weight M_w, measured by gel permeation chromatography (GPC), in the range of 500 to 5000 g/mol; preferably in the range of 1000 to 4000 g/mol and/or

- where the polyester plasticizer has a viscosity, measured according to DIN ISO 53019, in the range of 600 to 15000 mPas, preferably in the range of 700 to 6000 mPas; and/or

- where the polyester plasticizer has an acid number, measured according to DIN EN ISO 2114, of at most 3 mg KOH/g, preferably in the range of 0.1 to 2 mg KOH/g; and/or

- where the polyester plasticizer has an OH number, measured according to DIN 53240, of at most 120 mg KOH/g, more preferably of at most 50 mg KOH/g more preferably of at most 40 mg KOH/g more preferably of at most 30 mg KOH/g.

9. The plasticizer composition according to any one of the preceding claims, where the plasticizer compound has the following structure (l.x)

R¹-C(=0)- {O-CH(CH₃)-CH₂-O-C(=O)-C₂H₄-C(=O)-}₁₀0-CH(CH₃)-CH₂-0-C(=0)-R¹ (l.x) where R¹ is independently CnH₂₃ or CI₃H₂₇.

10. The plasticizer composition according to any one of the preceding claims, where the at least one polyester plasticizer is obtained using at least one of the following conditions/methods:

- The polyester is obtained via a polycondensation reaction.

- The polyester is obtained using a catalyst preferably selected from acid catalysts, tin catalysts, titanium catalysts, and more preferably selected from titanium complexes, more preferably tetra-n-butyl titanate.

- The polyester is obtained at elevated temperatures in the range of 100 to 290 °C, preferable in the range of 160 to 240 °C.

- The polyester is obtained at reduced pressure.

11. Use of a composition according to any one of claims 1 to 10 as plasticizer for polyhydroxyalkanoate-based polyesters derived from renewable resources and/or renewable origin, in particular homo- and/or co-polymer polyesters based on polyhydroxyalkanoates such as polylactide (PLA) and/or polyhydroxybutyrate (PHB), where the composition is preferably used for improving mechanical properties, in particular improving the elongation at break.

12. The use according to claim 11, where the polyhydroxyalkanoate-based polyesters are selected from polylactide (PLA) homopolymers and polyhydroxybutyrate (PHB) homopolymers and co polymers of polylactide and/or polyhydroxybutyrate.

13. A plasticized composition comprising - the plasticizer composition according to any one of claims 1 to 10, and

- at least one polyhydroxyalkanoate-based polyester, preferably at least one homo- and/or co-polymer polyester based on polyhydroxyalkanoates, as defined in claims 11 or 12.

14. The plasticized composition according to claim 13, comprising

- 5 to 30 wt.-% of the plasticizer composition according to any one of claims 1 to 10, and - 70 to 95 wt.-% of the least one polyhydroxyalkanoate-based polyester, preferably at least one homo- and/or co-polymer polyester based on polyhydroxyalkanoates, as defined in claims 11 or 12, where the wt.-% refer to the total of plasticizer and polyester.

15. The use of a composition according to claims 13 and/or 14 for processes selected from 3D printing, additive manufacturing, selective laser sintering (SLS), fused deposition modeling

(FDM), fused filament fabrication (FFF), extrusion, film extrusion, injection molding, blow molding.

16. The use of a composition according to claims 13 and/or 14 for applications selected from packaging materials, 3D printing materials, construction materials, materials for toys.