WO2022008051A1 - Compositions de plastifiant - Google Patents

Compositions de plastifiant Download PDF

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Publication number
WO2022008051A1
WO2022008051A1 PCT/EP2020/069303 EP2020069303W WO2022008051A1 WO 2022008051 A1 WO2022008051 A1 WO 2022008051A1 EP 2020069303 W EP2020069303 W EP 2020069303W WO 2022008051 A1 WO2022008051 A1 WO 2022008051A1
Authority
WO
WIPO (PCT)
Prior art keywords
plasticizer
polyester
composition according
acid
independently
Prior art date
Application number
PCT/EP2020/069303
Other languages
English (en)
Inventor
Peter Daute
Martin Schaefer
Thomas Schweichler
Original Assignee
Emery Oleochemicals Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Emery Oleochemicals Gmbh filed Critical Emery Oleochemicals Gmbh
Priority to PCT/EP2020/069303 priority Critical patent/WO2022008051A1/fr
Publication of WO2022008051A1 publication Critical patent/WO2022008051A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

Definitions

  • the present invention relates to plasticizer compositions
  • plasticizer compositions comprising at least one polyester plasticizer obtainable from a monomer composition comprising at least one aliphatic linear or branched, saturated or unsaturated C 2 -C 2 2 monocarboxylic acid; at least one aliphatic linear or branched saturated C 2 -Ci 2 dialcohol; and at least one dicarboxylic acid selected from aliphatic linear or branched saturated C 2 -Ci 2 dicarboxylic acids and heterocyclic saturated, unsaturated or aromatic C 6 -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.
  • the present invention relates to compounds and compositions, which at least partially are derived from renewable resources and/or renewable origin.
  • 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.
  • 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.
  • 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.
  • the present invention provides plasticizer compositions comprising at least one polyester plasticizer obtainable from a monomer composition comprising
  • dicarboxylic acid selected from aliphatic linear or branched saturated C 2 -Ci 2 dicarboxylic acids and heterocyclic saturated, unsaturated or aromatic C 6 -Ci 0 dicarboxylic acids.
  • 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.
  • plasticizer composition as claimed as plasticizer
  • plasticized composition comprising a plasticizer composition as claimed
  • the invention disclosed herein allows providing plasticizer compositions as well as plasticized polymer compositions based on renewable resources and/or renewable origin.
  • aliphatic linear or branched, saturated or unsaturated C 2 -C 22 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 C 12 fatty acids such as lauric acid and C M fatty acids such as myristic acid and myristoleic acid.
  • aliphatic linear or branched saturated C 2 -Ci 2 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.
  • aliphatic linear or branched saturated C 2 -Ci 2 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.
  • heterocyclic saturated, unsaturated or aromatic C 6 -Ci 0 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.
  • the plasticizer comprises at least one polyester plasticizer obtainable from a monomer composition comprising
  • dicarboxylic acid selected from aliphatic linear or branched saturated C 2 -Ci 2 dicarboxylic acids and heterocyclic saturated, unsaturated or aromatic C 6 -Ci 0 dicarboxylic acids.
  • 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.
  • 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.
  • 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.
  • the monomer composition comprises
  • At least one dicarboxylic acid selected from aliphatic linear or branched saturated C 2 -Ci 2 dicarboxylic.
  • the at least one dicarboxylic acid is usually selected from aliphatic linear or branched saturated C 2 -Ci 2 dicarboxylic acids and heterocyclic saturated, unsaturated or aromatic C 6 -Cio dicarboxylic acids.
  • Suitable heterocyclic saturated, unsaturated or aromatic C 6 -Ci 0 dicarboxylic acids are commonly known and include for example 2,5-furandicarboxylic acid.
  • the at least one monocarboxylic acid is selected from C 8 -Ci 8 fatty acids and mixtures thereof, that include linear and branched, saturated and unsaturated carboxylic acids.
  • the at least one monocarboxylic acid is selected Ci 2 -Ci 6 fatty acids such as Ci2 fatty acids, C M atty acids, Ci 6 fatty acids, where a mixture of C 12 fatty acids and C M fatty acids is particularly preferred.
  • the monocarboxylic acid is a combination of lauric acid and myristic acid.
  • the at least one dialcohol is selected from C 2 -C 6 -dialcohols including mixtures thereof.
  • the at least one dialcohol is preferably selected from 1,2-ethandiol,
  • the dialcohol is 1,2-propandiol.
  • the at least one dicarboxylic acid is selected from linear and branched C2-C12 dicarboxylic acids.
  • the decarboxylic acid is selected from C 2 -C 6 dicarboxylic acids, preferably C 4 dicarboxylic acid, more preferably succinic acid.
  • the dicarboxylic acid is selected from C 8 -Ci 2 dicarboxylic acids, preferably from C 9 and C10 dicarboxyclic acid, more preferably from azelaic acid and sebacic acid.
  • the at least one dicarboxylic acid is succinic acid.
  • plasticizer compositions comprise a plasticizer compound obtainable from a monomer composition comprising lauric acid, myristic acid, 1,2-propandiol and succinic acid.
  • 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)
  • R 1 is independently C 7 -Ci 7 alkyl
  • R 2 is independently C 2 -Ci 2 alkylene
  • R 3 is independently C 0 -Ci 0 alkylene; n is an integer from 1 to 100;
  • the polyester plasticizer has a structure of formula (I) where R 1 is independently Cn-Ci 5 alkyl, R 2 is independently C 3 alkylene, R 3 is independently C 2 alkylene, n is an integer from 2 to 40; and more preferably, where R 1 is independently Cn-Ci 5 alkyl, R 2 is independently C 3 alkylene, R 3 is independently C 2 alkylene, n is an integer from 5 to 30.
  • Preferred polyester plasticizers of formula (I) have the following structure (l.x):
  • polyester plasticizers of formula (I) are selected from the following structures (l.a) to (l.f):
  • 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)
  • R 1 is independently C 7 -Ci 7 alkyl
  • R 2 is independently C 2 -Ci 2 alkylene
  • R 3 is independently C 0 -Ci 0 alkylene; n is an integer from 1 to 100.
  • the polyester plasticizer composition comprises a structure of formula (II) where R 1 is independently Cn-Ci 5 alkyl, R 2 is independently C 3 alkylene, R 3 is independently C 2 alkylene, n is an integer from 2 to 40; and more preferably, where R 1 is independently Cn-Ci 5 alkyl, R 2 is independently C 3 alkylene, R 3 is independently C 2 alkylene, n is an integer from 5 to 30.
  • polyester plasticizers of formula (II) are selected from the following structures (II. a) to (II. c):
  • 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.
  • M w weight average molecular weight measured by gel permeation chromatography
  • the molecular weight is typically measured by measured by gel permeation chromatography (GPC), preferably using polyethylenglycol (PEG) standard and tetrahydrofuran (THF) solvent.
  • GPC gel permeation chromatography
  • 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.
  • 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.
  • 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.
  • the polyester plasticizer may be obtained via polymerization such as a polycondensation reaction.
  • the polyester plasticizer is obtained via a polycondensation reaction.
  • the polyester plasticizer may be obtained using a catalyst as commonly used for those reactions.
  • the catalyst is selected from acid catalysts, tin catalysts, titanium catalysts, and more preferably selected from titanium complexes, more preferably tetra- n-butyl titanate.
  • 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.
  • the polyester plasticizer may be obtained at normal or reduced pressure.
  • 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.
  • 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.
  • 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.
  • 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.
  • polylactide polymers in particular homopolymers are used.
  • polyhydroxybutyrate polymers in particular homopolymers are used.
  • plasticizer compositions are as plasticizer for polybutylene adipate terephthalate (PBAT).
  • PBAT polybutylene adipate terephthalate
  • 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.
  • plasticizer compositions are as plasticizer for improving mechanical properties, in particular improving the elongation at break.
  • 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).
  • PHA polylactide
  • PHB polyhydroxybutyrate
  • 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.
  • 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.
  • 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.
  • PBAT polybutylene adipate terephthalate
  • PBS polybutylene succinate
  • 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.
  • SLS selective laser sintering
  • FDM fused deposition modeling
  • FFF fused filament fabrication
  • the plasticized compositions are used for applications selected from packaging materials, 3D printing materials, construction materials, materials for toys.
  • 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 N 2 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.
  • 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 examples 8, 9 and 10 have improved elongation at break, where at the same time the tensile strength is still sufficiently good.

Abstract

La présente invention concerne des compositions de plastifiant comprenant au moins un plastifiant de polyester pouvant être obtenu à partir d'une composition de monomères comprenant au moins un acide monocarboxylique en C2-C22 aliphatique linéaire ou ramifié, saturé ou insaturé ; au moins un dialcool en C2-C12 aliphatique linéaire ou ramifié, saturé ; et au moins un acide dicarboxylique sélectionné parmi des acides dicarboxyliques en C2-C12 aliphatiques linéaires ou ramifiés saturés et des acides dicarboxyliques en C6-C10 saturés, insaturés ou aromatiques. La présente invention concerne également l'utilisation d'une composition de plastifiant selon l'invention en tant que plastifiant ; une composition plastifiée comprenant une composition de plastifiant selon l'invention ; ainsi qu'une utilisation associée.
PCT/EP2020/069303 2020-07-08 2020-07-08 Compositions de plastifiant WO2022008051A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/069303 WO2022008051A1 (fr) 2020-07-08 2020-07-08 Compositions de plastifiant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2020/069303 WO2022008051A1 (fr) 2020-07-08 2020-07-08 Compositions de plastifiant

Publications (1)

Publication Number Publication Date
WO2022008051A1 true WO2022008051A1 (fr) 2022-01-13

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PCT/EP2020/069303 WO2022008051A1 (fr) 2020-07-08 2020-07-08 Compositions de plastifiant

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1071525A (en) * 1963-08-29 1967-06-07 Lonza Ag Polyesters of succinic acid as plasticisers for vinyl chloride polymers
US6235825B1 (en) * 1998-03-05 2001-05-22 Mitsui Chemicals, Inc. Polylactic acid resin composition and film therefrom
US8722813B2 (en) * 2010-08-19 2014-05-13 Kao Corporation Resin composition
US20180282510A1 (en) * 2015-09-30 2018-10-04 Basf Se Plasticizer composition containing polymeric dicarboxylic acid esters and dicarboxylic acid diesters

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1071525A (en) * 1963-08-29 1967-06-07 Lonza Ag Polyesters of succinic acid as plasticisers for vinyl chloride polymers
US6235825B1 (en) * 1998-03-05 2001-05-22 Mitsui Chemicals, Inc. Polylactic acid resin composition and film therefrom
US8722813B2 (en) * 2010-08-19 2014-05-13 Kao Corporation Resin composition
US20180282510A1 (en) * 2015-09-30 2018-10-04 Basf Se Plasticizer composition containing polymeric dicarboxylic acid esters and dicarboxylic acid diesters

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