WO2018210609A1 - Mélange de polyester résistant aux chocs - Google Patents

Mélange de polyester résistant aux chocs Download PDF

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Publication number
WO2018210609A1
WO2018210609A1 PCT/EP2018/061782 EP2018061782W WO2018210609A1 WO 2018210609 A1 WO2018210609 A1 WO 2018210609A1 EP 2018061782 W EP2018061782 W EP 2018061782W WO 2018210609 A1 WO2018210609 A1 WO 2018210609A1
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components
acid
mol
weight
aliphatic
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PCT/EP2018/061782
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German (de)
English (en)
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Maximilian LEHENMEIER
Martin Bussmann
Elmar Poeselt
Norbert Effen
Gabriel Skupin
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Basf Se
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    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to a polyester mixture containing: i) from 65 to 94% by weight, based on the total weight of components i to iii, of a polyester composed of aliphatic dicarboxylic acids and aliphatic diols and ii) from 1 to 15% by weight, based on the Total weight of components i to iii, of an aliphatic-aromatic polyester comprising: ii-a) 30 to 70 mol%, based on the components ii-a to ii-b, of an aliphatic dicarboxylic acid, preferably a C6-Ci8 dicarboxylic acid; ii-b) 30 to 70 mol%, based on components ii-a to ii-b, of an aromatic dicarboxylic acid, preferably terephthalic acid; ii-c) 98 to 100 mol%, based on the components ii-a to ii-b, 1, 3 propanediol or 1,
  • polyesters composed of aliphatic dicarboxylic acids and aliphatic diols and their use as injection-molded articles are well known in the literature.
  • the aliphatic polyesters such as polybutylene succinate (PBS) have a low modulus of elasticity and at the same time a low impact strength.
  • PBS polybutylene succinate
  • Some injection molding applications are therefore out of the question for this class of polyester.
  • US 2009/0171023 describes polyester mixtures, wherein the above-mentioned polyesters block copolymers with different hard phase (polyester, polycarbonate, polyacrylate, polyacetal, polyolefin or polyurethane) and a soft phase of a polyetherol are added.
  • the polymer blends however, lack the inventive polyester component ii (aliphatic-aromatic polyester).
  • the polyester blends described in US 2009/0171023 can not always be fully satisfactory in terms of their modulus of elasticity and notched impact strength.
  • the aim was therefore to provide polyester blends which both have improved notched impact strength and at the same time have a sufficiently high modulus of elasticity.
  • Polyesters composed of aliphatic dicarboxylic acids and aliphatic diols and ii) 1 to 15% by weight, based on the total weight of components i to iii, of an aliphatic-aromatic polyester comprising: ii-a) 30 to 70 mol%, based on the components ii-a to ii-b, an aliphatic dicarboxylic acid, preferably a C6-Ci8 dicarboxylic acid; ii-b) 30 to 70 mol%, based on components ii-a to ii-b, of an aromatic dicarboxylic acid, preferably terephthalic acid; ii-c) 98 to 100 mol%, based on the components ii-a to ii-b, 1, 3 propanediol or 1, 4-butanediol; ii-d) 0 to 1% by weight, based on the components ii-a to ii-c of a chain
  • thermoplastic polyurethane or thermoplastic copolyester from 0 to 45% by weight, based on the total weight of components i to v, of polylactic acid; v) 0 to 45% by weight, based on the total weight of components i to v, of a mineral filler.
  • component iii) being a thermoplastic polyurethane. The invention will be described in more detail below.
  • Component i is understood as meaning polyesters composed of aliphatic dicarboxylic acid and aliphatic diols.
  • Suitable dicarboxylic acids are aliphatic C 2 -C 30 -diacids or mixtures thereof.
  • the dicarboxylic acids usually make up more than 50, preferably more than 70, mol% and especially preferably more than 99 mol% of the acid repeating units.
  • Examples of aliphatic C 2 -C 30 -dicarboxylic acids include: oxalic acid, malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, or the like
  • the dicarboxylic acids or their ester-forming derivatives may be used singly or as a mixture of two or more thereof.
  • Succinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures thereof are preferably used. Particular preference is given to using succinic acid, adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof. Succinic acid, azelaic acid, sebacic acid and brassylic acid also have the advantage that they are accessible from renewable raw materials.
  • Acid derivatives are to be understood as meaning C 1 -C 6 -alkyl esters, the methyl and ethyl esters being particularly preferred.
  • Suitable diols are aliphatic C 2 -C 18 diols, such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol,
  • Dimethyl-1, 3-propanediol are preferred.
  • the latter also have the advantage that they are accessible as a renewable resource. It is also possible to use mixtures of different alkanediols.
  • diols are cycloaliphatic C 6 -C 18 diols, such as 1,4-cyclohexanedimethanol
  • Aliphatic polyesters i are understood as meaning polyesters of aliphatic diols and aliphatic dicarboxylic acids such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene sucocyanate adipate (PBSA), polybutylene succinate sebacate (PBSSe), polybutylene sebacate (PBSe) or corresponding polyesteramides or polyester urethanes.
  • PBS polybutylene succinate
  • PBA polybutylene adipate
  • PBSA polybutylene sucocyanate adipate
  • PBSSe polybutylene succinate sebacate
  • PBSe polybutylene sebacate
  • aliphatic polyesters are marketed, for example, by the companies Showa Highpolymers under the name Bionolle and by Mitsubishi under the name GSPIa. More recent developments are described in WO 2010/03471 1.
  • aliphatic polyesters i contain the following components:
  • i-a 90 to 100 mol%, based on the components i-a to i-b, of succinic acid;
  • Preferred aliphatic polyesters are polybutylene succinate sebacate (PBSSe) and most preferably polybutylene succinate (PBS).
  • PBSSe polybutylene succinate sebacate
  • PBS polybutylene succinate
  • the polyesters ia to id (referred to below as A1) contain 0 to 2% by weight, preferably 0.05 to 1.0% by weight and more preferably 0.1 to 0.3% by weight to the total weight of the polyester, a branching agent and / or 0.1 to 1.0% by weight, based on the total weight of the polyester, of a chain extender.
  • the branching agent is preferably selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, peroxide, carboxylic anhydride, an at least trifunctional alcohol or an at least trifunctional carboxylic acid.
  • Particularly suitable chain extenders are difunctional isocyanates, isocyanurates, oxazolines, carboxylic anhydride or epoxides.
  • Particularly preferred branching agents have three to six functional groups.
  • Examples include: tartaric acid, citric acid, malic acid; Trimethylolpropane, trimethylolethane; Pentaerythritol; Polyether triols and glycerin, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic dianhydride. Preference is given to polyols such as trimethylolpropane, pentaerythritol and in particular glycerol.
  • the component can be used to build biodegradable polyesters with a structural viscosity. The biodegradable polyesters are easier to process.
  • a diisocyanate as chain extender is primarily linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclo) hexane), understood.
  • Particularly preferred aliphatic diisocyanates are isophorone diisocyanate and in particular 1,6-hexamethylene diisocyanate.
  • Polyfunctional epoxides as chain extenders are understood as meaning, in particular, an epoxide-group-containing copolymer based on styrene, acrylates and / or methacrylates.
  • the epoxy groups bearing units are preferably glycidyl (meth) acrylates.
  • Copolymers having a glycidyl methacrylate content of greater than 20, particularly preferably greater than 30 and especially preferably greater than 50% by weight, of the copolymer have proven to be advantageous.
  • the epoxy equivalent weight (EEW) in these polymers is preferably 150 to 3000, and more preferably 200 to 500 g / equivalent.
  • the weight average molecular weight Mw of the polymers is preferably from 2,000 to 25,000, in particular from 3,000 to 8,000.
  • the number-average molecular weight M n of the polymers is preferably from 400 to 6,000, in particular from 1,000 to 4,000.
  • the polydispersity (Q) is generally between 1 .5 and 5 epoxy groups-containing copolymers of the above type are sold for example by BASF Resins BV under the trademark Joncryl ® ADR.
  • Joncryl ® ADR As a chain Extender particularly suitable Joncryl ® ADR, for example, the 4368th
  • the polyesters A1 generally have a number average molecular weight (Mn) in the range from 5000 to 100,000, in particular in the range from 10,000 to 75,000 g / mol, preferably in the range from 15,000 to 38,000 g / mol, a weight average molecular weight (Mw) of 30,000 to 300,000, preferably 60000 to 200,000 g / mol and a Mw / Mn ratio of 1 to 6, preferably 2 to 4 on.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the viscosity number according to ISO 1628-5 (measured in 0.05 g / ml solution of phenol / o-dichlorobenzene (1: 1)) is between 30 and 450, preferably from 100 to 400, ml / g (measured in o-dichlorobenzene / phenol (Weight ratio 50/50)
  • the melting point is in the range of 85 to 130, preferably in the range of 95 to 120 ° C.
  • the preferred polyesters ii include polyesters which contain as essential components: ii-a) 30 to 70 mol%, preferably 40 to 60 and more preferably 50 to 60 mol%, based on the components ii-a) to ii b), an aliphatic dicarboxylic acid or mixtures thereof, preferably a C 6 -C 18 -dicarboxylic acids and particularly preferred: adipic acid, azelaic acid, sebacic acid and brassylic acid or mixtures thereof, ii-b) 30 to 70 mol%, preferably 40 to 60 and particularly preferably 40 to 50 mol%, based on components ii-a) and ii-b), of an aromatic dicarboxylic acid or mixtures thereof, preferably terephthalic acid,
  • a chain extender especially a di- or polyfunctional isocyanate, preferably hexamethylene diisocyanate and optionally a branching agent preferably: trimethylolpropane, pentaerythritol and especially glycerol.
  • polyesters ii comprising: ii-a) from 50 to 60 mol%, based on components ii-a) to ii-b), of an aliphatic dicarboxylic acid selected from the group consisting of adipic acid, azelaic acid, sebacic acid and Brassylic acid or mixtures thereof, ii-b) 40 to 50 mol%, based on the components ii-a) and ii-b), terephthalic acid, ii-c) 98.5 to 100 mol%, based on the components ii -a) to ii-b), 1, 4-butanediol; and
  • a chain extender hexamethylene diisocyanate 0.1 to 0.2 wt .-%, based on the components ii-a) to ii-c), of a chain extender hexamethylene diisocyanate and optionally a branching agent trimethylolpropane, pentaerythritol and in particular glycerol.
  • Suitable aliphatic diacids and the corresponding derivatives ii-a are generally those having 6 to 18 carbon atoms, preferably 6 to 13 carbon atoms. They can be both linear and branched. In principle, however, it is also possible to use dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms.
  • Examples which may be mentioned are: 2-methylglutaric acid, 3-methylglutaric acid, ⁇ -ketoglutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, brassylic acid, suberic acid (suberic acid), C 16 -dicarboxylic acid, cis-dicarboxylic acid and itaconic acid.
  • the dicarboxylic acids or their ester-forming derivatives may be used singly or as a mixture of two or more thereof.
  • Adipic acid, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures thereof are preferably used. Particular preference is given to using adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof. Particular preference is given to the following aliphatic-aromatic polyesters: polybutyleneadipate coterephthalate (PBAT), polybutylene sebacate coterephthalate (PBSeT) or mixtures of these two polyesters.
  • PBAT polybutyleneadipate coterephthalate
  • PBSeT polybutylene sebacate coterephthalate
  • the aromatic dicarboxylic acids or their ester-forming derivatives ii-b may be used singly or as a mixture of two or more thereof. Particular preference is given to using terephthalic acid or its ester-forming derivatives, such as dimethyl terephthalate.
  • terephthalic acid or its ester-forming derivatives such as dimethyl terephthalate.
  • the diols ii-c - 1, 4-butanediol and 1, 3-propanediol - are available as a renewable raw material. It is also possible to use mixtures of the diols mentioned.
  • a chain extender ii-d
  • the polyesters ii generally have a number average molecular weight (Mn) in the range from 5000 to 100,000, in particular in the range from 10,000 to 75,000 g / mol, preferably in the range from 15,000 to 38,000 g / mol, a weight average molecular weight (Mw) of 30,000 to 300,000, preferably 60000 to 200,000 g / mol and a Mw / Mn ratio of 1 to 6, preferably 2 to 4 on.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the viscosity number is between 50 and 450, preferably from 80 to 250 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50).)
  • the melting point is in the range of 85 to 150, preferably in the range of 95 to 140 ° C. ,
  • MVR Melt volume rate
  • EN ISO 1133-1 DE 190 ° C, 2.16 kg weight
  • the acid numbers according to DIN EN 12634 are generally from 0.01 to 1.2 mg KOH / g, preferably from 0.01 to 1.0 mg KOH / g and particularly preferably from 0.01 to 0.7 mg KOH / g ,
  • Component iii may be either a thermoplastic polyurethane (also referred to below as TPU) or a thermoplastic copolyester (also referred to below as TPE).
  • TPU thermoplastic polyurethane
  • TPE thermoplastic copolyester
  • the preparation is carried out by reacting (a) isocyanates (hard phase) with (b) isocyanate-reactive compounds / polyol having a number average molecular weight of from 0.5 ⁇ 10 3 g / mol to 5 ⁇ 10 3 g / mol (soft phase) and optionally (C) chain extenders having a molecular weight of 0.05 x 10 3 g / mol to 0.499 x 10 3 g / mol optionally in the presence of (d) catalysts and / or (e) conventional excipients and / or additives.
  • the components (a) isocyanate, (b) isocyanate-reactive compounds / polyol, (c) chain extenders are mentioned individually or together as structural components.
  • the synthesis components including the catalyst and / or the usual auxiliaries and / or additives are also called feedstocks.
  • the amounts used of the constituent components (b) and (c) can be varied in their molar ratios, the hardness and the melt viscosity increasing with increasing content of chain extender (c), while the melt flow index decreases.
  • thermoplastic polyurethanes for example those having a Shore A hardness (measured in accordance with DIN ISO 7619-1 (3s): 2012-02 of less than or equal to 95, preferably from 75 to 85 Shore A
  • harder TPU for example those having a hardness Shore A greater than 98, preferably from 55 to 75 Shore D
  • the molar ratios of (b) :( c) are in the range from 1: 5.5 to 1:15, preferably from 1: 6 to 1:12, so that the resulting mixtures of (b) and (c)
  • the synthesis components (a), (b), in a preferred embodiment also (c), in the presence of a catalyst (d) and optionally auxiliaries and / or additives (e) are reacted in amounts such that the Equivalence ratio of NCO groups of the diisocyanates (a) to the sum of the hydroxyl groups of components (b) and (c) 0.95 to 1, 10: 1, preferably 0.98 to 1, 08: 1 and in particular 0 0, 99 to 1, 02: 1.
  • TPUs are produced in which the TPU has a weight-average molecular weight of at least 10,000 g / mol.
  • the upper limit for the weight-average molecular weight of the TPU is generally determined by the processability as well as the desired property spectrum and is generally not more than 800,000 g / mol.
  • the average molecular weights given above for the TPU as well as the constituent components (a) and (b) are the weight average determined by gel permeation chromatography.
  • the weight average molecular weight of the TPUs is from 60,000 to 200,000 g / mol.
  • organic isocyanates it is preferred to use aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene diisocyanate -1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-iso-cyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis (isocyanatomethyl) cyclohexane and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI),
  • MDI or hexamethylene diisocyanate (HDI) is particularly preferably used.
  • isocyanate-reactive compounds (b) preference is given to those having a number-average molecular weight of between 500 g / mol and 8000 g / mol and preferably from 600 to 3000 g / mol.
  • the surface energy of the TPUs used is in the range of 25 to 50 mN / m, and preferably in the range of 30 to 45 mN / m.
  • the surface energies are determined using the Owens-Wendt-Raebel-Kaelble method according to DIN 55660-2: 201 1 -12.
  • TPUs which are based on polyesterols, which in turn are composed of 1,4-butanediol and succinic acid or 1,4-butanediol and adipic acid, are particularly compatible in the polyester mixtures according to the invention. Such TPUs are therefore preferred.
  • the isocyanate-reactive compound (b) has on statistical average at least 1, 8 and at most 3.0 Zerewitinoff-active hydrogen atoms, this number is also referred to as functionality of the isocyanate-reactive compound (b) and gives the theoretically down-converted from one amount of substance to a molecule Amount of the isocyanate-reactive groups of the molecule.
  • the functionality is preferably between 1, 8 and 2.6, more preferably between 1, 9 and 2.2 and especially 2.
  • the isocyanate-reactive compound is substantially linear and is an isocyanate-reactive substance or a mixture of various substances, in which case the mixture satisfies the said requirement. These long-chain compounds are used in a mole fraction of 1 equivalent mol% to 80 equivalent mol%, based on the isocyanate group content of the polyisocyanate.
  • the isocyanate-reactive compound (b) has a reactive group selected from the hydroxyl group, the amino group, the mercapto group or the carboxylic acid group. It is preferably the hydroxyl group.
  • the isocyanate-reactive compound (b) is particularly preferably selected from the group of the polyesterols, the polyetherols or the polycarbonate diols, which are also grouped together under the term "polyols".
  • polyester diols preferably polycaprolactone, and / or polyether polyols, preferably polyether diols, more preferably those based on ethylene oxide, propylene oxide and / or butylene oxide, preferably polypropylene glycol.
  • a particularly preferred polyether polyol is polytetrahydrofuran (PTHF), polyethylene glycol (PEG) or polypropylene glycol (PPG).
  • Particularly preferred polyols are those selected from the following group: copolyesters based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof and mixtures of 1,2-ethanediol and 1,4-butanediol, copolyesters based on adipic acid, succinic acid, pentanedioic acid, Sebazic acid or mixtures thereof and mixtures of 1,4-butanediol and 1,6-hexanediol, polyesters based on adipic acid and 3-methyl-pentanediol-1, 5 and / or polytetramethylene glycol (polytetrahydrofuran, PTHF), polyethylene glycol (PEG) or polypropylene glycol ( PPG) particularly preferably copolyester based on adipic acid and ethanediol, 1, 3-propanediol, 1, 4-butan
  • Typical number average molecular weights (Mn) for the polyesterols b) are 500 to 5000 g / mol and preferably 500 to 3000 g / mol.
  • chain extenders (c) are used, these are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 0.05 x 10 3 g / mol to 0.499 x 10 3 g / mol, preferably 2 with isocyanate reactive groups, which are also referred to as functional groups.
  • the chain extender (c) at least one chain extender selected from the group consisting of 1, 2-ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2,3- Butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanediol, 1, 4-dimethanolcyclohexane, hydroquinone bis (2-hydroxyethyl) ether (HQEE) and neopentyl glycol.
  • HQEE hydroquinone bis (2-hydroxyethyl) ether
  • chain extenders selected from the group consisting of ethane diol, 1, 4-butanediol and 1, 6-hexanediol.
  • catalysts (d) are used with the synthesis components. These are in particular catalysts which accelerate the reaction between the NCO groups of the isocyanates (a) and the hydroxyl groups of the isocyanate-reactive compound (b) and, if used, the chain extender (c).
  • Preferred catalysts are tertiary amines, in particular triethylamine, dimethylcyclohexylamine, N-methylmorpholine, ⁇ , ⁇ '-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane.
  • the catalysts are organic metal compounds such as titanic acid esters, iron compounds, preferably iron (II) acetylacetonate, tin compounds, preferably those of carboxylic acids, particularly preferably tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts, more preferably dibutyltin diacetate , Dibutyltin dilaurate, or bismuth salts of carboxylic acids, preferably bismuth decanoate.
  • titanic acid esters iron compounds, preferably iron (II) acetylacetonate
  • tin compounds preferably those of carboxylic acids, particularly preferably tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts, more preferably dibutyltin diacetate , Dibutyltin dilaurate, or bismuth salts of carboxylic acids, preferably bismut
  • catalysts are: tin dioctoate, bismuth decanoate. Titanium acid esters Further preferred are:
  • the catalyst (d) is preferably used in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of the isocyanate-reactive compound (b).
  • customary auxiliaries (e) can also be added to structural components (a) to (c). Mention may be made, for example, of surface-active substances, fillers, flameproofing agents, nucleating agents, oxidation stabilizers, lubricants and mold release agents, nucleating agents, dyes and pigments, optionally stabilizers, preferably against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and / or or plasticizer.
  • Stabilizers in the context of the present invention are additives which protect a plastic or a plastic mixture against harmful environmental influences.
  • examples are primary and secondary antioxidants, hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis protectors, quenchers and flame retardants.
  • examples of commercial stabilizers are given in Plastics Additives Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001 ([1]), p.98-S136.
  • the UV absorbers have a number average molecular weight of greater than 0.3 ⁇ 10 3 g / mol, in particular greater than 0.39 ⁇ 10 3 g / mol. Further The preferred UV absorbers should have a molecular weight of not greater than 5 ⁇ 10 3 g / mol, particularly preferably not greater than 2 ⁇ 10 3 g / mol.
  • UV absorber is the group of benzotriazoles.
  • benzotriazoles are Tinuvin ® 213, Tinuvin ® 234, Tinuvin ® 571 and Tinuvin ® 384 and the Eversorb ® 82nd
  • the UV absorbers are usually metered in amounts of from 0.01% by weight to 5% by weight, based on the total weight of TPU, preferably from 0.1% by weight to 2.0% by weight, in particular 0.2% by weight % to 0.5% by weight.
  • a UV stabilization based on an antioxidant and a UV absorber described above is still not sufficient to ensure good stability of the TPU according to the invention against the harmful influence of UV rays.
  • HALS hindered amine light stabilizer
  • the activity of the HALS compounds is based on their ability to form nitroxyl radicals, which interfere with the mechanism of the oxidation of polymers. HALS are considered to be highly efficient UV stabilizers for most polymers.
  • HALS compounds are well known and commercially available. Examples of commercially available HALS stabilizers can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Kunststoff, 2001, pp. 123-136.
  • Hindered Amine Light Stabilizers are preferably Hindered Amine Light Stabilizers in which the number average molecular weight is greater than 500 g / mol. Further, the molecular weight of the preferred HALS compounds should not be greater than 10 x 10 3 g / mol, more preferably no greater than 5 x 10 3 g / mol.
  • hindered amine light stabilizers are bis (1, 2,2,6,6-pentamethylpiperidyl) sebacate (Tinuvin ® 765, Ciba Specialty Chemicals Inc.) and the condensation product of 1 - hydroxyethyl-2,2,6,6-tetramethyl- 4-hydroxypiperidine and succinic acid (Tinuvin ® 622).
  • the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidines and succinic acid when the titanium content of the finished product is less than 150 ppm, preferably less than 50 ppm, in particular less than 10 ppm, based on the starting components used.
  • HALS compounds are preferably used in a concentration of 0.01 wt .-% to 5 wt .-%, more preferably from 0.1 wt .-% to 1 wt .-%, in particular of 0.15 Wt .-% to 0.3 wt .-% based on the total weight of the thermoplastic polyurethane based on the starting components used.
  • a particularly preferred UV stabilization comprises a mixture of a phenolic stabilizer, a benzotriazole and a HALS compound in the preferred amounts described above.
  • auxiliaries and additives mentioned above can be found in the specialist literature, e.g. from Plastics Additives Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001.
  • the preparation of the TPU can be carried out batchwise or continuously by the known processes, for example with reaction extruders or the strip process by the "one-shot” or the prepolymer process, preferably by the one-shof process.
  • the components (a), (b) reacting, in preferred embodiments, also the components (c), (d) and / or (e) are mixed successively or simultaneously with each other Polymerization reaction used immediately.
  • the synthesis components (a), (b) and in preferred embodiments also (c), (d) and / or (e) are introduced individually or as a mixture into the extruder and, preferably at temperatures of 100 ° C to 280 ° C, preferably 140 ° C to 250 ° C, reacted.
  • the resulting polyurethane is extruded, cooled and granulated.
  • the polymer In the extruder process, the polymer is usually processed directly after production into lenticular granules in underwater granulation. In the case of strip processes, in turn, a cube granulation can be carried out directly after production, or the material can be remelted directly or after storage in an extruder and then further processed into lentil granules.
  • thermoplastic polyurethane is prepared in a first step from the synthesis components isocanate (a), isocyanate-reactive compound (b) chain extenders (c) and in preferred embodiments the other starting materials (d) and / or (e) and incorporated in a second step (f).
  • Additives such as flame retardants are only added during granulation by means of underwater granulation in the case of the belt process, since an extruder is used for this purpose, which permits better mixing. It is also common to extrude solids such as fillers only after TPU synthesis, as some may affect TPU synthesis
  • the preparation described above is preferably used for the production as an injection molding calendering powder sinter or extrusion article.
  • a twin-screw extruder is used, since the twin-screw extruder works positively conveying and so a more precise adjustment of the temperature and discharge rate is possible on the extruder.
  • TPU is gently processed in injection molding and extrusion with a single-screw extruder. For blending etc. often a twin-screw extruder is used.
  • a thermoplastic copolyester TPE
  • component iii a thermoplastic copolyester
  • thermoplastic elastomers are for example thermoplastic polyester elastomers (TPEE), for example polyether esters or polyester esters and thermoplastic copolyamides (TPA) such as, for example, polyethercopolyamides.
  • TPEE thermoplastic polyester elastomers
  • TPA thermoplastic copolyamides
  • thermoplastic polyether esters and polyester esters can be prepared by all conventional methods known from the literature by transesterification or esterification of aromatic and aliphatic dicarboxylic acids having 4 to 20 C atoms or esters thereof with suitable aliphatic and aromatic diols and polyols. Corresponding preparation methods are described, for example, in "Polymer Chemistry", Interscience Publ., New York, 1961, p.1 1 1 -127, Kunststoffhandbuch, Volume VIII, C. Hanser Verlag, Kunststoff 1973 and Journal of Polymer Science, Part A1, 4, pages 1851 -1859 (1966).
  • Suitable aromatic dicarboxylic acids are, for example, phthalic acid, isophthalic acid and terephthalic acid or their esters.
  • Suitable aliphatic dicarboxylic acids are, for example, cyclohexane-1,4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids and maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids.
  • Suitable diol components are, for example, diols of the general formula HO- (CH 2) n -OH, where n is an integer from 2 to 20.
  • Suitable diols are, for example, ethylene glycol, propanediol (1, 3), butanediol (1, 4) or hexanediol (1, 6).
  • Polyetherols, by the transesterification of which the thermoplastic polyether ester can be prepared are preferably those of the general formula HO- (CH 2) n -O- (CH 2) m -OH, where n and m can be the same or different and n and m independently of one another in each case an integer between 2 and 20 mean.
  • Unsaturated diols and polyetherols which can be used to prepare the polyetherester are, for example, butene diol (1, 4) and aromatic moiety containing diols and polyetherols.
  • the hard phases of the block copolymers are usually formed from aromatic dicarboxylic acids and short-chain diols, the soft phases from preformed aliphatic, difunctional polyesters having a molecular weight Mw between 500 and 3000 g / mol.
  • a coupling of the hard and soft phases can additionally be effected by reactive compounds such as diisocyanates, which react, for example, with terminal alcohol groups.
  • Thermoplastic polyetheramides suitable for the process according to the invention can be obtained by all conventional methods known from the literature by reaction of amines and carboxylic acids or their esters. Amines and / or carboxylic acids hereby also contain ether units of the type R-O-R, where R is an aliphatic or aromatic organic radical. In general, monomers selected from the following classes of compounds are used:
  • R ' can be aromatic or aliphatic and preferably contains ether units of the type R-O-R.
  • R stands for an aliphatic or aromatic organic radical, aromatic dicarboxylic acids, for example phthalic acid, isophthalic acid and terephthalic acid or their esters and aromatic dicarboxylic acids containing ether units of the type ROR, where R is an aliphatic or aromatic organic radical, aliphatic dicarboxylic acids, for example cyclohexane 1, 4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids and maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydohydroterephthalic acid as unsaturated dicarboxylic acids, and aliphatic dicarboxylic acids containing ROR units, wherein
  • TPEEs suitable as component iii are: Hytrel, Arnitel, Riteflex or Pelprene and examples of suitable TPAs are: Pebax, Vestamid, Grilflex.
  • thermoplastic elastomers having a block copolymer structure used according to the invention preferably contain vinylaromatic, butadiene and isoprene as well as polyolefin and vinylic units, for example ethylene, propylene and vinyl acetate units. Preference is given to styrene-butadiene copolymers.
  • the thermoplastic elastomers used according to the invention preferably have a Shore hardness in the range of A40 to D80. Shore hardnesses in the range from A44 to D60 are preferred, in particular in the range from A65 to A99. Most preferably, the Shore hardness is in the range of A65 to A96. The Shore hardnesses are determined in accordance with DIN 53505.
  • the melting point of the thermoplastic elastomers used according to the invention is preferably below 300.degree. C., preferably at a maximum of 250.degree. C. and in particular at a maximum of 220.degree.
  • the elongation at break of the thermoplastic elastomers according to the invention is greater than 100% measured according to DIN EN ISO 527-2: 2012, preferably greater than 200%, more preferably greater than 300% and in particular greater than 400%. Furthermore, the elongation at break is preferably at most 1000%, preferably at most 800%.
  • thermoplastic elastomers used according to the invention may be partially crystalline or amorphous.
  • the TPEs may contain in effective amounts other additives such as dyes, pigments, fillers, flame retardants, synergists for flame retardants, antistatic agents, stabilizers, surface-active substances, plasticizers and infrared opacifiers.
  • additives such as dyes, pigments, fillers, flame retardants, synergists for flame retardants, antistatic agents, stabilizers, surface-active substances, plasticizers and infrared opacifiers.
  • PLA polylactic acid
  • Polylactic acid having the following property profile is preferably used: • a melt volume rate (MVR at 190 ° C and 2.16 kg according to ISO 1133-1 DE of 20 to 50 and especially from 30 to 40 cm 3/10 minutes)
  • Preferred polylactic acids are, for example, NatureWorks® 6201 D, 6202 D, 6251 D, 3051 D and in particular 3251 D and crystalline polylactic acid types from NatureWorks.
  • the polylactic acid iv is used in a percentage by weight, based on the components i and v, from 0 to 45%, preferably from 5 to 30%.
  • the polylactic acid iv preferably forms the disperse phase and the polyester i forms the continuous or is part of a co-continuous phase.
  • Polymer blends with polyester i in the continuous phase or as part of a co-continuous phase have a higher heat resistance than polymer blends in which polylactic acid iv forms the continuous phase.
  • the ratio of the component i to the component iv in the compound from which the articles were made are, preferably greater than 2.2 and especially preferably greater than 2.5.
  • the modulus of elasticity can be significantly increased.
  • the polymer blends 0 to 45 wt .-%, in particular 10 to 35% by weight, based on the total weight of components i to v, of at least one mineral filler v selected from the group consisting of: calcium carbonate, graphite, gypsum , Carbon black, iron oxide, calcium chloride, dolomite, kaolin, quartz, sodium carbonate, titanium dioxide, tungstonite, mica, montmorillonite, talc, thermoplasticized or non-thermoplasticized starch, and mineral fibers.
  • glass fibers and glass hollow spheres can be used as fillers.
  • the compound according to the invention of the components i to v may contain further additives known to the person skilled in the art.
  • plastics technology such as stabilizers; Nucleating agents such as the already mentioned mineral fillers iv or crystalline polylactic acid; Lubricants and release agents such as stearates (especially calcium stearate); Plasticizers such as citric acid esters (especially acetyl tributyl citrate), glyceric acid esters such as triacetylglycerol or ethylene glycol derivatives, surfactants such as polysorbates, palmitates or laurates; Waxes such as, for example, erucic acid amide, stearic acid amide or behenamide, beeswax or beeswax esters; Antistatic agent, UV absorber; UV-stabilizer; Antifog agents or dyes.
  • the additives are in Concentrations of 0 to 2 wt .-%, in particular 0.1 to 2 wt .-% based on the compound of the invention used i to v.
  • Plasticizers may be present in 0.1 to 10% by weight in the inventive compound i to v.
  • biodegradable for a substance or a substance mixture is fulfilled if this substance or the substance mixture according to DIN EN 13432 has a percentage degree of biodegradation of at least 90% after 180 days. In general, biodegradability causes the polyester (mixtures) to decompose in a reasonable and detectable time.
  • Degradation can be effected enzymatically, hydrolytically, oxidatively and / or by the action of electromagnetic radiation, for example UV radiation, and is usually effected for the most part by the action of microorganisms such as bacteria, yeasts, fungi and algae.
  • the biodegradability can be quantified, for example, by mixing polyesters with compost and storing them for a certain period of time. For example, according to DIN EN 13432 (referring to ISO 14855), C02-free air is allowed to flow through matured compost during composting and subjected to a defined temperature program.
  • biodegradability is determined by the ratio of the net CO 2 release of the sample (after deduction of CO 2 release by the compost without sample) to the maximum CO 2 release of the sample (calculated from the carbon content of the sample) as a percentage of biodegradation Are defined.
  • Biodegradable polyesters (mixtures) usually show clear degradation phenomena such as fungal growth, cracking and hole formation after only a few days of composting.
  • Injection molding which is also referred to as injection molding or injection molding is a molding process that is used very often in plastics processing. In injection molding can be produced very economically direct usable moldings in large quantities. The procedure is simplified as follows: In an injection molding machine consisting of a heatable cylinder in which the worm shaft rotates, the respective thermoplastic material ("molding compound”) is melted and injected into a mold made of metal (“tool"). The cavity of the tool determines the shape and surface texture of the finished part. Today, parts of well under one gram can be produced in the double-digit kilogram range.
  • Injection molding can produce commodities with high accuracy economically and in a short time.
  • the nature of the surface of the respective component can be chosen almost freely by the designers. From smooth surfaces for optimal From applications such as graining for touch-friendly areas to patterns or engraving, a variety of surface structures can be visualized.
  • the injection molding process is suitable for economic reasons, in particular for the production of larger quantities.
  • polymer mixtures particularly preferably 14 to 40 cm 3/10 are useful with a MVR (190 ° C, 2.16 kg) according to ISO 1133-1 from 01.03.2012 min from 8 to 50 cm 3/10 min, , Application-technical measurements:
  • the modulus of elasticity was determined by means of a tensile test on tensile bars with a thickness of about 420 ⁇ m in accordance with ISO 527-3: 2003.
  • the Charpy impact strength was determined according to DIN EN 179-2 / 1 eU: 2010 + Amd.A notched DIN EN 179-2 / 1 eA (measured at 23 ° C, 50% relative humidity).
  • the specimen 80mm x 10mm x4mm, stored near its ends as a horizontal bar, is stressed by a single impact of a pendulum with the impact line in the middle between the two specimen abutments and (the specimen) with a high Nominal constant speed (2.9 or 3.8 m / s) is bent.
  • the heat resistance HDT-B was determined according to DIN EN ISO 75-2: 2004-9. A standard specimen is subjected to a three-point bend under constant load to produce a bending stress (HDT / B 0.45 MPa), which is given in the relevant part of this International Standard. The temperature is increased at a uniform speed (120 K / h), and the temperature value at which a predetermined standard deflection corresponding to the fixed bending elongation increase (0.2%) is reached is measured.
  • Aliphatic-aromatic polyester ii II-1 polybutylene adipate-co-terephthalate: Ecoflex FS A1300 BASF SE (MVR company at 8.5 cm 3/10 min (190 ° C, 2.16 kg)
  • Polylactic acid IV IV-1 Polylactic acid (PLA) Ingeo® 3251 D from NatureWorks (MVR at 35 cm 3/10 min
  • the compounds listed in Table 1 were produced on a Coperion MC 40 extruder. The temperatures at the outlet were set to 220 ° C. Subsequently, the extrudate was granulated under water. Following granule preparation, the granules are dried at 60 ° C. in vacuo.
  • the compounded material is carried out on a Ferromatik Millacron K65 injection molding machine with a 30.00 mm screw.
  • the injection mold was a single or multiple cavity mold tool with open hot runner or cold runner.
  • the CAMPUS tools were manufactured according to the standards ISO 179/1 eU: 2010 and ISO 527-1 / -2: 2012.
  • the mold temperature was 25 ° C and filled with a pressure of 560 bar and a pressure of 800 bar.
  • Transmissive spectroscopic (TEM) images of the polymer mixtures listed in Table 2 each show a cocontinuous phase of the polybutylene succinate (component i) and the polylactic acid (component iv).
  • the TPU forms a core-shell structure, wherein component ii and possibly component i are located in the cell interior of the TPU. Comparative System V-3 does not form such a core-shell structure.

Abstract

L'invention concerne un mélange de polyester contenant : i) de 65 à 94 % en poids, rapportés au poids total des composants i à iii, d'un polyester constitué d'acides dicarboxyliques aliphatiques et de diols aliphatiques et ii) de 1 à 15 % en poids, rapportés au poids total des composants i à iii, d'un polyester aliphatique-aromatique contenant : ii-a) de 30 à 70 % en moles, rapportés aux composants ii‑a à ii‑b, d'un acide dicarboxylique aliphatique; ii-b) de 30 à 70 % en moles, rapportés aux composants ii‑a à ii‑b, d'un acide dicarboxylique aromatique; ii-c) de 98 à 100 % en moles, rapportés aux composants ii-a à ii-b, de 1,3-propanediol ou de 1,4-butanediol; ii-d) de 0 à 1 % en poids, rapportés aux composants ii-a à ii-c, d'un allongeur de chaîne ou d'un agent de ramification; iii) de 5 à 20 % en poids, rapportés au poids total des composants i à iii, d'un polyuréthane thermoplastique ou d'un copolyester thermoplastique; iv) de 0 à 45 % en poids, rapportés au poids total des composants i à v, d'acide polylactique; v) de 0 à 45 % en poids, rapportés au poids total des composants i à v, d'une charge minérale. L'invention concerne en outre des articles moulés par injection contenant ces mélanges de polyester.
PCT/EP2018/061782 2017-05-17 2018-05-08 Mélange de polyester résistant aux chocs WO2018210609A1 (fr)

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EP3696232B1 (fr) 2019-02-15 2021-08-25 Basf Se Article moulé par injection
IT202000007963A1 (it) * 2020-04-15 2021-10-15 Novamont Spa Composizione polimerica biodegradabile per la realizzazione di articoli stampati.
US11401413B2 (en) 2017-08-15 2022-08-02 Basf Se Injection-molded article containing surface-modified silicates

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EP0420017A2 (fr) * 1989-09-28 1991-04-03 BASF Aktiengesellschaft Masses moulables de polyurÀ©thane-polyester modifiés pour une résistance élevée aux chocs, leur procédé de préparation et leur utilisation
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EP0420017A2 (fr) * 1989-09-28 1991-04-03 BASF Aktiengesellschaft Masses moulables de polyurÀ©thane-polyester modifiés pour une résistance élevée aux chocs, leur procédé de préparation et leur utilisation
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US11401413B2 (en) 2017-08-15 2022-08-02 Basf Se Injection-molded article containing surface-modified silicates
EP3696232B1 (fr) 2019-02-15 2021-08-25 Basf Se Article moulé par injection
IT202000007963A1 (it) * 2020-04-15 2021-10-15 Novamont Spa Composizione polimerica biodegradabile per la realizzazione di articoli stampati.
WO2021209369A1 (fr) * 2020-04-15 2021-10-21 Novamont S.P.A. Composition polymère biodégradable pour la production d'articles moulés
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