WO2023025638A1 - Mélange maître antistatique à base de polyuréthane thermoplastique ayant des propriétés améliorées pour l'utilisation dans des polymères - Google Patents

Mélange maître antistatique à base de polyuréthane thermoplastique ayant des propriétés améliorées pour l'utilisation dans des polymères Download PDF

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WO2023025638A1
WO2023025638A1 PCT/EP2022/072989 EP2022072989W WO2023025638A1 WO 2023025638 A1 WO2023025638 A1 WO 2023025638A1 EP 2022072989 W EP2022072989 W EP 2022072989W WO 2023025638 A1 WO2023025638 A1 WO 2023025638A1
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perchlorate
mol
diol
weight
preferred
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PCT/EP2022/072989
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Marcus Harald BLUEMEL
Frank Schaefer
Anja OLTMANNS
Alexandra WORMSTALL
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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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C08G18/735—Polyisocyanates or polyisothiocyanates acyclic containing one isocyanate or isothiocyanate group linked to a primary carbon atom and at least one isocyanate or isothiocyanate group linked to a tertiary carbon atom
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/08—Polyurethanes from polyethers
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

Definitions

  • the current invention is directed to an antistatic masterbatch for the use in polymers with improved properties.
  • EP2170972 A1 and EP3058009 A1 describe ionic liquids as antistatic agents for thermoplastic polyurethane (TPU).
  • EP 3 058 009 A1 and PCT/EP 2021 1059230 describe antistatic thermoplastic polyurethanes (TPU) are blended with other polymers to equip them with antistatic properties.
  • thermoplastic polyurethane with perchlorate ensures low surface resistance of the blend even after weathering.
  • the invention further provides a process for producing the composition of the invention, the use of the composition of the invention as conductivity improver and the thermoplastic polyurethane specifically developed for use as conductivity improver.
  • a conductivity improver is understood as a substance, or a polymer composition added to a polymer for improving the conductivity of this polymer compared to the polymer not comprising the conductivity improver.
  • the conductivity of the polymer is determined by measuring the surface resistivity, preferably according to DIN EN 62631-3-2:2018-09, more preferably at 23 °C and 72% rel. humidity.
  • the surface conductivity is the inverse of the surface resistivity.
  • the conductivity enhancer is a substance or a polymer composition reducing the specific surface resistivity for at least a factor 2, preferably 5, more preferably 10.
  • a first aspect and embodiment 1 of the invention is a composition
  • a thermoplastic polyurethane where the thermoplastic polyurethane is prepared from a) an diisocyanate, b) a polyol, preferably a diol comprising a diol A comprising ethoxy and propoxy groups and a diol B comprising butoxy groups, and c) a chain extender, optionally with the aid of a catalysts, and optionally further comprising additives and/or auxiliaries, wherein a perchlorate is comprised in the composition.
  • the term composition indicates that the composition does not comprise the polyurethane only, but may comprise several polymers, additives and/or auxiliaries.
  • the thermoplastic polyurethane is prepared by reacting (a) an organic isocyanate, preferably an diisocyanate, with (b) a compound reactive with isocyanate, in a preferred embodiment a polyol, preferably having two functional groups reactive with isocyanate, also referred to as diol, preferably having a number average molecular weight of from 0.5 x 10 3 g /mol to 100 x 10 3 g /mol and, if desired, (c) a chain extender preferably having a molecular weight of from 0.05 x 10 3 g /mol to 0.499 x 10 3 g /mol, if desired in the presence of (d) a catalyst and/or (e) an auxiliary and/or an additive.
  • an organic isocyanate preferably an diisocyanate
  • a compound reactive with isocyanate in a preferred embodiment a polyol, preferably having two functional groups reactive with isocyanate, also referred to as diol, preferably having
  • the components (a) isocyanate, preferably diisocyanate, (b) compound reactive with isocyanate, in a preferred embodiment polyol, more preferred a diol, and (c) chain extender are also addressed individually or together as structural components.
  • the structural components including the catalyst and/or the auxiliary and/or the additive are also called input materials.
  • thermoplastic polyurethane TPU
  • the molar ratios of the quantities of the structural components can be varied, whereby the hardness and melt viscosity increase with increasing content of isocyanate or with increasing content of isocyanate and chain extender (c), while the melt flow index decreases.
  • polyisocyanate polyaddition product preferably thermoplastic polyurethanes, preferably those having a Shore A hardness of less than 95, preferably from 95 to 75 Shore A
  • the essentially difunctional polyols (b), also referred to as diols, and the chain extender (c) may advantageously be used in mole ratios of 1 :1 to 1 :5, preferably 1 :1.5 to 1 :4.5, such that the resulting mixtures of the structural components compound reactive with isocyanate, preferably polyol (b) and chain extender (c) have a hydroxyl equivalent weight of greater than 200, and in particular from 230 to 450, while for the production of harder TPU, e.g.
  • the molar ratios of compound reactive with isocyanate and chain extender being in the range of 1 :5.5 to 1 :15, preferably 1 :6 to 1 :12, such that the resulting mixtures of compound reactive with isocyanate (b) and chain extender (c) have a hydroxyl equivalent weight of 110 to 200, preferably 120 to 180.
  • the structural components isocyanate (a), compound reactive with isocyanate (b), in a preferred embodiment also the chain extender (c), are reacted in preferred embodiments in the presence of a catalyst (d), and optionally auxiliaries and/or additives (e) in such quantities that the equivalent ratio of NCO groups of the isocyanate, preferably the diisocyanates (a) to the sum of the hydroxyl groups of the component reactive with isocyanate (b) and chain extender (c) is 0.95 to 1.10:1 , preferably 0.98 to 1.08:1 and in particular approximately 1.0 to 1.05:1. In a very preferred embodiment the equivalent ratio is 1.0.
  • Polyisocyanate polyaddition product preferably thermoplastic polyurethane
  • the upper limit for the weight-average molecular weight of TPU is generally determined by the processability and the desired range of properties.
  • the weight-average molecular weight does not exceed 0.8 x10 6 g/mol.
  • the mean molecular weights and the weight-average molecular weight as outlined herein are determined by gel permeation chromatography, preferably according to DIN 55672-1.
  • the isocyanate preferably is an organic isocyanate, more preferred is a diisocyanate. Further preferred the isocyanate is selected from the group consisting of aliphatic, cycloaliphatic, arali- phatic and aromatic isocyanates, or is a mixture thereof.
  • the isocyanate more preferably is selected from the group comprising tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methyl-pentamethylene 1 ,5-diisocyanate, 2-ethyl-butylene-1 ,4-diisocyanate, 1 ,5-pen- tamethylene diisocyanate (PDI), 1 ,4- butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-iso- cyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1 ,4- bis(isocyanatomethyl)cyclo- hexane and/or 1 ,3-bis(isocyanatomethyl)cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-tetramethylene x
  • Aliphatic isocyanates are preferred when stability against electromagnetic waves e.g. light is of importance, whereas aromatic polyisocyanate is preferred when high mechanical strength of the polyurethane, especially the thermoplastic polyurethane is required.
  • a further advantage of aliphatic isocyanate is that it may be produced bio-based.
  • Aliphatic isocyanates are preferred. Very preferred aliphatic isocyanate are hexamethylene diisocyanate, in particular 1 ,6-hexamethylene diisocyanate (HDI).and pentamethlyenediisocyante, preferably 1 ,5-pentamethylene diisocyanate. This has the additional advantage, that it can be produced bio-based. The most preferred isocyanate is1 ,6 hexa- methylene-diisocyanate.
  • the isocyanate-reactive compound has on statistical average at least 1.8 and at most 3.0 Zere- witinoff-active hydrogen atoms, this number is also referred to as the functionality of the isocyanate-reactive compound and indicates the quantity of the isocyanate-reactive groups of the molecule calculated theoretically down to one molecule from a quantity of substance.
  • the functionality is preferred between 1 .8 and 2.6, further preferred between 1 .9 and 2.2 and especially preferred 2.
  • Compounds reactive with isocyanates are preferably those having a molecular weight between 0.500 g/mol and 8 x10 3 g/mol, preferably 0.7 x 10 3 g/mol to 6.0 x 10 3 g/mol, in particular 0.8 x 10 3 g/mol to 4.0 x 10 3 g/mol.
  • the isocyanate-reactive compound is essentially linear and is a single isocyanate-reactive compound or is a mixture of different such compounds, in which case the mixture meets the above requirement.
  • These long-chain compounds are used with a content of 1 mol% equivalent to 80 mol% equivalent, based on the isocyanate group content of the polyisocyanate.
  • the compound reactive with isocyanate (b) preferably has a reactive group selected from the hydroxyl group, the amino group, the mercapto group or the carboxylic acid group.
  • the preferred group is the hydroxyl group.
  • These compounds are also referred to as polyol or polyhydroxy polyol.
  • the polyol (b) preferably is selected from the group consisting of polyesterols, polyetherols or polycarbonate diols, more preferred from the group consisting of polyether polyol and polycarbonate. Particularly preferred is polyether polyol. More preferably the polyol is a diol.
  • the polyol which preferably is a diol, comprises a diol A comprising ethoxy and propoxy groups, and a diol B comprising butoxy groups,
  • the molar percentage of the ethoxy and propoxy groups and butoxy groups in the composition is at least 5 mol%, preferably at least 10 mol%, based on the mole weight of the total diol. Further preference is given to the proportion of ethoxy groups in the diol in the composition at the same time being at least 25 mol%, more preferably at least 40 mol%, more preferably at least 60 mol% and particularly preferably at least 65 mol%, based on the total diol.
  • the molar percentage of the ethoxy group being in the range from 70 mol% to 75 mol%, the proportion of the propoxy group being in the range from 12 mol% to 18 mol% and the proportion of the butoxy groups being in the range from 12 mol% to 18 mol%, based on the total polyol.
  • the diol B in the composition being a homopolymer.
  • a homopolymer is a polymer which is made up of virtually only one monomer group, i.e. essentially does not comprise any other monomers. "Essentially” means that at least 95 mol% of the homopolymer consists of only one monomer, more preferably at least 97.5 mol% and particularly preferably at least 99 mol%.
  • a preferred diol B is polybutylene oxide diol. More preferably diol B is polytetrahydrofuran.
  • the diol A in the composition is preferably a block copolymer having one block and two ends, with the block comprising ethoxy and propoxy groups and the two ends of the block copolymer comprising exclusively ethoxy groups.
  • the proportion of ethoxy groups in the two ends of the block copolymer is preferably more than 5 mol%, preferably at least 10 mol% and particularly preferably at least 15 mol%, based on the number average molecular weight of the total block copolymer.
  • the ends of the block copolymer very particularly preferably comprise from 10 mol% to 20 mol% of the ethoxy groups, based on the total block copolymer, and the block of the block copolymer comprises in the range from 60 mol% and 70 mol% of ethoxy groups and in addition from 15 mol% to 20 mol% of propoxy groups, based on the total block copolymer.
  • Diol A preferably is prepared by adding the desired cyclic alkylene oxides, in the present case ethylene oxide and propylene oxide, to a bifunctional starter molecule in a reactor in a 1st step, so that the cyclic alkylene oxides polymerize with ring opening to form a prepolymer.
  • Very particularly preferred examples are 1 ,2-ethylene glycol, also referred to as monoethyl glycol (MEG), diethylene glycol (DEG), monopropanediol (MPG), preferably 1 ,3-propyl- ene glycol, and also dipropanediol (DPG), preferably 4-oxa-1 ,7-heptanediol.
  • MEG monoethyl glycol
  • DEG diethylene glycol
  • MPG monopropanediol
  • DPG dipropanediol
  • DPG dipropanediol
  • the alkylene oxides react arbitrarily, which is also referred to as the mixed mode of operation.
  • the mixed mode of operation is preferred.
  • a person skilled in the art can control the structure of the polyol and the molar distribution of the monomers within a narrow range on the basis of the molecular weights of the alkylene oxides and control of the amounts added.
  • exclusively ethylene oxide is added in a step 2 to the prepolymer from step 1 , so that the diol A has ethoxy groups at the ends.
  • the ring-opening polymerization is carried out with the aid of catalysts.
  • basic catalysts such as alkali metal or alkaline earth metal hydroxides or alkali metal or alkaline earth metal alkoxides, preferably NaOH, KOH, CsOH or sodium methoxide and potassium methoxide.
  • Other preferred catalysts are ones which comprise functional amino groups; preferred examples are N,N-dimethylethanolamine (DMEOA) or imidazole.
  • a third group of preferred catalysts is carbenes, preferably N-heterocyclic carbenes.
  • step 2 The product obtained in step 2 is precipitated by means of a precipitant in step 3.
  • Precipitants are usually proton donors; examples of preferred precipitants are carbonic acid (H2CO3), phosphoric acid (H3PO4).
  • the polymer worked up in step 3 is filtered in a 4th step in order to remove the catalyst.
  • Binders are used as filtration aids; preferred examples of binders are cellulose or silica gel.
  • Diol B is prepared analogously, with exclusively butylene oxide being used in step 1 and step 2 being omitted.
  • a preferred diol A is the polyol which can be procured under the name Lupranol VP9243 from BASF Polyurethanes GmbH in October 2013.
  • the polyol is a polyol mixture of the diol A and diol B as outlined above with at least one further polyol, as indicated above.
  • the further polyol is used in an amount of less than 50 % by weight, preferably less than 35 % by weight, more preferably less than 15 % by weight, and most preferably less than 5 % by weight, based on the total weight of the polyol mixture.
  • the polyol is a mixture of diol A and diol B.
  • the further polyol in a preferred embodiment is a diol.
  • the polyol is also referred to as diol.
  • a chain extender is used in the synthesis of the polyurethane, preferably the thermoplastic polyurethane.
  • the chain extender preferably is an aliphatic, araliphatic, aromatic and/or cycloaliphatic compound, preferably with a molecular weight of 0.05 x 10 3 g/mol to 0.499 x 10 3 g/mol, preferably with 2 groups reactive with isocyanate, which are also referred to as functional groups.
  • the chain extender is either a single chain extender or a mixture of at least two chain extenders.
  • the chain extender is preferably a difunctional compound, preferred examples being diamines or alkane diols having 2 to 10 carbon atoms in the alkylene radical, or a mixture thereof.
  • the chain extender (c) is selected from the group consisting of 1 ,2- ethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butanediol, 2,3-butanediol, 1 ,5-pentane- diol, 1 ,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, okta-, nona- and/or deca alkylene glycole, dipropylene glycol, 1 ,4-cyclohexanediol, 1 ,4-dimethanol cyclohexane, neopentylglycol and hydroquinone bis (beta-hydroxyethyl) ether (HQEE), or is a mixture thereof.
  • HQEE hydroquinone bis (beta-hydroxyethyl
  • the chain extender selected from the group consisting of 1 ,2-ethylene glycol, 1 ,3-pro- panediol, 1 ,4-butanediol, and 1 ,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, okta-, nona- and/or deca alkylene glycol, preferably respective oligo- and/or polypropylene glycol, or is a mixture thereof.
  • Particularly preferred chain extender is 1 ,3-propanediol, 1 ,4-butanediol or 1 ,6-hexanediol, or is a mixture thereof.
  • the chain extender comprises, preferably is 1 ,6-hexandiol.
  • Catalysts (d) which, in particular, accelerate the reaction between the NCO groups of the isocyanates (a) and the hydroxyl groups of the polyol and the chain extenders, in a preferred embodiment is selected from the group consisting of tertiary amines and organic metal compound, or is a mixture thereof.
  • a preferred tertiary amine is selected from the group consisting of triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethyl-piperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2. octane], or is a mixture thereof;
  • a preferred organic metal compound is selected from the group consisting of titanic ester, iron compound, tin compound, and bismuth salt, or is a mixture thereof.
  • a preferred iron compound is iron(lll) acetylacetonate.
  • a preferred tin compound is selected from the group consisting of tin diacetate, tin dioctoate, tin dilaurate and dialkyl tin salts of aliphatic carboxylic acids, preferably tin dioctoate, or is a mixture thereof.
  • a preferred titanic ester is tetrabutyl orthotitanate.
  • the bismuth is present in the oxidation states 2 or 3, in particular 3, with preference being given to salts of carboxylic acids, preferably carboxylic acids having from 6 to 14 carbon atoms, particularly preferably from 8 to 12 carbon atoms.
  • a very preferred bismuth salt is bismuth(lll) neodecanoate, bismuth 2-ethylhexanoate, or bismuth octanoate, or is a mixture thereof.
  • the catalysts (d) is preferably used in an amount of from 0.0001 to 0.1 part by weight per 100 parts by weight of the compound reactive toward isocyanates, preferably polyol. Preference is given to using tin catalysts, in particular tin dioctoate.
  • a very preferred catalyst is SDO (tin (II) 2-ethylhexanoate), preferably used in quantities of 0.35- 0.4 parts per weight, referring to the composition.
  • an auxiliary or additive is added to the composition.
  • Preferred examples include surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricating and demolding aids, dyes and pigments, if necessary stabilizers, preferably against hydrolysis, light, heat or discoloration, inorganic and/or organic fillers, reinforcing agents and/or plasticizers.
  • Stabilizers in the sense of this invention are additives which protect a plastic or a plastic composition against harmful environmental influences.
  • Preferred examples are primary and secondary antioxidants, sterically hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis inhibitors, 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 absorber has a number average molecular weight greater than 0.3 x 10 3 g/Mol, in particular greater than 0.39 x 10 3 g/Mol. Furthermore, the preferred UV absorber has a molecular weight not exceeding 5 x 10 3 g/Mol, particularly preferred not exceeding 2 x 10 3 g/mol.
  • the UV absorber is preferably selected from the group consisting of cinnamates, oxanilides and benzotriazole, or is a mixture thereof, particularly suitable as UV absorbers is benzotriazole.
  • particularly suitable UV-absorbers are Tinuvin® 213, Tinuvin® 234, Tinuvin® 312, Tinuvin® 571 , Tinuvin® 384 and Eversorb® 82.
  • the UV absorbers is added in quantities of 0.01 wt.% to 5 wt.% based on the total weight of the composition, preferably 0.1 wt.% to 2.0 wt.%, in particular 0.2 wt.% to 0.5 wt.%.
  • a UV stabilization based on an antioxidant and a UV absorber as described above is not sufficient to guarantee a good stability of the composition against the harmful influence of UV rays.
  • a hindered-amine light stabilizer HALS
  • Examples of commercially available HALS stabilizers can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Kunststoff, 2001, pp. 123-136.
  • Particularly preferred hindered amine light stabilizers are bis-(1 ,2,2,6,6-penta- , methylpiperidyl) sebacat (Tinuvin® 765, Ciba Spezialitatenchemie AG) and the condensation product of 1-hy- droxyethyl-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 (Tinuvin® 622) is preferred, if 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 components used.
  • HALS compounds are preferably used in a concentration of from 0.01 wt.% to 5 wt.%, particularly preferably from 0.1 wt.% to 1 wt.%, in particular from 0.15 wt.% to 0.3 wt.%, based on the total weight of the composition.
  • a particularly preferred UV stabilization contains a mixture of a phenolic stabilizer, a benzotriazole and a HALS compound in the preferred amounts described above.
  • auxiliaries and additives can be found in the technical literature, e.g. Plastics Additives Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001.
  • the perchlorate is selected from the group consisting of ammonium perchlorate, calcium perchlorate, kalium perchlorate, magnesium perchlorate, sodium perchlorate, zinc perchlorate, or is a mixture thereof., most preferred the perchlorate comprises sodium perchlorate. With an amount of more than 50 weight % referring to the whole amount of perchlorate, more preferred more than 70 weight %, more preferred more than 90 weight%, more preferred more than 95 weight %, more preferred more than 99 weight %. Most preferred the perchlorate is sodium perchlorate.
  • the perchlorate is comprised in an amount of from 0.1% by weight to 25% by weight, preferably from 0.2 % by weight to 10 % by weight, more preferably from 0.3 % by weight to 7.5% by weight and particularly preferably from 0.5 % by weight to 4 % by weight, based on the thermoplastic polyurethane composition
  • the composition comprises at least one further polymer beside the thermoplastic polyurethane.
  • the polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyoxymethylene, ethylene-vinyl acetate, acryloni- trile-butadiene-styrene, polyvinyl chloride, and thermoplastic polyurethane.
  • the recipe of the thermoplastic polyurethane differs from that of the composition.
  • the polymer is selected from the group consisting of polyethylene, polypropylene and polystyrene, or is a mixture thereof.
  • the polymer is comprised in the composition with 1% by weight and less than 50% by weight, preferably more than 5% by weight and less than 35% by weight, particularly preferably more than 15% by weight and less than 30% by weight.
  • thermoplastic polyurethane Another aspect of the invention is the production of the composition comprising a thermoplastic polyurethane according to any of the precedent embodiments, or one their preferred embodiments.
  • composition comprising the thermoplastic polyurethane in an embodiment is produced discontinuously or continuously.
  • a preferred process is the reaction extruder process, the belt line process, the “one shot” process, preferably the “one-shot” process or the reaction extruder process, most preferably the reaction extruder-process.
  • Polyisocyanate prepolymers are obtainable by reacting above-described polyisocyanate in excess, at temperatures of 30 °C to 100 °C, preferably at 8 x10 °C, with the compound reactive isocyanate, preferably the polyol.
  • the building components diisocyanate and polyol, preferably polyol diol, and in a preferred embodiment also the chain extender, are mixed with each other. This is done either in succession or simultaneously, in preferred embodiment in the presence of the catalyst.
  • the building components diisocyanate and diol, in a preferred embodiment also the chain extender, and, in further preferred embodiments, also the catalyst are mixed.
  • the mixing in the reaction extruding process is done preferably at temperatures between 100°C and 280°C, preferably between 140°C and 250°C.
  • the thermoplastic polyurethane obtained preferably is in the form of a granulate or a powder.
  • auxiliaries and additives may be added during the synthesis preferred or are added to the thermoplastic polyurethane.
  • the latter is preferred especially, if the additive or auxiliary is not inert against isocyanate, the chain extender, the compound reactive with isocyanate, or the catalyst.
  • the auxiliaries and/ or perchlorate in one embodiment are added during synthesis of the thermoplastic polyurethane.
  • the auxiliary and/or the perchlorate is added to the thermoplastic polyurethane after its synthesis, more preferably in an extruder.
  • twin-screw extruder is preferred, as the twin-screw extruder operates with positive conveying and thus allows a more precise setting of the temperature and output quantity on the extruder. All components of the following production processes are described and preferred above.
  • thermoplastic polyurethane is prepared from an isocyanate a polyol comprising a diol A and a diol B and a chain extender, optionally with the aid of a catalysts and optionally further comprising additives and/or auxiliaries, wherein the diol A comprises ethoxy and propoxy groups and the diol B comprises butoxy groups.
  • thermoplastic polyurethane is prepared in a step A and this thermoplastic polyurethane is mixed with the perchlorate in a step B.
  • thermoplastic polyurethane in a step A and mixing this thermoplastic polyurethane with the perchlorate in a step B and then mixing the product from step A and B with a polymer as outlined and preferred above.
  • the composition comprising thermoplastic polyurethane according to one of the precedent embodiments or its preferred embodiments is in the form of a pellet or a powder.
  • the pellet or powder in a preferred embodiment is a compact material.
  • Another aspect of the invention and preferred embodiment is the use of the composition according to one of precedent embodiments or its preferred embodiment for improving the electric conductivity in an article.
  • composition as conductivity improver for a polymer.
  • composition of this invention is blended with a second composition comprising a polymer before forming the article.
  • the composition as such is also referred to as master batch
  • composition blended with another polymer as outlined above, is also referred to as blend.
  • the forming of these articles is preferably done by injection moulding, calendering, producing of films, powder sintering, or extrusion.
  • composition of this invention is used for polymers from which expanded beads, preferably those comprising thermoplastic polyurethane, are produced.
  • foamed beads and also articles produced therefrom may be used in various applications (see e.g. WO 94/20568, WO 2007/082838 A1 , WO2017030835, WO 2013/153190 A1 , WO2010010010), EP 21168694.4), herein incorporated by reference.
  • articles, as outlined and preferred herein, are produced from these expanded beads
  • Yet another aspect of the invention is the article produced with a composition according to one of the embodiments as outlined above or its preferred embodiments.
  • these article is selected from the group consisting of cable, cases, cell-phone, coating, covers, damping element, bellows, foil, fiber, film, moulded body, roofing or flooring for buildings or vehicles, non woven fabric, gasket, packaging material, roll, shoe sole, middle sole of a shoe, hose, cable, cable connector, cable sheathing, pillow, laminate, phone, profile, strap, saddle, foam, by additional foaming of the preparation, plug connection, television, trailing cable, solar module, lining in automobiles, wiper blade, elevator load bearing members, roping arrangements, drive belts for machines, preferably passenger conveyer, handrails for passenger conveyers modifier for thermoplastic materials, which means substance that influences the properties of another material.
  • Each of these articles itself is a preferred embodiment, also referred to as an application.
  • the product is selected from covers, packaging material, cases, film, phone, cell phones, television, or cable, more preferably for an electronic device.
  • the packaging material is a stretchable film, more preferably as outlined in PCT/EP2021/059230.
  • the cover is for electronic device, preferably as outlined in WO 2018/015504 Examples
  • Lupolen 4261 AG a typical high molecular weight, high-density polyethylene was used.
  • Lupolen 4161 AG exhibits a density (determined according to DIN EN ISO 1183-1 :2019, A) of 0.945 g em -3 , an MFR (determined according to DIN EN ISO 1133-1 :2011) at 190 °C and 21.6 kg of 6.0 g/(10 min), and a Vicat temperature (determined according to DIN EN ISO 306:2013, A) of 126 °C.
  • HDI hexamethylene diisocyanate
  • PTMG polytetramethylene glycol
  • TPU antistatic thermoplastic polyurethane
  • EMIN ETOSO3 3 wt% of a 1-ethyl-3-methyl-1-imidaz- olium ethylsulfate, (EMIN ETOSO3), 1.3 wt% of an additive mixture comprising antioxidant (AO, hindered phenol derived from pentaerythritol and di-tert-butyl hydroxyphenylpropanamide), hindered amine light stabilizer (HALS, condensation product of i-hydroxyethyl-2,2,6,6-tetramethyl-4- hydroxypiperidine and succinic acid), UV filter (2-(2H-benzotriazol-2-yl)-4,6-bis(1 -methyl-1-phe- nylethyl)phenol), chain regulator (octanol), and lubricant (distearamide).
  • antioxidant hindered phenol derived from pentaerythritol and di-tert-butyl hydroxyphenylpropanamide
  • HALS hindere
  • HDI hexamethylene diisocyanate
  • PTMG polytetramethylene glycol
  • M w number average molecular weight
  • TPU thermoplastic polyurethane
  • compositions are also incorporated 1.75 wt% of an additive mixture comprising antioxidant (AO, hindered phenol derived from pentaerythritol and di-tert-butyl hydroxyphenylpropanamide), hindered amine light stabilizer (HALS, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypi- peridine and succinic acid), UV absorber (2-propenoic acid, 2-cyano-3,3-diphenyl-, 2,2-bis[[(2- cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]methyl]-1 ,3-propanediyl ester) and chain regulator (octanol).
  • antioxidant hindered phenol derived from pentaerythritol and di-tert-butyl hydroxyphenylpropanamide
  • HALS hindered amine light stabilizer
  • UV absorber (2-propenoic acid, 2-cyano-3,3
  • an antistatic TPU polymer blend 82 wt% of the base polymer (e.g. Lupolen 4261 AG) and 18 wt% of the antistatic TPU composition 1 or 2 were compounded in an extruder and formed to test plates of 10 cm x 10 cm x 2 mm by injection molding.
  • the base polymer e.g. Lupolen 4261 AG
  • 18 wt% of the antistatic TPU composition 1 or 2 were compounded in an extruder and formed to test plates of 10 cm x 10 cm x 2 mm by injection molding.
  • test plates (10 cm x 10 cm x 2 mm ) prepared via injection molding was conducted according to ISO 4892-2A Cycle 1 (Atlas).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un mélange maître antistatique comprenant du polyuréthane thermoplastique, le polyuréthane thermoplastique étant préparé à partir d'un isocyanate, un polyol comprenant un diol A comprenant des groupes éthoxy et des groupes propoxy et un diol B comprenant des groupes butoxy, et un allongeur de chaîne, un perchlorate étant compris dans la composition. D'autres aspects de l'invention sont des mélanges fabriqués avec ce mélange maître, des procédés de production respectifs et l'utilisation du mélange maître.
PCT/EP2022/072989 2021-08-27 2022-08-17 Mélange maître antistatique à base de polyuréthane thermoplastique ayant des propriétés améliorées pour l'utilisation dans des polymères WO2023025638A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020568A1 (fr) 1993-03-11 1994-09-15 Basf Aktiengesellschaft Mousses a base de polyurethannes thermoplastiques
WO2007082838A1 (fr) 2006-01-18 2007-07-26 Basf Se Mousse a base de polyurethane thermoplastique
WO2009086246A1 (fr) * 2007-12-26 2009-07-09 Lubrizol Advanced Materials, Inc. Feuille multicouche transparente ayant des propriétés de dissipation électrostatique
WO2010010010A1 (fr) 2008-07-25 2010-01-28 Basf Se Mélanges de polymères thermoplastiques à base de polyuréthanne thermoplastique et de polymère de styrène, mousses fabriquées à partir de ces mélanges et procédés de fabrication correspondants
EP2170972A1 (fr) 2007-07-17 2010-04-07 Basf Se Polyuréthanne thermoplastique à propriétés antistatiques
WO2013153190A1 (fr) 2012-04-13 2013-10-17 Basf Se Procédé de production de granulés expansés
EP3058009A1 (fr) 2013-10-15 2016-08-24 Basf Se Polyuréthane thermoplastique conducteur
WO2017030835A1 (fr) 2015-08-19 2017-02-23 Nike Innovate C.V. Procédé de préparation de mousse élastomère thermoplastique et article en mousse
WO2018015504A1 (fr) 2016-07-21 2018-01-25 Basf Se Soudage par micro-onde d'une poudre d'élastomère
CN112745659A (zh) * 2020-01-15 2021-05-04 昆山科信高分子材料有限公司 含抗静电母粒的热塑性聚氨酯弹性体材料及其制法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020568A1 (fr) 1993-03-11 1994-09-15 Basf Aktiengesellschaft Mousses a base de polyurethannes thermoplastiques
WO2007082838A1 (fr) 2006-01-18 2007-07-26 Basf Se Mousse a base de polyurethane thermoplastique
EP2170972A1 (fr) 2007-07-17 2010-04-07 Basf Se Polyuréthanne thermoplastique à propriétés antistatiques
WO2009086246A1 (fr) * 2007-12-26 2009-07-09 Lubrizol Advanced Materials, Inc. Feuille multicouche transparente ayant des propriétés de dissipation électrostatique
WO2010010010A1 (fr) 2008-07-25 2010-01-28 Basf Se Mélanges de polymères thermoplastiques à base de polyuréthanne thermoplastique et de polymère de styrène, mousses fabriquées à partir de ces mélanges et procédés de fabrication correspondants
WO2013153190A1 (fr) 2012-04-13 2013-10-17 Basf Se Procédé de production de granulés expansés
EP3058009A1 (fr) 2013-10-15 2016-08-24 Basf Se Polyuréthane thermoplastique conducteur
US20160260516A1 (en) * 2013-10-15 2016-09-08 Basf Se Conductive thermoplastic polyurethane
WO2017030835A1 (fr) 2015-08-19 2017-02-23 Nike Innovate C.V. Procédé de préparation de mousse élastomère thermoplastique et article en mousse
WO2018015504A1 (fr) 2016-07-21 2018-01-25 Basf Se Soudage par micro-onde d'une poudre d'élastomère
CN112745659A (zh) * 2020-01-15 2021-05-04 昆山科信高分子材料有限公司 含抗静电母粒的热塑性聚氨酯弹性体材料及其制法

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