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WO2010124459A1 - Polyuréthane ayant un plastifiant à base de l'ester d'un acide tricarboxylique - Google Patents

Polyuréthane ayant un plastifiant à base de l'ester d'un acide tricarboxylique Download PDF

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Publication number
WO2010124459A1
WO2010124459A1 PCT/CN2009/071551 CN2009071551W WO2010124459A1 WO 2010124459 A1 WO2010124459 A1 WO 2010124459A1 CN 2009071551 W CN2009071551 W CN 2009071551W WO 2010124459 A1 WO2010124459 A1 WO 2010124459A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane
tricarboxylic acid
acid
mol
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2009/071551
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English (en)
Inventor
Bin-Eric Chen
Frank Schaefer
Dirk Kempfert
Christoph Bahr
Guenter Scholz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Polyurethane Specialties China Co Ltd
BASF SE
Original Assignee
BASF Polyurethane Specialties China Co Ltd
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Polyurethane Specialties China Co Ltd, BASF SE filed Critical BASF Polyurethane Specialties China Co Ltd
Priority to PCT/CN2009/071551 priority Critical patent/WO2010124459A1/fr
Priority to KR1020117028565A priority patent/KR101801687B1/ko
Priority to PCT/EP2010/055490 priority patent/WO2010125009A1/fr
Priority to CN2010800190010A priority patent/CN102414236B/zh
Priority to EP10718929.2A priority patent/EP2424912B1/fr
Priority to ES10718929.2T priority patent/ES2449300T3/es
Priority to US13/266,199 priority patent/US8993690B2/en
Priority to JP2012507699A priority patent/JP5654000B2/ja
Priority to BRPI1015965 priority patent/BRPI1015965B1/pt
Publication of WO2010124459A1 publication Critical patent/WO2010124459A1/fr
Anticipated expiration legal-status Critical
Priority to US14/600,106 priority patent/US20150133610A1/en
Ceased legal-status Critical Current

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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
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/18—Plasticising macromolecular compounds
    • 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
    • C08G2120/00—Compositions for reaction injection moulding processes
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids

Definitions

  • the invention relates to novel plasticizers for polyurethanes.
  • TPU thermoplastic polyurethanes
  • Plasticizers too, are widely known in the market. These are frequently phthalates or benzoates for polyester-polyurethanes (EP 1 556 433) or phosphates for polyether-TPU (EP 1 344 55).
  • the plasticizers used in the market are frequently not completely toxicologically safe.
  • the processing, in particular of benzoates is disadvantageous since benzoates influence the reaction sequence and thus hinder the build up of molar mass. This problem occurs especially when the plasticizer is added directly to the polyurethane during the synthesis.
  • Other plasticizers from the group consisting of the adipates, hydrogenated phthalates, fatty acids, as described in EP 1108735, or even polyolefins are not sufficiently miscible with PU. Owing to their acid content, plasticizers from the group consisting of the phosphates are less suitable for use in PU based on ester-polyols since the acid group may result in cleavage of the ester.
  • thermoplastic polyurethanes where the plasticizer should be able to be thoroughly incorporated into the polyurethane, should migrate out and/or evaporate only slightly, should not adversely affect the properties of the polyurethane, such as processibility, heat stability and UV stability, should not promote the degradation of the polyurethane and should be stable to liquid media and in particular should also be suitable as a material for use in articles which are in contact with foods or human body parts.
  • the mechanical properties of the TPU for example the abrasion and the elastomeric properties, must not become poorer than those of comparable plasticizers.
  • the polyurethane itself should have flexible properties, form readily demoldable molding materials and have little shrinkage and good low-temperature properties.
  • the plasticizer must additionally be chosen so that it does not lose its property profile during the customary thermoplastic processing, such as injection molding or extrusion, and can be expediently processed technologically and economically.
  • polyurethane comprising the ester of a tricarboxylic acid.
  • the invention therefore relates to a polyurethane preparation, preferably a thermoplastic polyurethane preparation, comprising from 50% by weight to 99% by weight of a polyurethane, preferably thermoplastic polyurethane, prepared from at least one isocyanate, preferably diisocyanate, and polyol, preferably polymer diol, having a molar mass of from 0.5 kg/mol to 8 kg/mol, which comprises the ester of a tricarboxylic acid with at least one alcohol, all acid groups of the triester having been esterified with an alcohol.
  • the invention relates to preparation processes for the polyurethanes according to the invention, articles produced therefrom and the use of tricarboxylic esters as plasticizers in polyurethanes.
  • Preparations of polyurethanes, preferably thermoplastic polyurethanes, with the tricarboxylic ester according to the invention which preferably acts as a plasticizer have the advantage that the plastics are also suitable for applications where they come into contact with foods since they have been toxicologically substantially safe as plasticizers to date.
  • the plasticizer can be readily incorporated, has little tendency to migrate out or evaporate and simultaneously improves the properties of the polyurethane, such as processibility, heat stability and UV stability, and does not promote the degradation of the plastic.
  • a further advantage of the polyurethane preparation according to the invention is the possibility of use in the food sector and in direct contact with foods or the body surface.
  • the polyurethane preparation has high thermal stability and therefore has a broad processing window in the thermoplastic conversion process.
  • the present invention relates to polyurethane preparations comprising:
  • thermoplastic polyurethane prepared from
  • chain extenders (c) having molecular weights of from 0.06 kg/mol to 0.5 kg/mol
  • diisocyanates (a), compounds (b) active toward isocyanates and chain extenders (c) are also discussed as synthesis components.
  • the tricarboxylic ester is present in the polyurethane, preferably the thermoplastic polyurethane, in an amount of from 1% by weight to 50% by weight, preferably from 5% by weight to 40% by weight, in particular from 15% by weight to 35% by weight, based in each case on the total weight of the polyurethane plastic comprising the tricarboxylic ester.
  • the tricarboxylic acid has an aliphatic structure, the aliphatic structure being branched and comprising 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, particularly preferably 5 to 10 carbon atoms and very particularly preferably 6 carbon atoms.
  • the carbons in the branched aliphatic structure are bonded to one another directly via a single or double bond.
  • the aliphatic structure has only single bonds between the carbons.
  • the invention also comprises all combinations and embodiments listed here which are not expressly mentioned but which are directly evident to a person skilled in the art through combinations of the embodiments listed.
  • the tricarboxylic acid comprises at least one hydroxyl group.
  • the at least one hydroxyl group is bonded directly to a carbon atom of the above-described aliphatic structure of the tricarboxylic acid so that the at least one hydroxyl group is bonded, in addition to the three acid groups, to the aliphatic structure.
  • a hydroxyl group on the aliphatic structure of the tricarboxylic acid is particularly preferred.
  • a particularly preferred tricarboxylic acid is citric acid.
  • all three acid groups of the tricarboxylic acid are esterified with an alcohol.
  • the alcohols may have aromatic and/or aliphatic structures. Alcohols which comprise 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms and particularly preferably 1 to 6 carbon atoms are more preferred. Alcohols having an aliphatic structure are preferably used, linear aliphatic structures of the alcohols being more preferred and aliphatic structures which have no double bonds being particularly preferred.
  • the alcohols comprise a multiple of 2 carbon atoms, i.e. 2, 4, 6, 8, 10, 12, 14, 16 etc. carbon atoms.
  • the alcohol is ethanol. In a second very particularly preferred embodiment, the alcohol is a butanol. More preferably, all three acid groups of the tricarboxylic acid are esterified with the same alcohol. In a very particularly preferred embodiment, the ester is tributyl 2-acetoxy-1 ,2,3-tricarboxylate.
  • the at least one hydroxyl group of the tricarboxylic acid is additionally esterified with a carboxylic acid.
  • the carboxylic acid is selected from aromatic or aliphatic carboxylic acids having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 2 to 22 carbon atoms, in particularly preferred embodiments the number of carbon atoms being a multiple of 2.
  • the at least one hydroxyl group of the tricarboxylic acid is etherified.
  • the ether comprises 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 2 to 22 carbon atoms, in particularly preferred embodiments the number of carbon atoms being a multiple of 2.
  • polyethylene glycol or polypropylene glycol is employed, polyethylene glycol being preferred.
  • the tricarboxylic acid comprises at least one amino group.
  • a carboxylic acid forms an acid amide with this amino group.
  • This carboxylic acid is selected from aromatic or aliphatic carboxylic acids having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 22 carbon atoms, in particularly preferred embodiments the number of carbon atoms in the carboxylic acid being a multiple of 2.
  • the at least one amino group of the tricarboxylic acid forms a secondary amine with at least one radical R' or a tertiary amine with a second radical R".
  • the radicals R' and R" independently of one another, comprise 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 2 to 22 carbon atoms, in particularly preferred embodiments the number of carbon atoms being a multiple of 2.
  • the radical is a polyethylene glycol, or polypropylene glycol, polyethylene glycol being preferred.
  • the polyurethanes can be prepared by reacting (a) isocyanates with (b) compounds reactive toward isocyanates and having a molecular weight of from 0.5 kg/mol to 6 kg/mol and, if appropriate, (c) chain extenders having a molecular weight of from 0.05 to 0.5, if appropriate in the presence of (d) catalysts and/or (e) customary assistants and/or (f) additives.
  • the plasticizers (i) according to the invention may be added both to the compounds (b) reactive toward isocyanates before or during the preparation of the polyurethane, preferably TPU, and to the prepared polyurethane, preferably TPU, for example to the molten or softened TPU.
  • thermoplastic polyurethane A particular advantage of use in thermoplastic polyurethane is that TPU can be processed by a thermoplastic method without the effect of the plasticizer being lost.
  • the components (a), (b), (c) and, if appropriate, (d) and/or (e) usually used in the preparation of the TPU are described by way of example below:
  • Organic isocyanates (a) used are customary aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates, preferably diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene 1 ,5-diisocyanate, 2-ethylbutylene 1 ,4-diisocyanate, pentamethylene 1 ,5-diisocyanate, butylene 1 ,4-diisocyanate, 1-isocyanato- S.S. ⁇ -trimethyl- ⁇ -isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1 ,4- and/or 1 ,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1 ,4-diisocyanate
  • the organic isocyanate is an isocyanate which comprises at least 90% by weight, more preferably at least 95% by weight, particularly preferably at least 99% by weight, of methylenediphenyl diisocyanates (MDI).
  • MDI methylenediphenyl diisocyanates
  • polyesterols for example polyesterols, polyetherols and/or polycarbonatediols, which are usually summarized by the term "polyols", having molecular weights of from 0.5 kg/mol to 8 kg/mol, preferably from 0.6 kg/mol to 6 kg/mol, in particular from 0.8 kg/mol to 3 kg/mol, and preferably an average functionality with respect to isocyanates of from 1.8 to 2.3, preferably from 1.9 to 2.2, in particular 2, can be used as compounds (b) reactive toward isocyanates.
  • These are particularly preferably linear hydroxyl- terminated polyols. As a result of the production, these polyols often comprise small amounts of nonlinear compounds.
  • the term "substantially linear polyols” is therefore also frequently used. Polyesterdiols, polyetherdiols, polycarbonatediols or mixtures of these are preferred.
  • Polyetherpolyols are preferably used, for example those based on generally known initiator substances and customary alkylene oxides, for example ethylene oxide, epichlorohydrin, propylene oxide and/or 2, 3-butylene oxide, preferably polyetherols based on 1 ,2-propylene oxide and ethylene oxide. Polyoxytetramethylene glycols are particularly preferred.
  • the alkylene oxides may be used individually, alternately in succession or as mixtures.
  • initiator molecules water, amino alcohols, such as N- alkyldiethanolamines, for example N-methyldiethanolamine, and diols, ethylene glycol, 1 ,3-propylene glycol, 1 ,4-butanediol and 1 ,6-hexanediol. If appropriate, mixtures of initiator molecules can also be used.
  • Suitable polyetherols are furthermore the polymerization products of tetrahydrofuran which contain hydroxyl groups.
  • polyetherols used may be so-called polyetherols having a low degree of unsaturation.
  • polyols having a low degree of unsaturation are understood as meaning in particular polyether alcohols having a content of unsaturated compounds of less than 0.02 meq/g, preferably less than 0.01 meq/g.
  • Such polyether alcohols are generally prepared by an addition reaction of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, with the diols or triols described above in the presence of highly active catalysts.
  • Such highly active catalysts are, for example, potassium and cesium hydroxide and multimetal cyanide catalysts, also referred to as DMC catalysts.
  • DMC catalysts A frequently used DMC catalyst is zinc hexacyanocobaltate.
  • the DMC catalyst may be left in the polyether alcohol after the reaction; usually, it is removed, for example by sedimentation or filtration.
  • thermoplastic polyurethane according to the invention is based on polytetrahydrofuran having a molecular weight of from 0.6 kg/mol to 2 kg/mol, preferably from 0.8 kg/mol to 1.4 kg/mol, particularly preferably from 0.95 kg/mol to 1.05 kg/mol, as component (b).
  • Chain extenders (c) used may be generally known aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds having a molecular weight of from 0.06 kg/mol to 0.5 kg/mol, preferably difunctional compounds, for example diamines and/or alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular 1 ,4-butanediol, 1 ,6-hexanediol and/or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/or decaalkylene glycols having 3 to 8 carbon atoms, preferably corresponding oligo- and/or polypropylene glycols, it also being possible to use mixtures of the chain extenders.
  • difunctional compounds for example diamines and/or alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular 1
  • Suitable catalysts (d) which accelerate in particular the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the synthesis components (b) and (c) are the customary tertiary amines known according to the prior art, such as, for example, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethyl- aminoethoxy)ethanol, diazabicyclo-(2,2,2)-octane and similar and in particular organic metal compounds, such as titanic esters, iron compounds, such as, for example, iron(lll) acetylacetonate, tin compounds, e.g.
  • tin diacetate, tin dioctanoate, tin dilaurate or the dialkyl tin salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like.
  • the catalysts are usually used in amounts of from 0.0001 to 0.1 part by weight per 100 parts by weight of polyhydroxy compound (b). Tin catalysts are preferably used, in particular tin dioctanoate.
  • customary assistants (e) may be added to the synthesis components (a) to (c), in addition to the ester of a tricarboxylic acid.
  • Surface-active substances, flame proofing agents, nucleating agents, oxidation stabilizers, lubricants and demolding agents, dyes and pigments, stabilizers, for example against hydrolysis, light, heat or discoloration, inorganic and/or organic fillers and reinforcing agents may be mentioned by way of example.
  • hydrolysis stabilizers are oligomeric and/or polymeric aliphatic or aromatic carbodiimides.
  • stabilizers can preferably be added to the TPU.
  • stabilizers are additives which protect a plastic or a plastic mixture from harmful environmental influences.
  • examples are primary and secondary antioxidants, hindered amine light stabilizers, UV absorbers, hydrolysis stabilizers, quenchers and flame proofing agents.
  • examples of commercial stabilizers are given in Plastics Additive Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Kunststoff, 2001 ([1]), page 98 - page 136.
  • antioxidants may be added.
  • Phenolic antioxidants are preferably used. Examples of phenolic antioxidants are given in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Kunststoff, 2001 , pages 98 -107 and page 116 - page 121.
  • Preferred phenolic antioxidants are those whose molecular weight is greater than 0.7 kg/mol.
  • An example of a preferably used phenolic antioxidant is pentaerythrityl tetrakis(3-(3,5-bis(1 ,1-dimethylethyl)-4-hydroxyphenyl)propionate) (Irganox® 1010).
  • the phenolic antioxidants are used in general in concentrations of from 0.1% by weight to 5% by weight, preferably from 0.1% by weight to 2% by weight, in particular from 0.5% by weight to 1.5% by weight.
  • UV absorbers are generally known and are molecules which absorb high-energy UV light and dissipate the energy.
  • Conventional UV absorbers which are used in industry belong, for example, to the group consisting of the cinnamic esters, the diphenyl cyanoacrylates, the formamidines, the benzylidene malonates, the diarylbutadienes, triazines and the benzotriazoles. Examples of commercial UV absorbers are to be found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Kunststoff, 2001 , pages 116-122.
  • the UV absorbers have a number average molecular weight greater than 0.3 kg /mol, in particular greater than 0.39 kg/mol. Furthermore, the preferably used UV absorbers should have a molecular weight not greater than 5 kg/mol, particularly preferably not greater than 2 kg/mol.
  • the group consisting of the benzotriazoles is particularly suitable as UV absorbers.
  • examples of particularly suitable benzotriazoles are Tinuvin® 213, Tinuvin® 328, Tinuvin® 571 , and Tinuvin® 384 and Eversorb® 82.
  • the UV absorbers are metered in in amounts of from 0.01 to 5% by weight, based on the total mass of TPU, preferably 0.1 - 2.0% by weight, in particular 0.2 - 0.5% by weight.
  • HALS hindered amine light stabilizer
  • HALS compounds are generally known and commercially available. Examples of commercially available HALS stabilizers are to be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Kunststoff, 2001 , pages 123-136.
  • Preferably used hindered amine light stabilizers are hindered amine light stabilizers in which the number average molecular weight is greater than 0.5 kg/mol.
  • the molecular weight of preferred HALS compounds should not be greater than 10 kg/mol, particularly preferably not greater than 5 kg/mol.
  • Particularly preferred hindered amine light stabilizers are bis(1 ,2,2,6,6-pentamethylpiperidyl) sebacate (Tinuvin® 765, Ciba Spezialitatenchemie AG) and the condensate of 1-hydroxy- ethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622).
  • the condensate of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622) is particularly preferred if the titanium content of the product is ⁇ 150 ppm, preferably ⁇ 50 ppm, in particular ⁇ 10 ppm.
  • HALS compounds are preferably used in a concentration of from 0.01 to 5% by weight, particularly preferably from 0.1 to 1% by weight, in particular from 0.15 to 0.3% by weight.
  • a particularly preferred UV stabilization comprises a mixture of a phenolic stabilizer, a benzotriazole and a HALS compound in the preferred amounts described above.
  • the synthesis components (b) and (c) can be varied within relatively wide molar ratios.
  • the reaction can be effected with customary indices, preferably at an index of from 60 to 120, particularly preferably at an index of from 80 to 110.
  • the index is defined by the ratio of the isocyanate groups of component (a) which are used altogether in the reaction to the groups reactive toward isocyanates, i.e.
  • the preparation of the polyurethanes can be effected by the known processes continuously, for example using reaction extruders or the one-shot belt process or the prepolymer process, or batchwise by the prepolymer process.
  • the components (a), (b) and, if appropriate, (c), (d) and/or (e) which are reacted can be mixed with one another in succession or simultaneously, the reaction starting immediately.
  • the synthesis components (a), (b) and, if appropriate, (c), (d) and/or (e) are introduced individually or as a mixture into the extruder, and are reacted, for example at temperatures of from 100 to 280 0 C, preferably from 140 to 250 0 C, and the TPU obtained is extruded, cooled and granulated.
  • the polyurethane composition comprising the tricarboxylic esters has a Shore hardness, measured according to DIN 53505, of less than 80 Shore A, preferably of less than 70 and particularly preferably of less than 65.
  • the Shore hardness, measured according to DIN 53505, is less than 80 Shore A
  • the tensile strengths of the polyurethane composition, measured according to DIN 53504 are greater than 15 MPa, preferably 20 MPa
  • an abrasion resistance, measured according to DIN 53516 is less than 200 mm 3 , preferably less than 150 mm 3 , particularly preferably less than 100 mm 3 .
  • the processing of the polyurethanes according to the invention, preferably TPU, comprising the ester of a tricarboxylic acid is effected by customary methods, such as, for example, injection molding, calandering, powder sintering or extrusion.
  • the polyurethanes according to the invention are usually present in the form of granules or in powder form and are processed by said methods to give products such as films, fibers, and shaped articles, for example coatings, damping elements, seals, bellows, fibers, floors for buildings and transport, cables, cable connectors, cable sheaths, laminates, profiles, belts, rollers, tubes, towing cables, shoe soles, solar modules, plug connectors, claddings in automobiles or wiper blades; automotive parts, fibers, film, cable, tube or shoe being preferred.
  • the polyurethane according to the invention preferably thermoplastic polyurethane is used as the modifier for thermoplastic materials.
  • a chemical and/or physical blowing agent or a gas is added to the polyurethane according to the invention, preferably the thermoplastic polyurethane.
  • foamed products are produced, in addition to the abovementioned articles in particular shoes, handles and damping elements.
  • thermoplastic polyurethane is prepared in the one-shot process, introduced onto a belt system and processed to give granules, preferably by an extruder which is connected directly to the belt system and which melts the polyurethane and extrudes it to give an extrudate which is then comminuted mechanically to give granules or cut off directly, preferably under water, as emerging melt at the die plate.
  • the reaction mixture is likewise synthesized in the one-shot process in a twin-screw extruder to give a polyurethane and granulated directly as described above.
  • the products prepared in this manner also have the advantages of the polyurethane composition which were described at the outset.
  • a hydrolysis stabilizer oligomeric carbodiimide from TMDXI
  • an antioxidant hindered phenol obtained from tetramethylxylene and polyethylene glycol
  • 3.58 g of lubricant partly hydrolyzed montanic ester
  • an antioxidant hindered phenol obtained from tetramethylxylene and polyethylene glycol
  • 3.58 g of lubricant partly hydrolyzed montanic ester
  • TPU 700 g of 4,4'-methyl diisocyanate, 161.97 g of 1 ,4-butanediol and 1000 g of polytetrahydrofuran having a number average molar mass of 1 kg/mol are synthesized in a reaction extruder to give TPU. Furthermore, 18.85 g of an antioxidant (hindered phenol obtained from tetramethylxylene and polyethylene glycol) and 3.77 g of lubricant (partly hydrolyzed montanic ester) are added.
  • the TPU granules thus prepared are converted by injection molding into test specimens, and S2 test bars punched out therefrom (according to DIN 53504) are subjected to mechanical tests.
  • the maximum temperature of the melt in the production of the test specimens is 210 0 C.
  • plasticizer according to the invention is at least comparable in its activity to the commercially available ones in thermoplastic polyurethane, as can be seen here from the direct comparison of Example 9 and Example 10.
  • the plasticizer according to the invention can also be used for the preparation of TPU having low Shore hardnesses.
  • the formulation from Example 1 is presented as a more flexible variant by way of example.
  • methyl 4,4'-diisocyanate MDI
  • 76.92 g of 1 ,4-butanediol 1000 g of a polymer diol having a number average molar mass of 2 kg/mol and obtained from adipic acid, 1 ,2-ethanediol and 1 ,4-butanediol, the latter in the mass ratio 1 :1 , are synthesized in a reaction extruder to give TPU.
  • a hydrolysis stabilizer oligomeric carbodiimide from TMDXI
  • 3.21 g of an antioxidant hindered phenol obtained from tetramethylxylene and polyethylene glycol
  • 3.21 g of lubricant partially hydrolyzed montanic ester
  • 160.2 g of the plasticizer tributyl 2-acetoxy-1 ,2,3-tricarboxylate
  • the TPU granules are converted by injection molding into test specimens, and S2 test bars punched out therefrom (according to DIN 53504) are subjected to mechanical tests.
  • the maximum temperature of the melt in the production of the test specimens is 210 0 C.
  • Example 15 The data applicable are the same as those under Example 13, 248.63 g (15% by weight) of the plasticizer having been added.
  • the data applicable are the same as those under Example 13, 345.92 g (20% by weight) of the plasticizer having been added.
  • the data applicable are the same as those under Example 13, the plasticizer being a commercially available dipropylene glycol dibenzoate and 345.92 g (20% by weight) having been added.
  • a hydrolysis stabilizer oligomeric carbodiimide from TMDXI
  • 3.21 g of an antioxidant hindered phenol obtained from tetramethylxylene and polyethylene glycol
  • 3.21 g of lubricant partially hydrolyzed montanic ester
  • 252.8 g of a plasticizer tributyl 2-acetoxy-1 ,2,3-tricarboxylate
  • the data applicable are the same as those under Example 13, the plasticizer being a commercially available dipropylene glycol dibenzoate and 351.75 g (20% by weight) having been added.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur un polyuréthane, au moins préparé à partir d'un diisocyanate organique (a) et de composés (b) réactifs aux isocyanates, ledit polyuréthane comportant l'ester d'un acide tricarboxylique avec au moins un alcool et tous les groupes acides de l'acide tricarboxylique ayant été estérifiés avec un alcool.
PCT/CN2009/071551 2009-04-29 2009-04-29 Polyuréthane ayant un plastifiant à base de l'ester d'un acide tricarboxylique Ceased WO2010124459A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
PCT/CN2009/071551 WO2010124459A1 (fr) 2009-04-29 2009-04-29 Polyuréthane ayant un plastifiant à base de l'ester d'un acide tricarboxylique
ES10718929.2T ES2449300T3 (es) 2009-04-29 2010-04-26 Poliuretano termoplástico blando basado en éster del ácido tricarboxílico
PCT/EP2010/055490 WO2010125009A1 (fr) 2009-04-29 2010-04-26 Polyuréthane thermoplastique souple à base de l'ester d'un acide tricarboxylique
CN2010800190010A CN102414236B (zh) 2009-04-29 2010-04-26 基于三羧酸的酯的软质热塑性聚氨酯
EP10718929.2A EP2424912B1 (fr) 2009-04-29 2010-04-26 Polyuréthane thermoplastique souple à base de l'ester d'un acide tricarboxylique
KR1020117028565A KR101801687B1 (ko) 2009-04-29 2010-04-26 트리카르복실산 에스테르계 연성 열가소성 폴리우레탄
US13/266,199 US8993690B2 (en) 2009-04-29 2010-04-26 Soft thermoplastic polyurethane based on the ester of a tricarboxylic acid
JP2012507699A JP5654000B2 (ja) 2009-04-29 2010-04-26 トリカルボン酸エステル系の軟質熱可塑性ポリウレタン
BRPI1015965 BRPI1015965B1 (pt) 2009-04-29 2010-04-26 poliuretano termoplástico, processo para produzir um poliuretano termoplástico, produto, e, uso de um éster
US14/600,106 US20150133610A1 (en) 2009-04-29 2015-01-20 Soft thermoplastic polyurethane based on the ester of a tricarboxylic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2009/071551 WO2010124459A1 (fr) 2009-04-29 2009-04-29 Polyuréthane ayant un plastifiant à base de l'ester d'un acide tricarboxylique

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US20110275733A1 (en) * 2010-05-10 2011-11-10 Basf Se Thermoplastic polyurethane comprising, as plasticizer, glycerol esterified with at least one aliphatic carboxylic acid
CN104379672A (zh) * 2012-04-05 2015-02-25 巴斯夫欧洲公司 热塑性聚氨酯组合物及其制备方法
WO2020174040A1 (fr) * 2019-02-28 2020-09-03 Basf Se Mousse particulaire douce en polyuréthane thermoplastique

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JP2002226700A (ja) * 2001-02-01 2002-08-14 Bando Chem Ind Ltd ベルト成形用材料及び伝動ベルト
US20040132899A1 (en) * 2002-01-23 2004-07-08 Sullivan Michael J. Golf ball comprising a plasticized polyurethane
US20050137030A1 (en) * 2003-12-19 2005-06-23 Sullivan Michael J. Plasticized polyurethanes for use in golf balls
US20070049685A1 (en) * 2005-08-25 2007-03-01 Lanxess Deutschland Gmbh Thermoplastic polyurethanes

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JP2002226700A (ja) * 2001-02-01 2002-08-14 Bando Chem Ind Ltd ベルト成形用材料及び伝動ベルト
US20040132899A1 (en) * 2002-01-23 2004-07-08 Sullivan Michael J. Golf ball comprising a plasticized polyurethane
US20050137030A1 (en) * 2003-12-19 2005-06-23 Sullivan Michael J. Plasticized polyurethanes for use in golf balls
US20070049685A1 (en) * 2005-08-25 2007-03-01 Lanxess Deutschland Gmbh Thermoplastic polyurethanes

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110275733A1 (en) * 2010-05-10 2011-11-10 Basf Se Thermoplastic polyurethane comprising, as plasticizer, glycerol esterified with at least one aliphatic carboxylic acid
US9181382B2 (en) * 2010-05-10 2015-11-10 Basf Se Thermoplastic polyurethane comprising, as plasticizer, glycerol esterified with at least one aliphatic carboxylic acid
CN104379672A (zh) * 2012-04-05 2015-02-25 巴斯夫欧洲公司 热塑性聚氨酯组合物及其制备方法
WO2020174040A1 (fr) * 2019-02-28 2020-09-03 Basf Se Mousse particulaire douce en polyuréthane thermoplastique

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