WO2003031506A1 - Melange stabilisant et polyurethanes stabilises - Google Patents

Melange stabilisant et polyurethanes stabilises Download PDF

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Publication number
WO2003031506A1
WO2003031506A1 PCT/EP2002/010799 EP0210799W WO03031506A1 WO 2003031506 A1 WO2003031506 A1 WO 2003031506A1 EP 0210799 W EP0210799 W EP 0210799W WO 03031506 A1 WO03031506 A1 WO 03031506A1
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Prior art keywords
weight
stabilizer mixture
polyurethanes
compound
amount
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PCT/EP2002/010799
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German (de)
English (en)
Inventor
Christa Hackl
Hauke Malz
Thomas Flug
Sylvia Rybicki
Ursula HÜNNIGER
Thomas Brey
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Basf Aktiengesellschaft
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Priority to DE10294585T priority Critical patent/DE10294585D2/de
Publication of WO2003031506A1 publication Critical patent/WO2003031506A1/fr

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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • 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
    • C08K5/49—Phosphorus-containing compounds

Definitions

  • the invention relates to a stabilizer mixture comprising an antioxidant (i), a HALS compound (ii), a UV absorber (iii) and a phosphorus compound (iv), and the use thereof for stabilizing polyurethanes.
  • the invention further relates to polyurethanes containing the above-mentioned stabilizer mixture.
  • TPU thermoplastic polyurethanes
  • thermal and UV stabilizers in order to minimize the decrease in mechanical properties and the discoloration of the products due to oxidative damage.
  • UV absorbers which absorb high-energy UV light and dissipate energy.
  • Common UV absorbers that are used in technology include e.g. to the group of cinnamic acid esters, diphenylcyanoacrylates, diarylbutadienes and benzotriazoles.
  • HALS hindered amine light stabilizers
  • UV absorbers can be combined with phenolic stabilizers or UV absorbers with HALS compounds, HALS compounds with phenolic stabilizers and also combinations of HALS, UV absorbers and phenolic stabilizers.
  • stabilizers Another problem with stabilizers is their migration behavior, i.e. e.g. their volatility and their tendency to bloom. With the latter there is visible coating of the stabilizer on the surface of the workpiece. The stabilizer is removed from the workpiece and can no longer work. In addition, such coverings often lead to customer complaints due to the visual impairment of the workpiece. This is a problem especially with thick workpieces with a small surface / volume ratio.
  • Volatility of the stabilizers becomes a relevant problem when the surface / volume ratio becomes large.
  • the stabilizers evaporate from the plastic, which is therefore unprotected and damaged by UV light.
  • This so-called “fogging" can be used in special applications e.g. in the interior of automobiles, the volatilizing portion of UV stabilization means that the customer's limit values for the total amount of volatile constituents are exceeded and the plastic is rejected.
  • Polyurethanes are generally constructed from an isocyanate and a polyol, e.g. a polyetherol or a polyesterol and optionally a chain extender, e.g. a low molecular weight diol.
  • the choice of polyol generally plays a crucial role in the stability of the product.
  • polyesterols are oxidatively very stable, but tend to hydrolise. This sensitivity to hydrolysis can be increased by the wrong choice of stabilizers.
  • Polyether oils are hydrolytically stable, but are more sensitive to oxidation.
  • the choice of the hardness of the product also has an influence on the sensitivity to oxidation of the polyurethane. For example, soft polyetherol types are more sensitive to oxidation than hard polyetherol types.
  • a stabilizer mixture it is important for the manageability of a stabilizer mixture that it can be incorporated in different ways in order to be as flexible as possible; For example, it should be possible to meter in the stabilizer as a concentrate in the manufacture of the finished parts, for example in an injection molding and / or extrusion process, ensuring a homogeneous distribution in the product. It should also be possible to use the individual components of the stabilizer mixture to form the reaction mixture in the production of the polyurethane, for example in a belt process or in a reactive extrusion admit. It is important that the material can be worked in quickly and homogeneously, does not stick in the dosing unit, and does not contain any volatile components that lead to problems in workplace hygiene or safety problems such as explosion protection during processing.
  • the object of the invention was therefore to provide a stabilizer mixture for polyurethanes, preferably for thermoplastic polyurethanes, which
  • the object was achieved by a mixture containing an antioxidant, a HALS compound, a UV absorber and a phosphor compound.
  • the invention thus relates to a stabilizer mixture containing
  • Another object is the use of the stabilizer mixture according to the invention for stabilization, preferably for UV stabilization, of compact and cellular polyurethanes, preferably of thermoplastic polyurethanes.
  • This invention also relates to polyurethanes, preferably thermoplastic polyurethanes, which contain the stabilizer mixture according to the invention.
  • the subject of the invention is a process for the production of the polyurethanes according to the invention and their use for the production of molded articles.
  • Substances which inhibit or prevent undesirable oxidative processes in the plastic to be protected are generally suitable as antioxidants, which are component (i) in the stabilizer mixture.
  • antioxidants are commercially available. Phenolic antioxidants are preferably suitable for use in the stabilizer mixture according to the invention.
  • the antioxidants (i), in particular the phenolic antioxidants have a molar mass of greater than 350 g / mol, particularly preferably greater than 700 g / mol. It is also preferred that the molar mass of the antioxidants (i) is less than 5000 g / mol, particularly preferably less than 1500 g / mol. Furthermore, the antioxidants (i) preferably have a melting point of less than 180 ° C., particularly preferably less than 130 ° C. Furthermore, antioxidants which are amorphous or liquid are particularly preferably used. Mixtures of two or more antioxidants can also be used as component (i).
  • Suitable phenolic antioxidants are molecules which contain structure 1 as an active ingredient group.
  • X and Y independently of one another denote a hydrogen atom, straight-chain, branched or cyclic alkyl radicals having 1 to 12 carbon atoms and
  • Z is a covalent bond via which the active substance group is connected to the remaining molecule of the antioxidant (i).
  • Those compounds which contain the radical 2 are preferably used as the phenolic antioxidant (i),
  • phenolic antioxidants which contain active ingredient group 1 are triethylene glycol bis (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate) (Irganox 245, Ciba Specialty Chemicals AG), hexamethylene bis ( 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irgano 259), pentaerythrityl tetrakis (3- (3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl) propionate 5-di-tert) (Irganox 1010), octadecyl-3- (3, 5-di-tert .butyl- 4-hydroxyphenyl) propionate (Irganox ® 1076), N, N'-hexamethylene bis- (3, .butyl-4-hydroxy-hydrocinnamic acid amide) (Irganox ® 1098), phenol, 2,4-d
  • Particularly preferred phenolic antioxidants are Irgano 1010, Irganox ® 245, Irganox ® 259 and stabilizers based on polyetherols.
  • antioxidants (i) can be described by the general formulas 3A and 3B.
  • the preferred stabilizers 3A and 3B accordingly represent mixtures of different compounds which differ only in the size of n.
  • the proportion of the molecules n, n, n 3 to n m is chosen so that the number-average molar mass of the antioxidant mixture corresponds to the molar mass recognized as advantageous.
  • the proportion of the molecules ni, n 2 , n to n m is preferably selected such that the number-average molar mass of the stabilizer 3A and / or 3B is greater than 350 g / mol, particularly preferably> 700 g / mol. It is also preferred that the molar mass of the antioxidants (i) is less than 5000 g / mol, particularly preferably less than 1500 g / mol.
  • antioxidant mixtures are used whose polydispersity Pa is greater than 1, ie their number average molecular weight is smaller than their weight average molecular weight. This is generally fulfilled if the antioxidant consists of a mixture of different molecules of structure 3A or 3B with different n. It can be advantageous if not a single phenolic antioxidant is used, but rather mixtures of phenolic antioxidants are used for stabilization. In principle, all phenolic antioxidants which correspond to the molar mass and melting point conditions described above can be used.
  • Mixtures which contain Irganox 1010 and / or mixtures which contain phenolic antioxidants according to 10 of the general formulas 3A and 3B are particularly preferred.
  • 2, 2 v -methylene-bis- (4-methyl-6th tert.butyl-phenol), 2, 2 '-isobutylidenes-bis- (4, 6 -dimethyl-15 phenol) and 4,4'-butylidenes-bis- (2-tert. butyl-5-methyl-phenol) can be used as preferred antioxidants (i).
  • Sterically hindered amines also called 'hindered amine light stabilizers' (HALS compounds) constitute component (ii) of the
  • HALS hydroxybenzyl sulfate
  • the activity of the HALS compounds is based on their ability to form nitroxyl radicals which intervenes in the mechanism of the oxidation of polymers. HALS are considered to be highly efficient UV stabilizers for most polymers. Accordingly, all sterically hindered amines that are in the
  • HALS compounds are well known and commercially available.
  • Oligomeric hindered amine light stabilizers are generally used as hindered amine light stabilizers. Oligomeric hindered amine light stabilizers mean that the molecular weight of the hindered amine light stabilizers is greater than 400 g / mol. Furthermore, the molar mass of the preferred HALS compounds should not be greater than 10000 g / mol, particularly preferably not greater than 35 5000 g / mol.
  • Preferred HALS compounds (ii) are, for example, those molecules which contain a radical according to general formula 4 as an active ingredient group,
  • X ⁇ X 2 1 2 mean straight-chain, branched or cyclic alkyl radicals having 1 to 12 carbon atoms in the X ⁇ X 2 1 2 are independently hydrogen
  • Ki a hydrogen atom, an alkyl radical with 1 to 14 carbon atoms, an acyl radical with 2 to 18 carbon atoms, an aryl radical with 6 to 15 carbon atoms, an alkoxy radical with 2 to 19 carbon atoms and an aryloxy-carbonyl radical with 7 to 12 Is carbon atoms
  • K is a hydrogen atom or a covalent bond via which the active ingredient group 4 is connected to the remaining molecule of the HALS compound.
  • oligomeric hindered amine light stabilizers (II) are bis- (2, 2, 6, 6-tetramethylpiperidyl) sebacate, bis- (1,2,2,6,6-pentamethylpiperidyl) sebacate (Tinuvin ® 765, Ciba Specialty Chemicals Inc. ), n-butyl-3, 5-di-tert.
  • mixtures of HALS compounds are used as component (ii).
  • a HALS with a molecular weight> 2000 g / mol with an HALS with a molecular weight ⁇ 1000 g / mol.
  • UV absorbers are used as component (iii) in the stabilizer mixture according to the invention.
  • those UV absorbers which can be considered are compounds which absorb UV light in the UV-A and UV-B region of the spectral range. Such compounds are generally known and commercially available.
  • UV absorbers (iii) derivatives of diphenylcyanoacrylates, benzotriazoles, benzophenones and / or derivatives of diarylbutadienes are used as UV absorbers (iii).
  • UV absorbers based on benzotriazoles are used.
  • the UV absorbers (iii) have a molar mass of greater than 300 g / mol, in particular greater than 390 g / mol.
  • the preferably used UV absorbers (iii) should have a molecular weight of not more than 5000 g / mol, particularly preferably of not more than 2000 g / mol.
  • the UV absorbers (iii) contain radicals which contain chemical functionalities which can react with isocyanate groups or OH groups.
  • residues can be, for example, alcohols, primary and secondary amines, acid groups, ester groups, epoxides.
  • Benzotriazole used.
  • benzotriazoles are examples of benzotriazoles.
  • Mixtures of two or more of the UV absorbers (iii) mentioned can preferably also be used as component (iii) of the stabilizer mixture according to the invention.
  • a phosphorus compound is used as component (iv) in the stabilizer mixture according to the invention.
  • a mixture of two or more phosphorus compounds can also be used.
  • organophosphorus compounds of trivalent phosphorus such as, for example, phosphites and phosphonites
  • suitable phosphorus compounds are tri phenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di-stearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite , Di-isodecyl pentaerythritol diphosphite, di- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, t
  • the phosphorus compounds are particularly suitable if they are difficult to hydrolyze, since hydrolysis of a phosphorus compound to the corresponding acid can damage the polyurethane, in particular the polyester urethane. Accordingly, the phosphorus compounds which are particularly difficult to hydrolyze are particularly suitable for polyester urethanes.
  • Examples of such phosphorus compounds are dipropylene glycol phenyl phosphite, tri-isodecyl phosphite, triphenyl monodecyl phosphite, trisisononyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2, 4-di-tert- butylphenyl) 4, 4'-diphenylenediphosphonite and di- (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite or mixtures thereof.
  • the proportion of components (i) to (iv) is generally not limited.
  • the antioxidant (i) in an amount of 10 to 50% by weight, particularly preferably 20 to 40% by weight
  • the HALS compound (ii) in an amount of 10 to 50% by weight. %, particularly preferably from 15 to 40% by weight
  • of the UV absorber (iii) in an amount of 1 to 50% by weight, particularly preferably from 10 to 25% by weight
  • the stabilizer mixture according to the invention can be used to stabilize polyurethanes or to produce stabilized polyurethanes. In general, the use for compact and cellular polyurethanes is possible.
  • the stabilizer mixture according to the invention is preferably used to stabilize elastomeric polyurethane, in particular thermoplastic polyurethane.
  • polyurethanes in particular TPUs
  • polyurethanes preferably TPUs
  • polyurethanes can be reacted with (a) isocyanates with (b) isocyanate-reactive compounds with a molecular weight of 500 to 10,000 and optionally (c) chain extenders with a molecular weight of 50 to 499, optionally in the presence of (d) catalysts and / or (e) customary auxiliaries and / or additives are produced.
  • organic isocyanates for example tri, tetra, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl pentamethylene diisocyanate-1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, l-isocyanato-3, 3, 5-trimethyl-5- isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, l-methyl-2, 4- and / or -2, 6-cyclohexane di
  • polyesterols polyetherols and / or polycarbonate diols, which are usually also summarized under the term "polyols”, with molecular weights of 500 to 8000, preferably 600 to 6000, in particular 800 to 4000, and preferably an average functionality of 1.8 to 2.3, preferably 1.9 to 2.2, in particular 2.
  • chain extenders for example diamines and / or alkanediols with 2 to 10 carbon atoms in the alkylene radical, in particular butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols with 3 to 8 carbon atoms , preferably corresponding oligo- and / or polypropylene glycols, it also being possible to use mixtures of the chain extenders.
  • chain extenders for example diamines and / or alkanediols with 2 to 10 carbon atoms in the alkylene radical, in particular butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa-, hepta-, o
  • Accelerating hydroxyl groups of the structural components (b) and (c) are those known in the prior art and customary tertiary amines, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters , Iron compounds such as, for example, iron (III) acetylacetonate, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like.
  • the catalysts are usually used in amounts of 0.0001 to 0.1 part by weight per 100 parts by weight of polyhydroxy compound (b).
  • auxiliaries and / or additives (e) can also be added to the structural components (a) to ( ⁇ ).
  • blowing agents, surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and pigments if appropriate in addition to the stabilizer mixture according to the invention, further stabilizers, e.g. against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers.
  • component (e) also includes hydrolysis stabilizers such as, for example, polymeric and low-molecular carbodiimides.
  • chain regulators usually with a molecular weight of 31 to 499, can also be used.
  • Such chain regulators are compounds which have only one functional group which is reactive toward isocyanates, such as, for. B. monofunctional alcohols, monofunctional amines and / or monofunctional polyols.
  • a flow behavior in particular with TPUs, can be set in a targeted manner.
  • Chain regulators can generally be used in an amount of 0 to 5, preferably 0.1 to 1 part by weight, based on 100 parts by weight of component b), and by definition fall under component c).
  • the build-up components (b) and (c) can be varied in relatively wide molar ratios.
  • Molar ratios of component (b) to chain extenders (c) of to be used overall have proven successful 10: 1 to 1: 10, in particular from 1: 1 to 1: 4, the hardness of the TPU increasing with increasing content of (c).
  • Chain extenders (c) are also preferably used to produce the TPU.
  • the conversion can be carried out using conventional key figures, preferably a key figure of 60 to 120, particularly preferably a key figure of 80 to 110.
  • the key figure is defined by the ratio of the total isocyanate groups of component (a) used in the reaction to the groups reactive toward isocyanates, ie the active hydrogens, of components (b) and (c). If the index is 100, there is one active hydrogen atom for one isocyanate group of component (a) ' , ie one function of components (b) and (c) which is reactive towards isocyanates. With key figures above 100, there are more isocyanate groups than OH groups.
  • the TPU can be produced continuously using the known processes, for example using reaction extruders or the belt process using one-shot or the prepolymer process, or batchwise using the known prepolymer process.
  • the components (a), (b) and optionally (c), (d) and / or (e) coming into the reaction can be mixed with one another in succession or simultaneously, the reaction commencing immediately.
  • the structural components (a), (b) and optionally (c), (d) and / or (e) are introduced into the extruder individually or as a mixture, e.g. reacted at temperatures of 100 to 280 ° C, preferably 140 to 250 ° C, the TPU obtained is extruded, cooled and granulated.
  • the TPUs produced according to the invention which are usually in the form of granules or in powder form, are processed into the desired films, moldings, rollers, fibers, claddings in automobiles, hoses, cable connectors, bellows, trailing cables, cable sheathing, seals, belts or damping elements usual methods, such as Injection molding or extrusion.
  • components (i) to (iv) are introduced into the polyurethane.
  • the stabilized polyurethanes according to the invention contain the stabilizer mixture according to the invention.
  • the polyurethane to be stabilized generally contains 0.1 to 5% by weight of antioxidant (i), based on the total weight of the polyurethane.
  • the antioxidant (i) is usually used in concentrations of 0.1 to 5% by weight (% by weight), preferably 0.1 to 1% by weight. -%, particularly preferably 0.5 to 1 wt .-%, based on the total weight of the TPU used.
  • the antioxidant (i) is usually used in concentrations of 0.1 to 5% by weight, preferably 0.1 to 1 % By weight, particularly preferably 0.15 to 0.5% by weight, based on the total weight of the TPU.
  • the HALS compounds (ii) are usually used to stabilize polyurethanes in concentrations of 0.1 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.1 to 1% by weight, based on the total weight of the polyurethane.
  • the UV absorbers (iii) are usually used in concentrations of 0.01 to 2% by weight, preferably 0.05 to 1% by weight, particularly preferably 0.15 to 0.25% by weight, based on the total weight of the polyurethane used.
  • the phosphorus compounds (iv) are usually used in concentrations of from 0.01 to 5% by weight, preferably from 0.02 to 0.5% by weight, particularly preferably from 0.05 to 0.25% by weight , based on the total weight of the polyurethane used.
  • an anti-hydrolysis agent is preferably added.
  • Preferred hydrolysis protection agents are polymeric and low molecular weight carbodiimides. Hydrolysis protection agents are generally added in a concentration of 0.05 to 5% by weight, preferably 0.2 to 2% by weight, in particular 0.5 to 1% by weight, based on the total weight of the TPU.
  • the four components (i) to (iv) of the stabilizer mixture can be metered into the raw materials before the synthesis of the polyurethane, preferably if components (i) to (iv) are miscible with the starting materials of the polyurethane.
  • components (i) to (iv) of the polyol component (b) or the isocyanate component (a) can be added.
  • different stabilizer components can be added to different components for the production of the polyurethane.
  • components (i) to (iii) of the polyol component (b) and the stabilizer component (iv) of the isocyanate component (a) can be added.
  • Stabilizer components (i) to (iv) can also be used during the synthesis of the polyurethanes, e.g. of the TPU.
  • the four stabilizer components (i), (ii), (iii) and (iv) can be metered individually into the educt streams of the reactor or, if the TPU is produced via a reaction extrusion process, directly into the extruder. It is particularly advantageous here if the four active ingredient components can be mixed before metering and then metered in as a finished premix.
  • the four components (i) to (iv) of the stabilizer mixture according to the invention can only be processed, e.g. be added to the TPU during an extrusion or injection molding process. It is also particularly advantageous here if the four active ingredient components can be mixed before metering and then metered in as a finished premix.
  • the four components of the stabilization can also be incorporated in a TPU in high concentration. This concentrate is then granulated and added as an additive during the processing of an unstabilized TPU.
  • the process according to the invention for the production of stabilized polyurethanes thus comprises the implementation of
  • polyisocyanates with b) compounds with at least two hydrogen atoms reactive towards isocyanates and c) optionally chain extenders, d) optionally catalysts and e) optionally additives,
  • a phenolic antioxidant (i), a HALS compound (ii), a UV absorber (iii) and a phosphorus compound (iv) one or more of components a) to e) or that from the reaction of components a ) to e) resulting polyurethane are added, the addition of the compounds (i) to (iv) can be carried out separately or in a mixture.
  • thermoplastic polyurethanes are preferably used for the production of molded articles, preferably foils, shoe soles, rollers, fibers, linings in automobiles, wiper blades, hoses, cable plugs, bellows, trailing cables, cable jackets, seals, belts or damping elements, where these have the advantages described at the beginning.
  • UV tests according to DIN 75 202 were carried out with an atlas
  • the yellowness indices were determined with a colorimeter
  • Irganox ® and Tinuvin ® are trade names of Ciba Specialty Chemicals Lampertheim GmbH.
  • Naugard ® is a trade name of Uniroyal Chemical.
  • Uvinul ® is a trade name of BASF Aktiengesellschaft
  • Table 1 Overview of the stabilizer content of the test samples. All products additionally contain the hydrolysis protection additive Elastostab H01 ® (Elastogran GmbH)
  • Example 2 The spray plates from Example 1 were irradiated in accordance with DIN 75202 or in a QUV test device (UVA fluorescent lamp UVA-340). The yellowness index of the sample was then measured. The results are summarized in Table 2. If the yellowness indices of sample 1.1 (0 sample) and the further comparison samples are compared with those of the samples stabilized according to the invention, the effectiveness of the stabilizer mixtures according to the invention becomes clear.
  • Example 3 The spray plates from Example 3 were irradiated in accordance with DIN 75 202 or in a QUV test device (UVA fluorescent lamp UVA-340). The yellowness index of the sample was then measured. The results are summarized in Table 4. If the yellowness indices of sample 3.1 (0 sample) and those of the other comparison tests are compared with those of the stabilized samples, the effectiveness of the stabilizer mixtures according to the invention becomes clear.
  • ⁇ Stabilizer produced in this way is amorphous and liquid.
  • a mixture was prepared in a ratio of 2: 1: 1: 1 from the stabilizer prepared in Example 5 and also from Tinuvin ® 40 765, Tinuvin ® 571 and Naugard ® P.
  • the individual components were weighed into a screw cap glass and then heated to 80 ° C. After the heating-up phase, the components were mixed homogeneously for 30 seconds using a KPG stirrer. The product obtained in this way was so low-viscosity at 80 ° C. that it was no problem with the corresponding pumps could be promoted. Even after cooling to room temperature, the mixture is optically homogeneous, so that there is no segregation in this system, which is a great technological advantage since the mixture can be metered into the polymer via only one metering unit.
  • PTHF 1000 polyether MW: 1000 g / mol, BASF Aktiengesellschaft
  • the stabilizer mixture and 31 g of 1,4-butanediol were then added with stirring. After the solution had subsequently been heated to 85 ° C., 150 g of 4,4 , -MDI were added and the mixture was stirred until the solution was homogeneous. The reaction mass was then poured into a flat dish, which was then stored on a hot table heated to 125 ° C. for 10 minutes. The casting plate thus obtained was then heated in a heating cabinet at 100 ° C. for 24 h. The rind was then granulated in a mill. The concentrate thus produced can be metered in to stabilize TPU during processing.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un mélange stabilisant contenant un antioxydant (i), un composé HALS (hindered amine light stabilizer / stabilisant lumineux à amine à encombrement stérique) (ii), un absorbant U.V. (iii) et un composé de phosphore (iv), et des polyuréthanes comprenant ledit mélange stabilisant.
PCT/EP2002/010799 2001-10-02 2002-09-26 Melange stabilisant et polyurethanes stabilises WO2003031506A1 (fr)

Priority Applications (1)

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DE10148702.9 2001-10-02

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1529814A2 (fr) * 2003-10-09 2005-05-11 BASF Aktiengesellschaft Polymères thermoplastiques, de préférence des polyuréthanes thermoplastiques contenant un plastifiant
WO2014057057A1 (fr) 2012-10-10 2014-04-17 Basf Se Dispositif anti-chute en polyuréthane thermoplastique
EP1730097B1 (fr) 2004-02-27 2016-06-22 SI Group, Inc. Préparation d'esters d'acide hydroxyphenylcarboxylique à encombrement stérique

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA06000426A (es) * 2003-07-11 2006-03-17 Eastman Chem Co Adicion de absorbedores uv al proceso de pet para rendimiento maximo.
DE10336883A1 (de) * 2003-08-08 2005-03-10 Basf Ag Kunststoff, insbesondere Polyurethan enthaltend ein sterisch gehindertes, verestertes Amin
MY139524A (en) * 2004-06-30 2009-10-30 Ciba Holding Inc Stabilization of polyether polyol, polyester polyol or polyurethane compositions
CN109100383A (zh) * 2018-08-31 2018-12-28 深圳市必发达科技有限公司 一种RoHS检测用标准样品

Citations (6)

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EP0214292A1 (fr) * 1985-03-04 1987-03-18 Kao Corporation Composition de stabilisation de polyurethane
DE3725926A1 (de) * 1987-08-05 1989-02-16 Basf Ag Gemisch zum stabilisieren von polyurethanen
US4925888A (en) * 1987-10-21 1990-05-15 Basf Aktiengesellschaft Mixture for stabilizing polyurethanes
EP0430650A1 (fr) * 1989-11-28 1991-06-05 Hoechst Celanese Corporation Compositions à moules de nylon présentant une protection améliorée contre la dégradation par la lumière ultraviolette
DE19806846A1 (de) * 1997-02-21 1998-08-27 Ciba Geigy Ag Stabilisatorengemisch für organische Materialien
EP0992533A1 (fr) * 1998-10-09 2000-04-12 Basf Aktiengesellschaft Produits polyisocyanate-polyaddition contenant des colorants liés par liaison covalante et stabilisateurs

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0214292A1 (fr) * 1985-03-04 1987-03-18 Kao Corporation Composition de stabilisation de polyurethane
DE3725926A1 (de) * 1987-08-05 1989-02-16 Basf Ag Gemisch zum stabilisieren von polyurethanen
US4925888A (en) * 1987-10-21 1990-05-15 Basf Aktiengesellschaft Mixture for stabilizing polyurethanes
EP0430650A1 (fr) * 1989-11-28 1991-06-05 Hoechst Celanese Corporation Compositions à moules de nylon présentant une protection améliorée contre la dégradation par la lumière ultraviolette
DE19806846A1 (de) * 1997-02-21 1998-08-27 Ciba Geigy Ag Stabilisatorengemisch für organische Materialien
EP0992533A1 (fr) * 1998-10-09 2000-04-12 Basf Aktiengesellschaft Produits polyisocyanate-polyaddition contenant des colorants liés par liaison covalante et stabilisateurs

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1529814A2 (fr) * 2003-10-09 2005-05-11 BASF Aktiengesellschaft Polymères thermoplastiques, de préférence des polyuréthanes thermoplastiques contenant un plastifiant
EP1529814A3 (fr) * 2003-10-09 2006-04-05 BASF Aktiengesellschaft Polymères thermoplastiques, de préférence des polyuréthanes thermoplastiques contenant un plastifiant
EP1730097B1 (fr) 2004-02-27 2016-06-22 SI Group, Inc. Préparation d'esters d'acide hydroxyphenylcarboxylique à encombrement stérique
EP1730097B2 (fr) † 2004-02-27 2019-07-24 SI Group, Inc. Préparation d'esters d'acide hydroxyphenylcarboxylique à encombrement stérique
WO2014057057A1 (fr) 2012-10-10 2014-04-17 Basf Se Dispositif anti-chute en polyuréthane thermoplastique

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DE10148702A1 (de) 2003-04-10

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