EP1117724A1 - Body add-on parts based on thermoplastic polyketones - Google Patents

Body add-on parts based on thermoplastic polyketones

Info

Publication number
EP1117724A1
EP1117724A1 EP99948854A EP99948854A EP1117724A1 EP 1117724 A1 EP1117724 A1 EP 1117724A1 EP 99948854 A EP99948854 A EP 99948854A EP 99948854 A EP99948854 A EP 99948854A EP 1117724 A1 EP1117724 A1 EP 1117724A1
Authority
EP
European Patent Office
Prior art keywords
thermoplastic
polyketones
parts
acid
line
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.)
Withdrawn
Application number
EP99948854A
Other languages
German (de)
French (fr)
Inventor
Matthias Müller
Detlev Joachimi
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.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1117724A1 publication Critical patent/EP1117724A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers

Definitions

  • the invention relates to body attachments based on thermoplastic polyketones and their blends with other polymers, and the use of thermoplastic polyketones for the production of body attachments.
  • plastics in the exterior of modern automobile bodies are increasing more and more.
  • Plastic parts painted in car colors are becoming increasingly important.
  • Automotive plastic add-on parts (automotive plastic add-on parts) allow a considerably greater freedom of design than the use of metal.
  • the use of plastic add-on parts offers enormous cost advantages, especially for large exterior parts of the bodywork, which are greater the smaller the number of pieces of the motor vehicle series.
  • the plastic automotive parts are mostly painted off-line, either at a supplier or in a plastic painting facility at the automobile plant. Attachments painted off-line are mounted on the body at the end of the initial painting line in a completely painted condition.
  • the off-line painting has the advantage of being able to use tailor-made paint structures, which in their
  • in-line or on-line painting In order to overcome the disadvantages of off-line painting, there is the possibility of introducing plastic add-on parts into the body painting process and partially or completely coating them in the painting process of the body. With this type of Integration of the plastic add-on part in the painting process of the body is referred to as in-line or on-line painting.
  • plastic add-on parts are introduced into the primary painting line after the priming (for example: cathodic electro-dip painting) and before or after the filler application.
  • the plastic add-on part must optionally be paintable using electrostatic application processes. This is achieved by using electrically conductive plastics or with, for example, an off-line painted primer.
  • the plastic of the plastic component must withstand temperatures of up to 160 ° C for some time (e.g. 30 minutes) without damage.
  • the disadvantage of the in-line method is that separate cleaning of the plastic add-on parts is necessary.
  • the introduction of the plastic add-on parts after the primer into the painting line poses a risk of contamination.
  • thermoplastics for example glass fibers, talc, kaolin, wollastonite
  • incorporation of impact modifiers increases the heat resistance and reduces the coefficient of thermal expansion, but leads to a loss of toughness at low temperatures.
  • impact modifiers for example
  • PPO / PA polyphenylene oxide / polyamide blends
  • fenders that are painted using the in-line or on-line process.
  • Disadvantages of PPO / PA blends are deficits in low-temperature toughness and high water absorption. The water absorption leads to dimensional changes and influences the properties of the applied coating.
  • Another disadvantage is that PPO / PA blends are composed of an amorphous and a partially crystalline thermoplastic, which are not readily miscible. In order to achieve a sufficient phase connection with reproducible phase morphology and to avoid segregation phenomena, the use of compatibilizers is necessary. In addition to an increase in costs, the chemical and physical complexity of the PPO / PA blends also leads to production conditions
  • thermoplastic polyketones and their blends with other thermoplastics show an ideal property profile for in-line and on-line paintable automotive add-on parts.
  • Polyketones are semicrystalline thermoplastics, which with the high temperatures occurring in-line and on-line
  • Polyketones and their blends with other thermoplastics are characterized by excellent impact strength at low temperatures and hardly absorb any moisture from the environment. They are stable against hydrolysis and show a very good fuel resistance and barrier. They show very good reset behavior. Polyketones can be flame-retarded without halogen and phosphorus. They are also based on very inexpensive raw materials such as Carbon monoxide, ethylene and propylene.
  • polyketones and their blends with other thermoplastics have an excellent combination of properties of heat resistance and low-temperature impact strength.
  • they can be processed using conventional plastics processing techniques such as Process injection molding, extrusion, thermoforming and deep drawing, pressing, welding and stamping and combinations of the techniques.
  • the invention relates to vehicle attachments or body attachments based on thermoplastic polyketones.
  • Vehicle attachments based on thermoplastic polyketones and, if applicable, their blends with other thermoplastics are preferably suitable for in-line and online painting. In particular, these vehicle attachments can be used for on-line painting.
  • thermoplastic polyketones can be mixed with other thermoplastics, thermoplastic elastomers or mixtures thereof as blend partners.
  • This Thermoplastic molding compounds containing thermoplastic polyketones and other blend partners are also ideal for automotive add-on parts.
  • the invention further relates to the use of thermoplastic polyketones and their blends with other thermoplastics, thermoplastic elastomers and their mixture for the production of automotive add-on parts or body add-on parts.
  • thermoplastic polyketones have a linear alternating structure and essentially contain 1 molecule of carbon monoxide per molecule of unsaturated hydrocarbon.
  • Suitable ethylenically unsaturated hydrocarbons as monomers for the construction of the polyketone polymer have up to 20 carbon atoms, preferably up to 10 carbon atoms and are aliphatic such as ethylene and other olefins, e.g. Propylene, 1-butene, 1-isobutylene, 1-hexene, 1-octene and 1-dodecene, or are arylaliphatic and contain an aryl substituent on one
  • arylaliphatic monomers are styrene, ⁇ -methylstyrene, p-ethylstyrene and m-isopropylstyrene.
  • Preferred polyketones are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated
  • Hydrocarbon with at least 3 carbon atoms especially an ⁇ -olefin such as e.g. Propylene.
  • Terpolymers of at least 2 monomer units are particularly preferred, one of which is ethylene and the other a second hydrocarbon. About 10 to 100 monomer units of the second hydrocarbon are preferably used.
  • the polymer chain of the preferred polyketone is represented by the following formula CO (CH 2 CH 2 ) [C0 (G)] (I)
  • the ratio y: x is not greater than about 0.5.
  • terpolymers are used and the units -CO- (CH 2 CH 2 ) - and -CO- (G) - are statistically distributed over the polymer chain.
  • the preferred ratio of y: x is 0.01 to 0.1.
  • a polyketone or a mixture of polyketones can be used.
  • blending partners include: polyalkylene terephthalates, thermoplastic vinyl (co) polymers, graft polymers (eg ABS rubbers, acrylate rubbers), polyolefins, thermoplastic elastomers such as thermoplastic Polyurethanes, EP (D) M rubbers, polypropylene (PP) / EPDM rubbers, polyphenylene ethers and their mixtures.
  • polyalkylene terephthalates are reaction products made from aromatic dicarboxylic acid or its reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms according to known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-HanserNerlag, Kunststoff 1973).
  • Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, 1,3-ethylene glycol and / or propanediol and / or butanediol-1,4-residues.
  • the preferred polyalkylene terephthalates can contain up to 20 mol% residues of other aromatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, ⁇ aphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates can contain up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to Contain 21 carbon atoms, e.g.
  • the polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acid, e.g. are described in DE-OS 19 00 270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol.
  • polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (eg its dialkyl esters) and ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components, particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.
  • the polyalkylene terephthalates generally have an intrinsic viscosity of approximately 0.4 to 1.5, preferably 0.5 to 1.3, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
  • Thermoplastic polyurethanes in the sense of the invention are built up from linear polyols, mostly polyester or polyether polyols, organic diisocyanates and short-chain diols (chain extenders). To accelerate educational reaction can also be added to catalysts.
  • the molar ratios of the structural components can be varied over a wide range, whereby the properties of the product can be adjusted. Molar ratios of polyols to chain extenders from 1: 1 to 1:12 have proven successful. This results in products in the range from 70 Shore A to 75 Shore D.
  • the build-up of the thermoplastically processable polyurethane elastomers can take place either step by step (prepolymer process) or by the simultaneous reaction of all components in one step (one-shot process).
  • an isocyanate-containing prepolymer is formed from the polyol and the Dusoeyanat, which is reacted with the chain extender in a second step.
  • the TPU can be manufactured continuously or discontinuously.
  • the best known technical manufacturing processes are the belt process and the extruder process.
  • thermoplastically processable polyurethanes are obtainable by implementing the polyurethane-forming components
  • organic diisocyanates A are aliphatic, cycloaliphatic. araliphatic, heteroeyclic and aromatic diisocyanates, as described in Justus Liebigs Annalen der Chemie, 562, pp.75-136.
  • Examples include: aliphatic diisocyanates such as hexamethylene diisocyanate, cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6- cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2,2'-dicyclohexylmethane diisocyanate as well as the corresponding isomer mixtures, aromatic diisocyanates such as 2 , 4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-dipheny
  • 1,5-naphthylene diisocyanate 1,5-naphthylene diisocyanate.
  • the diisocyanates mentioned can be used individually or in the form of mixtures with one another. They can also be used together with up to 15% by weight (based on the total amount of Dusoeyanat) of a polyisocyanate, for example triphenylmethane-4,4 ', 4 "-triisocyanate or polyphenyl-polymethylene-polyisocyanates.
  • Linear hydroxyl-terminated polyols with a molecular weight of 500 to 5000 are used as component B). Due to production, these often contain small amounts of non-linear compounds. One therefore often speaks of "essentially linear polyols". Polyester, polyether, polycarbonate are preferred
  • Suitable polyether diols can be prepared by reacting one or more alkylene oxides with 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains two active hydrogen atoms bonded.
  • alkylene oxides examples include: ethylene oxide, 1,2-propylene oxide, epichlorohydrin and 1, 2-butylene oxide and 2,3-butylene oxide. Ethylene oxide, propylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide are preferably used.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • suitable starter molecules are: water, amino alcohols, such as N-alkyl-diethanolamines, for example N-methyl-diethanolamine, and
  • Diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. If appropriate, mixtures of starter molecules can also be used.
  • Suitable polyether diols are also the hydroxyl-containing polymerization products of tetrahydrofuran.
  • Trifunctional polyethers can also be used in proportions of 0 to 30% by weight, based on the bifunctional polyethers, but at most in such an amount that a thermoplastically processable product is formed.
  • the essentially linear polyether diols have molecular weights of 500 to 5000. They can be used both individually and in the form of mixtures with one another.
  • Suitable polyester diols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols.
  • suitable dicarboxylic acids are: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid,
  • dicarboxylic acids can be used individually or as mixtures, e.g. in the form of a mixture of succinic, glutaric and adipic acids.
  • dicarboxylic acids for the preparation of the polyester diols it may be advantageous to replace the dicarboxylic acids with the corresponding dicarboxylic acid derivatives, such as carboxylic acid diesters with 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides or
  • polyhydric alcohols are glycols with 2 to 10, preferably 2 to 6, carbon atoms, such as ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2, 2-dimethyl-1,3-propanediol, 1,3-propanediol and dipropylene glycol.
  • the polyhydric alcohols can be used alone or, if appropriate, as a mixture with one another.
  • esters of carbonic acid with the Diols mentioned in particular those with 4 to 6 carbon atoms, such as 1,4-butanediol or 1,6-hexanediol, condensation products of hydroxycarboxylic acids, for example hydroxycaproic acid and polymerization products of lactones, for example optionally substituted caprolactones.
  • polyester diols are ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-1,4-butanediol-polyadipates, 1,6-hexanediol-neopentylglycol polyadipates, 1,6-hexanediol-1,4 - Butanediol polyadipate and poly-caprolactone.
  • the polyester diols have molecular weights of 500 to 5000 and can be used individually or in the form of mixtures with one another.
  • Chain extenders C) used are diols or diamines with a molecular weight of 60 to 500, preferably aliphatic diols with 2 to 14 carbon atoms, such as e.g. Ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol.
  • diesters of terephthalic acid with glycols having 2 to 4 carbon atoms such as e.g. Terephthalic acid bis-ethylene glycol or terephthalic acid bis-l, 4-butanediol, hydroxyalkylene ether of hydroquinone, such as e.g.
  • 1,4-di (-hydroxyethyl) hydroquinone ethoxylated bisphenols
  • (cyclo) aliphatic diamines e.g. Isophoronediamine, ethylenediamine, 1,2-propylene-diamine, 1,3-propylene-diamine, N-methyl-propylene-1,3-diamine, N, N'-dimethyl-ethylenediamine and aromatic diamines such as e.g. 2,4-tolylene diamine and 2,6-tolylene diamine, 3,5-
  • thermoplastic polyurethanes can be produced in small quantities, for example as chain terminators or mold release aids.
  • examples include alcohols such as octanol and stearyl alcohol or amines such as butylamine and stearylamine.
  • the structural components if appropriate in the presence of catalysts, auxiliaries and additives, can be reacted in such amounts that the equivalence ratio of NCO groups to the sum of the NCO-reactive groups, in particular the OH groups of the low molecular weight diols / Triols and polyols 0.9: 1.0 to 1.2: 1.0, preferably 0.95: 1.0 to 1.10: 1.0.
  • Suitable catalysts are the conventional tertiary amines known and known in the art, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo-
  • organic metal compounds such as titanium acid esters, iron compounds, tin compounds, e.g. Tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or the like.
  • Preferred catalysts are organic metal compounds, in particular titanium acid esters, iron or tin compounds.
  • thermoplastic polyurethane or a mixture of thermoplastic polyurethanes can be used.
  • the TPU can continuously in the so-called extruder process, e.g. in a multi-screw extruder.
  • the dosage of the TPU components A), B) and C) can be carried out simultaneously, i.e. experienced in one-shot-V, or one after the other, i.e. by a prepolymer process.
  • the prepolymer can either be introduced batchwise or else be produced continuously in part of the extruder or in a separate upstream prepolymer unit.
  • Polyolefins are, for example, polyethylene, polypropylene, poly-1-baten and poly-methylpentene, which can still contain small amounts of non-conjugated dienes in copolymerized form. These polymers are known and are used in Roempp's chemistry Lexicon, 8th edition 1987, Vol. 5, p. 3307 and described in the literature cited therein.
  • thermoplastic vinyl (co) polymers are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles),
  • (Meth) acrylic acid (C r C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids are suitable.
  • (Co) polymers of are preferably suitable
  • Dl 50 to 99 preferably 60 to 80 parts by weight of vinyl aromatics and / or nucleus-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C, -C 4 ) alkyl esters such as eg methyl methacrylate, ethyl methacrylate), and
  • Nitriles such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (C, - C g ) alkyl esters (such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or unsaturated carboxylic acids (such as maleic acid) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic anhydride and N-phenyl-maleimide).
  • C, - C g alkyl esters
  • unsaturated carboxylic acids such as maleic acid
  • derivatives such as anhydrides and imides
  • the (co) polymers are resinous, thermoplastic and rubber-free.
  • Copolymers of D.l styrene and D.2 acrylonitrile are particularly preferred.
  • the (co) polymers are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
  • One or more graft polymers of are suitable as graft polymers
  • E.2 95 to 5, preferably 70 to 20% by weight of one or more graft bases with glass transition temperatures ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -20 ° C.
  • the graft base E.2 generally has an average particle size (d 50 value) of 0.05 to 5 ⁇ m.
  • Monomers E.1 are preferably mixtures of
  • El.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C, -C 8 ) alkyl esters (such as methyl methacrylate, methyl acrylate, n-butyl acrylate, t-butyl acrylate ) and or
  • Derivatives such as anhydrides and imides
  • unsaturated carboxylic acids e.g. maleic anhydride and N-phenyl-maleimide
  • Preferred monomers E.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers E.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride, methyl acrylate and methyl methacrylate.
  • Particularly preferred monomers are E.1.1 styrene and E.1.2 acrylonitrile.
  • Graft bases E.2 suitable for the graft polymers are, for example, diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and, if appropriate, diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
  • Preferred graft bases E.2 are diene rubbers (for example based on butadiene, isoprene etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to El .1 and E.1.2), with the proviso that the glass transition temperature of component E.2 below ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferred
  • Pure polybutadiene rubber is particularly preferred.
  • Particularly preferred polymers are e.g. ABS polymers (emulsion,
  • the graft polymers are obtained by radical polymerization, e.g. prepared by emulsion, suspension, solution or bulk polymerization, preferably by emulsion polymerization.
  • Suitable acrylate rubbers according to E.2 are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on E.2, of other polymerizable, ethylenically unsaturated monomers.
  • the preferred poly Merizable acrylic acid esters include C 1 -C 8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen C 1 -C 8 alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
  • Monomers with more than one polymerizable double bond can be copolymerized for crosslinking.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as e.g. Ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, e.g. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers trialyll cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes.
  • the amount of crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2,% by weight, based on the graft base E.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base E.2 are, for. B. acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl
  • Graft base E.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • graft bases according to E.2 are silicone rubbers with graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
  • the gel content of the graft base E.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
  • the average particle size d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).
  • Polyphenylene ethers in the sense of the present invention are described, for example, in EP-A 164 767.
  • Fillers and reinforcing materials can be any suitable fillers and reinforcing materials, especially mineral fillers.
  • Polyketones or polyketone blends are added.
  • fillers and reinforcing materials e.g. Kaolin, talc, wollastonite, glass fibers (including long glass and continuous glass fibers and glass fabrics and glass mats), glass balls, calcium carbonate, carbon fibers, aramid fibers or mica, natural fibers or mixtures thereof can be used.
  • the fillers are usually used in an amount of up to 50% by weight, preferably 5 to 30% by weight, based on the mixture as a whole.
  • the molding compositions made of polyketone and polyketone blends can contain conventional additives such as lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers and dyes and pigments.
  • Graphite, conductive polymers, metal fibers and other conventional additives to increase the conductivity can be added.
  • the motor vehicle add-on parts or exterior parts of the body made of polyketone or polyketone blends are produced by conventional plastic processing techniques such as injection molding, extrusion, thermoforming, deep drawing, pressing, welding, embossing, sintering, blow molding, gas injection technology or a combination of these techniques.
  • the polyketone is optionally mixed with the blend partner (s) and, if appropriate, with customary fillers, reinforcing materials and / or additives in a known manner and either directly to produce a semi-finished product (for example plates, foils, profiles) or the invention Shaped parts (automotive add-on part) used with conventional plastic processing techniques or at elevated temperatures, preferably 200-350 ° C, in conventional units such as
  • Extruders internal kneaders, twin-screw extruders melt-compounded into thermoplastic molding compounds and then granulated, for example.
  • the granulate made of polyketone or polyketone blends is processed further using conventional plastic processing techniques, as already enumerated, to give semi-finished products (for example plates, foils, profiles) or the molded parts according to the invention (vehicle attachments).
  • the semifinished products are further processed by conventional techniques such as thermoforming to the motor vehicle add-on parts according to the invention.
  • the motor vehicle add-on parts made of polyketone or polyketone blends according to the invention can also be combined with other materials such as metal or plastic.
  • the Lacquer layers are located directly on the molding compounds made of polyketone or polyketone blends and / or on the materials used in the composite.
  • Blends or the semi-finished products made of polyketone or polyketone blends can also be produced using conventional techniques for connecting and joining together several components or parts such as, for example, coextrusion, film injection molding, sandwich injection molding, back pressing, back embossing, overmolding of inserts, multi-component injection molding, welding , Pressing, gluing, melting, screwing or
  • Brackets in combination with other materials or themselves can be used for the production of automotive add-on parts.
  • Fender, bumper, rear wall door, trunk lid, side door trim, bonnet, car roof, radiator grille, exterior mirrors are preferably mentioned as vehicle attachments.
  • ABS graft rubber
  • Particle diameter dso of 420 nm and a gel content of 85% by weight produced graft rubber with a rubber content of 50% by weight and 50% by weight of a graft shell built up by graft polymerization of a mixture of 27% by weight of acrylonitrile and 73% by weight . Parts styrene.
  • the polyketone and the rubber were mixed in a ZSK32 extruder at 220-240 ° C.
  • Thermoplastic polyurethane (TPU) Desmopan ® 385, Bayer AG, Leverkusen, Germany
  • the polyketone and the TPU were mixed in a ZSK 32/1 extruder at 220 to 240 ° C.
  • the moldings required for the tests are produced on an Arburg 320-210-500 injection molding machine at the melt and mold temperatures recommended by the thermoplastic manufacturers.
  • the dynamic mechanical measurement of the complex thrust module is measured in the torsional vibration test depending on the temperature with a measuring frequency of 1 Hz on 80 * 10 * 4 mm 3 test bars with an RDS II device from Rheometrics.
  • the thrust module G ' makes a statement about the rigidity and serves as a measure of the heat resistance and dimensional stability.
  • a thrust module G 'of approx. 80 - 100 MPa at the appropriate paint baking temperature is considered sufficient to be able to paint vehicle attachments without deformation.
  • the behavior under impact stress in the biaxial puncture test is investigated on 60 mm round disks with a thickness of 3 mm according to ISO 6603-2.
  • the modulus of elasticity is measured in the tensile test according to ISO 527.2 on shoulder bars.
  • the surface of the molded parts was assessed visually.
  • Polyketone and PBT are semi-crystalline thermoplastics. Although the glass transition temperature of polyketone is around 12 ° C below room temperature, the stiffness (shear modulus) at high temperatures is much higher than that of PBT and other comparable semi-crystalline thermoplastics. In contrast to other typical semi-crystalline thermoplastics, polyketon therefore has sufficient heat resistance for in-line and on-line paintable automotive add-on parts. Compared to PBT and PPO / PA blends, polyketone with a toughness / brittle transition of approx. -30 ° C shows a significantly better low-temperature impact strength.
  • the impact-modified PC / PBT blend is a typical blend system for automotive paintable parts that can be painted off-line, has very good low-temperature toughness but is completely inadequate in heat resistance for in-line or on-line painting.
  • the examples polyketone / ABS and polyketone / TPU show that the favorable properties of polyketones for in-line and on-line paintable attachments are retained even in polyketone blends.

Abstract

The invention relates to body add-on parts based on thermoplastic polyketones and blends thereof with other polymers. The invention also relates to the use of thermoplastic polyketones for producing body add-on parts.

Description

Karosserie- Anbauteile auf Basis thermoplastischer PolyketoneBody attachments based on thermoplastic polyketones
Die Erfindung betrifft Karosserie- Anbauteile auf Basis thermoplastischer Polyketone und deren Blends mit anderen Polymeren sowie die Verwendung von thermoplastischen Polyketonen zur Herstellung von Karosserie-Anbauteilen.The invention relates to body attachments based on thermoplastic polyketones and their blends with other polymers, and the use of thermoplastic polyketones for the production of body attachments.
Aus Gestaltungs- und Kostengründen nimmt der Einsatz von Kunststoffen im Außenbereich moderner Automobilkarossen immer mehr zu. Wagenfarbig lackierte Kunststoffanbauteile gewinnen dabei zunehmend an Bedeutung. Kfz-Kunststoffan- bauteile (Kraftfahrzeug-Kunststoffanbauteile) ermöglichen gegenüber dem Einsatz von Metall eine wesentlich größere Designfreiheit. Der Einsatz von Kunststoffanbauteilen bietet insbesondere bei großflächigen Karosserieaußenteilen enorme Kostenvorteile, die um so größer ausfallen, je kleiner die Stückzahl der Kfz-Serie ist.For design and cost reasons, the use of plastics in the exterior of modern automobile bodies is increasing more and more. Plastic parts painted in car colors are becoming increasingly important. Automotive plastic add-on parts (automotive plastic add-on parts) allow a considerably greater freedom of design than the use of metal. The use of plastic add-on parts offers enormous cost advantages, especially for large exterior parts of the bodywork, which are greater the smaller the number of pieces of the motor vehicle series.
Die Lackierung von Kfz-Kunststoffanbauteilen erfolgt überwiegend off-line, entweder bei einem Zulieferanten oder in einer Kunststofflackieranlage des Automobilwerkes. Off-line lackierte Anbauteile werden in komplett lackiertem Zustand am Ende der Erstlackierungsstraße an die Karosse montiert. Die off-line Lackierung hat den Vorteil, maßgeschneiderte Lackaufbauten einsetzen zu können, welche in ihrenThe plastic automotive parts are mostly painted off-line, either at a supplier or in a plastic painting facility at the automobile plant. Attachments painted off-line are mounted on the body at the end of the initial painting line in a completely painted condition. The off-line painting has the advantage of being able to use tailor-made paint structures, which in their
Eigenschaften spezifisch auf den Kunststoff und den Anwendungszweck zugeschnitten sind. Die Auswahl der Kunststoffe aus dem Bereich der Thermoplaste ist dabei nahezu unbeschränkt. Nachteile der off-line Lackierung sind jedoch die Möglichkeit von Farbton- und Glanzabweichungen, hohe Lackmaterial-, Investitions- und Betriebskosten, ein hoher Serviceaufwand und eine aufwendige Logistik.Properties are specifically tailored to the plastic and the application. The choice of plastics from the field of thermoplastics is almost unlimited. Disadvantages of off-line painting, however, are the possibility of color and gloss deviations, high paint material, investment and operating costs, high service costs and complex logistics.
Um die Nachteile der off-line-Lackierung zu überwinden, besteht die Möglichkeit, Kunstoffanbauteile in den Karosserielackierprozeß einzuschleusen und teilweise oder vollständig im Lackierprozeß der Karosserie mitzubeschichten. Bei dieser Art der Integration des Kunststoffanbauteiles in den Lackierprozeß der Karosserie spricht man von in-line bzw. on-line Lackierung.In order to overcome the disadvantages of off-line painting, there is the possibility of introducing plastic add-on parts into the body painting process and partially or completely coating them in the painting process of the body. With this type of Integration of the plastic add-on part in the painting process of the body is referred to as in-line or on-line painting.
Bei der in-line Lackierung werden Kunststoffanbauteile nach der Grundierung (zum Beispiel: kathodische Elektrotauchlackierung) und vor oder nach der Füller-Applikation in die Erstlackierstraße eingeschleust. Das Kunststoffanbauteil muß bei dem in- line Verfahren gegebenenfalls mit elektrostatischen Auftragsverfahren lackierbar sein. Dies wird durch Einsatz elektrisch leitfähiger Kunststoffe oder mit einer zum Beispiel off-line lackierten Leitgrundierung erreicht. Für das Einbrennen des Füllers und der nachfolgenden Lackschichten (im allgemeinen zunächst der Basis- und anschließend der Klarlack) muß der Kunststoff des Kunststoffbauteils Temperaturen bis zu 160°C für einige Zeit (z.B. 30 Minuten) unbeschadet überstehen. Nachteil des in-line Verfahrens ist, daß eine separate Reinigung der Kunststoffanbauteile nötig ist. Zudem birgt das Einschleusen der Kunststoffanbauteile nach der Grundierung in die Lackierstraße eine Verschmutzungsgefahr.With in-line painting, plastic add-on parts are introduced into the primary painting line after the priming (for example: cathodic electro-dip painting) and before or after the filler application. In the in-line process, the plastic add-on part must optionally be paintable using electrostatic application processes. This is achieved by using electrically conductive plastics or with, for example, an off-line painted primer. To burn in the filler and the subsequent layers of paint (generally first the base coat and then the clear coat), the plastic of the plastic component must withstand temperatures of up to 160 ° C for some time (e.g. 30 minutes) without damage. The disadvantage of the in-line method is that separate cleaning of the plastic add-on parts is necessary. In addition, the introduction of the plastic add-on parts after the primer into the painting line poses a risk of contamination.
Von on-line Lackierung spricht man, wenn der Anbau des Kunststoffanbauteiles an die Karosse vor der Grundierung der Karosserie erfolgt und die Kunststoffanbauteile den kompletten Prozeß der Erstlackierung durchlaufen. Bei der on-line Lackierung findet also ein vollständiger Anlagendurchlauf des Kunstoffanbauteiles durch dieOne speaks of on-line painting if the plastic add-on part is attached to the body before the body is primed and the plastic add-on parts go through the complete process of initial painting. With online painting, there is a complete system run of the plastic add-on part through the
Lackierstraßen statt. Bei der on-line Lackierung wird die gesamte Karosserie mit den bereits montierten bzw. auf Montagehaltern mitlaufenden Kunststoffanbauteilen zunächst zum Beispiel in Tauchbädern entfettet, phosphatiert, grundiert (im allgemeinen durch kathodische Tauchlackierung) und die Grundierung bei Temperaturen bis 230°C eingebrannt. Die weitere Lackierung erfolgt wie beim in-line Verfahren beschrieben. Da bei dem on-line Verfahren das Einschleusen der Kunststoffanbauteile zwischen zwei Lackierstationen entfällt, wird die Gefahr der Verschmutzung verhindert. Aufgrund der direkten Montage ergeben sich gegenüber dem off-line und in-line Verfahren deutliche Kostenvorteile. Die on-line Lackierung erfordert den Einsatz von Kunststoffen, die Temperaturen von bis zu 230°C (im allgemeinen 160 bis 210°C) für einige Zeit (z.B. 30 Minuten) standhalten können. On-line geeignete Kunststoffe, die nicht elektrisch leitfähig sind, benötigen gegebenenfalls eine Vorbeschichtung mit einem elektrisch leitfähigen Primer.Painting lines instead. In the case of on-line painting, the entire body is first degreased, phosphated, primed (generally by cathodic dip painting) and the primer is baked at temperatures up to 230 ° C, for example in immersion baths, with the plastic add-on parts already installed or attached to the mounting brackets. Further painting is carried out as described for the in-line process. Since the on-line process eliminates the need to insert the plastic add-on parts between two painting stations, the risk of contamination is prevented. Due to the direct assembly there are significant cost advantages compared to the off-line and in-line process. Online painting requires the use of plastics that can withstand temperatures of up to 230 ° C (generally 160 to 210 ° C) for some time (eg 30 minutes). Suitable on-line Plastics that are not electrically conductive may require a pre-coating with an electrically conductive primer.
Die Vorteile der Integration von Kfz-Anbauteilen in die Karosserielackierung sowohl beim in-line, als auch beim on-line Lackierverfahren sind: Reduktion der Lackierkosten, Vereinfachung der Lackierprozesse, bessere Farbton- und Effektübereinstimmung zur Karosserie und einfachere Logistik.The advantages of integrating automotive add-on parts in the body painting for both in-line and on-line painting processes are: reduction of painting costs, simplification of the painting processes, better color and effect matching to the body and easier logistics.
Die Forderung beim in-line und on-line Verfahren nach einer hohen Wärmeformbe- ständigkeit in Kombination mit einer guten Tieftemperaturzähigkeit verbieten nahezu allen kostengünstigen Thermoplasten die Integration in die Karosserielackierung. Einarbeitung von Verstärkungsstoffen (zum Beispiel Glasfasern, Talkum, Kaolin, Wollastonit) in Thermoplaste erhöht die Wärmeformbeständigkeit und reduziert den Wärmeausdehnungskoeffizienten, führt jedoch zu einem Verlust der Zähigkeit bei niedrigen Temperaturen. Einarbeitung von Schlagzähmodifikatoren (zum BeispielThe requirement in the in-line and on-line process for a high heat resistance in combination with good low-temperature toughness forbid almost all inexpensive thermoplastics to be integrated into the body painting. Incorporation of reinforcing materials (for example glass fibers, talc, kaolin, wollastonite) in thermoplastics increases the heat resistance and reduces the coefficient of thermal expansion, but leads to a loss of toughness at low temperatures. Incorporation of impact modifiers (for example
ABS -Kautschuk, EPDM-Kautschuk) in Thermoplaste verbessert die Tieftemperaturzähigkeit, führt jedoch zu einer unzureichenden Wärmeformbeständigkeit. Aus dem Bereich der Thermoplaste sind lediglich Polyphenylenoxid/Polyamid-Blends (PPO/PA), die die geforderte Wärmeformbeständigkeit aufweisen, von kommerziel- 1er Bedeutung. PPO/PA-Blends werden zur Zeit hauptsächlich für Kotflügel eingesetzt, die nach dem in-line oder on-line Verfahren lackiert werden. Nachteile von PPO/PA-Blends sind jedoch Defizite in der Tieftemperaturzähigkeit und eine hohe Wasseraufnahme. Die Wasseraufnahme führt zu Dimensionsänderungen und beeinflußt die Eigenschaften der aufgebrachten Lackierung. Ein weiterer Nachteil ist, daß sich PPO/PA-Blends aus einem amorphen und einem teilkristallinen Thermoplasten zusammensetzen, die nicht gut mischbar sind. Um eine ausreichende Phasen- anbindung mit reproduzierbarer Phasenmorphologie zu erzielen und um Entmischungsphänomene zu vermeiden, ist der Einsatz von Verträglichkeitsmachern (Compatabilizern) notwendig. Neben einer Kostenerhöhung führt die chemische und physikalische Komplexität der PPO/PA-Blends unter Produktionsbedingungen zuABS rubber, EPDM rubber) in thermoplastics improves low-temperature toughness, but leads to inadequate heat resistance. In the field of thermoplastics, only polyphenylene oxide / polyamide blends (PPO / PA) that have the required heat resistance are of commercial importance. PPO / PA blends are currently mainly used for fenders that are painted using the in-line or on-line process. Disadvantages of PPO / PA blends are deficits in low-temperature toughness and high water absorption. The water absorption leads to dimensional changes and influences the properties of the applied coating. Another disadvantage is that PPO / PA blends are composed of an amorphous and a partially crystalline thermoplastic, which are not readily miscible. In order to achieve a sufficient phase connection with reproducible phase morphology and to avoid segregation phenomena, the use of compatibilizers is necessary. In addition to an increase in costs, the chemical and physical complexity of the PPO / PA blends also leads to production conditions
Problemen bei der Sicherstellung einer gleichbleibenden Produktqualität. Es wurde nun gefunden, daß thermoplastische Polyketone und deren Blends mit anderen Thermoplasten ein ideales Eigenschaftsprofil für in-line und on-line lackierbare Kfz-Anbauteile zeigen. Bei Polyketonen handelt es sich um teilkristalline Thermoplaste, die bei den auftretenden hohen Temperaturen des in-line und on-lineProblems in ensuring a constant product quality. It has now been found that thermoplastic polyketones and their blends with other thermoplastics show an ideal property profile for in-line and on-line paintable automotive add-on parts. Polyketones are semicrystalline thermoplastics, which with the high temperatures occurring in-line and on-line
Lackierverfahrens eine ausreichende Steifigkeit, Wärmeformbeständigkeit und Dimensionsstabilität aufweisen. Polyketone und deren Blends mit anderen Thermoplasten zeichnen sich durch eine hervorragende Schlagzähigkeit bei tiefen Temperaturen aus und nehmen kaum Feuchtigkeit aus der Umgebung auf. Sie sind stabil gegen Hydrolyse und zeigen eine sehr gute Treibstoffbeständigkeit und -barriere. Sie zeigen sehr gutes Rückstellverhalten. Polyketone lassen sich halogen- und phosphorfrei flammschützen. Sie basieren außerdem auf sehr preiswerten Rohstoffen wie z.B. Kohlenmonoxid, Ethylen und Propylen.Painting process have sufficient rigidity, heat resistance and dimensional stability. Polyketones and their blends with other thermoplastics are characterized by excellent impact strength at low temperatures and hardly absorb any moisture from the environment. They are stable against hydrolysis and show a very good fuel resistance and barrier. They show very good reset behavior. Polyketones can be flame-retarded without halogen and phosphorus. They are also based on very inexpensive raw materials such as Carbon monoxide, ethylene and propylene.
Insbesondere weisen Polyketone und deren Blends mit anderen Thermoplasten eine ausgezeichnete Eigenschaftskombination aus Wärmeformbeständigkeit und Tieftemperatur-Schlagzähigkeit auf. Außerdem lassen sie sich mit üblichen Kunststoffverarbeitungstechniken wie z.B. Spritzguß, Extrusion, Thermoformen und Tiefziehen, Pressen, Schweißen und Prägen und Kombinationen der Techniken verarbeiten.In particular, polyketones and their blends with other thermoplastics have an excellent combination of properties of heat resistance and low-temperature impact strength. In addition, they can be processed using conventional plastics processing techniques such as Process injection molding, extrusion, thermoforming and deep drawing, pressing, welding and stamping and combinations of the techniques.
Gegenstand der Erfindung sind Kfz-Anbauteile bzw. Karosserie- Anbauteile auf Basis thermoplastischer Polyketone.The invention relates to vehicle attachments or body attachments based on thermoplastic polyketones.
Kfz-Anbauteile auf Basis thermoplastischer Polyketone und gegebenenfalls deren Blends mit anderen Thermoplasten sind vorzugsweise geeignet für in-line und online Lackierung. Insbesondere sind diese Kfz-Anbauteile zur on-line-Lackierung einsetzbar.Vehicle attachments based on thermoplastic polyketones and, if applicable, their blends with other thermoplastics are preferably suitable for in-line and online painting. In particular, these vehicle attachments can be used for on-line painting.
Die thermoplastischen Polyketone können mit anderen Thermoplasten, thermoplasti- sehen Elastomeren oder deren Mischungen als Blendpartner gemischt werden. Diese thermoplastischen Formmassen, enthaltend thermoplastische Polyketone und andere Blendpartner, eignen sich ebenfalls ausgezeichnet für Kfz-Anbauteile.The thermoplastic polyketones can be mixed with other thermoplastics, thermoplastic elastomers or mixtures thereof as blend partners. This Thermoplastic molding compounds containing thermoplastic polyketones and other blend partners are also ideal for automotive add-on parts.
Gegenstand der Erfindung ist weiterhin die Verwendung von thermoplastischen Polyketonen und deren Blends mit anderen Thermoplasten, thermoplastischen Elastomeren und deren Mischung zur Herstellung von Kfz-Anbauteilen bzw. Karosserie- Anbauteilen.The invention further relates to the use of thermoplastic polyketones and their blends with other thermoplastics, thermoplastic elastomers and their mixture for the production of automotive add-on parts or body add-on parts.
Die thermoplastischen Polyketone haben eine lineare alternierende Struktur und ent- halten im wesentlichen 1 Molekül Kohlenmonoxid pro Molekül ungesättigtem Kohlenwasserstoff. Geeignete ethylenisch ungesättigte Kohlenwasserstoffe als Mono- mere zum Aufbau des Polyketonpolymeren haben bis zu 20 Kohlenstoffatome, vorzugsweise bis zu 10 Kohlenstoffatome und sind aliphatisch wie beispielsweise Ethylen und andere Olefine, z.B. Propylen, 1 -Buten, 1-Isobutylen, 1 -Hexen, 1-Octen und 1-Dodecen, oder sind arylaliphatisch und enthalten einen Arylsubstituenten an einemThe thermoplastic polyketones have a linear alternating structure and essentially contain 1 molecule of carbon monoxide per molecule of unsaturated hydrocarbon. Suitable ethylenically unsaturated hydrocarbons as monomers for the construction of the polyketone polymer have up to 20 carbon atoms, preferably up to 10 carbon atoms and are aliphatic such as ethylene and other olefins, e.g. Propylene, 1-butene, 1-isobutylene, 1-hexene, 1-octene and 1-dodecene, or are arylaliphatic and contain an aryl substituent on one
Kohlenstoffatom der linearen Kette. Beispielhaft genannt werden für arylaliphatische Monomere Styrol, α-Methylstyrol, p-Ethylstyrol und m-Isopropylstyrol.Carbon atom of the linear chain. Examples of arylaliphatic monomers are styrene, α-methylstyrene, p-ethylstyrene and m-isopropylstyrene.
Bevorzugte Polyketone sind Copolymere aus Kohlenmonoxid und Ethylen oder Ter- polymere aus Kohlenmonoxid, Ethylen und einem zweiten ethylenisch ungesättigtenPreferred polyketones are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated
Kohlenwasserstoff mit wenigstens 3 Kohlenstoffatomen, insbesondere ein α-Olefin wie z.B. Propylen.Hydrocarbon with at least 3 carbon atoms, especially an α-olefin such as e.g. Propylene.
Besonders bevorzugt sind Terpolymere von wenigstens 2 Monomereinheiten, wovon eine Ethylen und die andere ein zweiter Kohlenwasserstoff ist. Vorzugsweise werden von dem zweiten Kohlenwasserstoff ungefähr 10 bis 100 Monomereinheiten eingesetzt.Terpolymers of at least 2 monomer units are particularly preferred, one of which is ethylene and the other a second hydrocarbon. About 10 to 100 monomer units of the second hydrocarbon are preferably used.
Die Polymerkette des bevorzugten Polyketons wird durch die folgende Formel dar- gestellt CO(CH2CH2) [ C0(G)] (I)The polymer chain of the preferred polyketone is represented by the following formula CO (CH 2 CH 2 ) [C0 (G)] (I)
wobeiin which
eine Monomereinheit auf Basis eines ethylenisch ungesättigten Kohlenwasserstoffs mit wenigstens 3 Kohlenstoffatomen, vorzugsweise 3 bis 10 C- Atomen, welche aufgrund der ethylenischen Doppelbindung polymerisiert ist unda monomer unit based on an ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, preferably 3 to 10 carbon atoms, which is polymerized on account of the ethylenic double bond and
das Verhältnis y:x nicht größer als ungefähr 0,5 ist.the ratio y: x is not greater than about 0.5.
y = 0 für Copolymere aus Kohlenmonoxid und Ethylen.y = 0 for copolymers of carbon monoxide and ethylene.
Falls y von 0 verschieden ist, werden Terpolymere eingesetzt und die Einheiten -CO-(CH2CH2)- und -CO-(G)- sind statistisch über die Polymerkette verteilt.If y is different from 0, terpolymers are used and the units -CO- (CH 2 CH 2 ) - and -CO- (G) - are statistically distributed over the polymer chain.
Das bevorzugte Verhältnis von y:x ist 0,01 bis 0,1.The preferred ratio of y: x is 0.01 to 0.1.
Polyketone mit einem mittleren Molekulargewicht (Zahlenmittel) von ungefähr 1.000 bis 200.000, insbesondere 20.000 bis 90.000, bestimmt durch Gelpermeations- Chromatographie, sind bevorzugt.Polyketones with a number average molecular weight of approximately 1,000 to 200,000, in particular 20,000 to 90,000, determined by gel permeation chromatography, are preferred.
Zur weiteren Charakterisierung und zur Herstellung der Polyketone wird auf US-A 5.166.252 verwiesen.For further characterization and for the production of the polyketones, reference is made to US Pat. No. 5,166,252.
Es kann ein Polyketon oder ein Gemisch von Polyketonen eingesetzt werden.A polyketone or a mixture of polyketones can be used.
Als Blendpartner seien beispielsweise genannt: Polyalkylenterephthalate, thermoplastische Vinyl(co)polymere, Pfropfpolymere (z.B. ABS-Kautschuke, Acrylat- kautschuke), Polyolefine, thermoplastische Elastomere wie z.B. thermoplastische Polyurethane, EP(D)M-Kautschuke, Polypropylen (PP)/EPDM-Kautschuke, Poly- phenylenether und deren Mischungen.Examples of blending partners include: polyalkylene terephthalates, thermoplastic vinyl (co) polymers, graft polymers (eg ABS rubbers, acrylate rubbers), polyolefins, thermoplastic elastomers such as thermoplastic Polyurethanes, EP (D) M rubbers, polypropylene (PP) / EPDM rubbers, polyphenylene ethers and their mixtures.
Polyalkylenterephthalate im Sinne der Erfindung sind Reaktionsprodukte aus aroma- tischen Dicarbonsäure oder ihren reaktionsfähigen Derivaten (z.B. Dimethylestern oder Anhydriden) und aliphatischen, cycloaliphatischen oder araliphatisehen Diolen und Mischungen dieser Reaktionsprodukte.For the purposes of the invention, polyalkylene terephthalates are reaction products made from aromatic dicarboxylic acid or its reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
Bevorzugte Polyalkylenterephthalate lassen sich aus Terephthalsäure (oder ihren reaktionsfähigen Derivaten) und aliphatischen oder cycloaliphatischen Diolen mit 2 bis 10 C-Atomen nach bekannten Methoden herstellen (Kunststoff-Handbuch, Bd. VIII, S. 695 FF, Karl-HanserNerlag, München 1973).Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms according to known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-HanserNerlag, Munich 1973).
Bevorzugte Polyalkylenterephthalate enthalten mindestens 80, vorzugsweise 90 Mol.-%, bezogen auf die Dicarbonsäure, Terephthalsäurereste und mindestens 80, vorzugsweise mindestens 90 Mol.-%, bezogen auf die Diolkomponente, Ethylen- glykol- und/oder Propandiol-1,3- und/oder Butandiol-l,4-reste.Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, 1,3-ethylene glycol and / or propanediol and / or butanediol-1,4-residues.
Die bevorzugten Polyalkylenterephthalate können neben Terephthalsäureresten bis zu 20 Mol-% Reste anderer aromatischer Dicarbonsäuren mit 8 bis 14 C-Atomen oder aliphatischer Dicarbonsäuren mit 4 bis 12 C-Atomen enthalten, wie Reste von Phthalsäure, Isophthalsäure, Νaphthalin-2,6-dicarbonsäure, 4,4'-Diphenyldicarbon- säure, Bernstein-, Adipin-, Sebacinsäure, Azelainsäure, Cyclohexandiessigsäure.In addition to terephthalic acid residues, the preferred polyalkylene terephthalates can contain up to 20 mol% residues of other aromatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, Νaphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
Die bevorzugten Polyalkylenterephthalate können neben Ethylen- bzw. Propan- diol-1,3- bzw. Butandiol-l,4-glykolresten bis zu 20 Mol.-% anderer aliphatischer Diole mit 3 bis 12 C-Atomen oder cycloaliphati scher Diole mit 6 bis 21 C-Atomen enthalten, z.B. Reste von Propandiol-1,3, 2-Ethylpropandiol-l,3, Neopentylglykol, Pentan-diol-1,5, Hexandiol-1.6, Cyclohexan-dimethanol-1,4, 3-Methylpentandiol- 2,4, 2-Methylpentandiol-2,4, 2,2,4-Trimethylpentandiol-l,3 und -1 ,5, 2-Ethylhexan- diol-1,3 2,2-Diethylpropandiol-l,3, Hexandiol-2,5, l,4-Di-(ß-hydroxyethoxy)- - o -In addition to ethylene or propanediol-1,3- or butanediol-1,4-glycol residues, the preferred polyalkylene terephthalates can contain up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to Contain 21 carbon atoms, e.g. residues of 1,3-propanediol, 2-propanediol-2, 3, neopentylglycol, pentane-1,5-diol, 1,6-hexanediol, 1,4-cyclohexane-dimethanol, 3-methylpentanediol-2 , 4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1, 3 and -1, 5, 2-ethylhexanediol-1,3, 2,2-diethyl propanediol-1,3, hexanediol-2 , 5, 1, 4-di- (ß-hydroxyethoxy) - - o -
benzol, 2,2-Bis-(4-hydroxycyclohexyl)-propan, 2,4-Dihydroxy-l,l,3,3-tetramethyl- cyclobutan, 2,2-bis-(3-ß-hydroxyethoxyphenyl)-propan und 2,2-bis-(4-hydroxy- propoxyphenyl)-propan (DE-OS 24 07 674, 24 07 776, 27 15 932).benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-l, l, 3,3-tetramethylcyclobutane, 2,2-bis (3-ß-hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxy-propoxyphenyl) propane (DE-OS 24 07 674, 24 07 776, 27 15 932).
Die Polyalkylenterephthalate können durch Einbau relativ kleiner Mengen 3- oder 4- wertiger Alkohole oder 3- oder 4-basischer Carbonsäure, wie sie z.B. in der DE-OS 19 00 270 und der US-PS 3 692 744 beschrieben sind, verzweigt werden. Beispiele für bevorzugte Verzweigungsmittel sind Trimesinsäure, Trimellitsäure, Tri- methylolethan und -propan und Pentaerythrit.The polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acid, e.g. are described in DE-OS 19 00 270 and US Pat. No. 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol.
Es ist ratsam, nicht mehr als 1 Mol.-% des Verzweigungsmittels, bezogen auf die Säurekomponente, zu verwenden.It is advisable not to use more than 1 mol% of the branching agent, based on the acid component.
Besonders bevorzugt sind Polyalkylenterephthalate, die allein aus Terephthalsäure und deren reaktionsfähigen Derivaten (z.B. deren Dialkylestern) und Ethylenglykol und/oder Propandiol-1,3 und/oder Butandiol-1 ,4 hergestellt worden sind (Poly- ethylen- und Polybutylentherephthalat), und Mischungen dieser Polyalkylenterephthalate.Particularly preferred are polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (eg its dialkyl esters) and ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.
Bevorzugte Polyalkylenterephthalate sind auch Copolyester, die aus mindestens zwei der obengenannten Säurekomponenten und/oder aus mindestens zwei der obengenannten Alkoholkomponenten hergestellt sind, besonders bevorzugte Copolyester sind Poly-(ethylenglykol/butandiol- 1 ,4)-terephthalate.Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components, particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.
Die Polyalkylenterephthalate besitzen im allgemeinen eine intrinsische Viskosität von ca. 0,4 bis 1,5, vorzugsweise 0,5 bis 1,3, jeweils gemessen in Phenol/o-Dichlor- benzol (1 : 1 Gew.-Teile) bei 25°C.The polyalkylene terephthalates generally have an intrinsic viscosity of approximately 0.4 to 1.5, preferably 0.5 to 1.3, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
Thermoplastische Polyurethane im Sinne der Erfindung werden aus linearen Polyolen, meist Polyester- oder Polyether-Polyolen, organischen Diisocyanaten und kurzkettigen Diolen (Kettenverlängerern) aufgebaut. Zur Beschleunigung der Bildungs- reaktion können zusätzlich Katalysatoren zugesetzt werden. Die molaren Verhältnisse der Aufbaukomponenten können über einen breiten Bereich variiert werden, woduch sich die Eigenschaften des Produkts einstellen lassen. Bewährt haben sich molare Verhältnisse von Polyolen zu Kettenverlängerern von 1 :1 bis 1 :12. Hierdurch ergeben sich Produkte im Bereich von 70 Shore A bis 75 Shore D. Der Aufbau der thermoplastisch verarbeitbaren Polyurethanelastomeren kann entweder schrittweise (Prepoly- merverfahren) oder durch die gleichzeitige Reaktion aller Komponenten in einer Stufe erfolgen (one-shot- Verfahren). Beim Prepolymerverfahren wird aus dem Polyol und dem Dusoeyanat ein isocyanathaltiges Prepolymer gebildet, das in einem zweiten Schritt mit dem Kettenverlängerer umgesetzt wird. Die TPU können kontinuierlich oder diskontinuierlich hergestellt werden. Die bekanntesten technischen Herstellverfahren sind das Bandverfahren und das Extruderverfahren.Thermoplastic polyurethanes in the sense of the invention are built up from linear polyols, mostly polyester or polyether polyols, organic diisocyanates and short-chain diols (chain extenders). To accelerate educational reaction can also be added to catalysts. The molar ratios of the structural components can be varied over a wide range, whereby the properties of the product can be adjusted. Molar ratios of polyols to chain extenders from 1: 1 to 1:12 have proven successful. This results in products in the range from 70 Shore A to 75 Shore D. The build-up of the thermoplastically processable polyurethane elastomers can take place either step by step (prepolymer process) or by the simultaneous reaction of all components in one step (one-shot process). In the prepolymer process, an isocyanate-containing prepolymer is formed from the polyol and the Dusoeyanat, which is reacted with the chain extender in a second step. The TPU can be manufactured continuously or discontinuously. The best known technical manufacturing processes are the belt process and the extruder process.
Die thermoplastisch verarbeitbaren Polyurethane sind erhältlich durch Umsetzung der polyurethanbildenden KomponentenThe thermoplastically processable polyurethanes are obtainable by implementing the polyurethane-forming components
A) organisches Dusoeyanat,A) organic Dusoeyanat,
B) lineares hydroxylterminiertes Polyol mit einem Molekulargewicht von 500 bis 5000,B) linear hydroxyl-terminated polyol with a molecular weight of 500 to 5000,
C) Diol- oder Diamin-Kettenverlängerer mit einem Molekulargewicht von 60 bis 500,C) diol or diamine chain extenders with a molecular weight of 60 to 500,
wobei das Molverhältnis der NCO-Gruppen in A) zu den gegenüber Isocyanat reaktiven Gruppen in B) und C) 0,9 bis 1,2 beträgt.wherein the molar ratio of the NCO groups in A) to the isocyanate-reactive groups in B) and C) is 0.9 to 1.2.
Als organische Diisocyanate A) kommen beispielsweise aliphatische, cycloalipha- tische. araliphatische, heteroeyclische und aromatische Diisocyanate in Betracht, wie sie in Justus Liebigs Annalen der Chemie, 562, S.75-136 beschrieben werden. Im einzelnen seien beispielhaft genannt: aliphatische Diisocyanate, wie Hexamethylen- diisocyanat, cycloaliphatische Diisocyanate, wie Isophorondiisocyanat, 1,4-Cyclo- hexan-diisocyanat, l-Methyl-2,4-cyclohexan-diisocyanat und 1 -Methyl-2,6-cyclohe- xan-diisocyanat sowie die entsprechenden Isomerengemische, 4,4'-Dicyclohexyl- methan-diisocyanat, 2,4'-Dicyclohexylmethan-diisocyanat und 2,2'-Dicyclohexyl- methan-diisocyanat sowie die entsprechenden Isomerengemische, aromatische Diisocyanate, wie 2,4-Toluylendiisocyanat, Gemische aus 2,4-Toluylendiisocyanat und 2,6- Toluylendiisocyanat, 4,4'-Diphenylmethandiisocyanat, 2,4'-Diphenylmethandiiso- cyanat und 2,2'-Diphenylmethandiisocyanat, Gemische aus 2,4'-Diphenylmethandiiso- cyanat und 4,4'-Diphenylmethandiisocyanat, urethanmodifizierte flüssige 4,4'-Di- phenylmethandiisocyanate und 2,4'-Diphenylmethandiisocyanate, 4,4'-Diisocyanato- diphenyl-ethan-(l,2) und 1 ,5-Naphthylendiisocyanat. Vorzugsweise verwendet werden 1 ,6-Hexamethylendiisocyanat, Isophorondiisocyanat, Dicyclohexylmethandiisocyanat, Diphenylmethandiisocyanat-Isomerengemische mit einem 4,4'-Diphenylmethandiiso- cyanatgehalt von >96 Gew.-% und insbesondere 4,4'-Diphenylmethandiisocyanat undExamples of organic diisocyanates A) are aliphatic, cycloaliphatic. araliphatic, heteroeyclic and aromatic diisocyanates, as described in Justus Liebigs Annalen der Chemie, 562, pp.75-136. Examples include: aliphatic diisocyanates such as hexamethylene diisocyanate, cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6- cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2,2'-dicyclohexylmethane diisocyanate as well as the corresponding isomer mixtures, aromatic diisocyanates such as 2 , 4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, mixtures of 2,4'-diphenylmethane diisocyanate - Cyanate and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'-diphenylmethane diisocyanates and 2,4'-diphenylmethane diisocyanates, 4,4'-diisocyanato-diphenyl-ethane (1,2) and 1,5-naphthylene diisocyanate . 1,6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate isomer mixtures with a 4,4'-diphenylmethane diisocyanate content of> 96% by weight and in particular 4,4'-diphenylmethane diisocyanate and
1 ,5-Naphthylendiisocyanat. Die genannten Diisocyanate können einzeln oder in Form von Mischungen untereinander zur Anwendung kommen. Sie können auch zusammen mit bis zu 15 Gew.-% (berechnet auf die Gesamtmenge an Dusoeyanat) eines Polyiso- cyanates verwendet werden, beispielsweise Triphenylmethan-4,4',4"-triisocyanat oder Polyphenyl-polymethylen-polyisocyanaten.1,5-naphthylene diisocyanate. The diisocyanates mentioned can be used individually or in the form of mixtures with one another. They can also be used together with up to 15% by weight (based on the total amount of Dusoeyanat) of a polyisocyanate, for example triphenylmethane-4,4 ', 4 "-triisocyanate or polyphenyl-polymethylene-polyisocyanates.
Als Komponente B) werden lineare hydroxylterminierte Polyole mit einem Molekulargewicht von 500 bis 5000 eingesetzt. Produktionsbedingt enthalten diese oft kleine Mengen an nichtlinearen Verbindungen. Häufig spricht man daher auch von "im wesentlichen linearen Polyolen". Bevorzugt sind Polyester-, Polyether-, Polycarbonat-Linear hydroxyl-terminated polyols with a molecular weight of 500 to 5000 are used as component B). Due to production, these often contain small amounts of non-linear compounds. One therefore often speaks of "essentially linear polyols". Polyester, polyether, polycarbonate are preferred
Diole oder Gemische aus diesen.Diols or mixtures of these.
Geeignete Polyether-Diole können dadurch hergestellt werden, daß man ein oder mehrere Alkylenoxide mit 2 bis 4 Kohlenstoffatomen im Alkylenrest mit einem Startermolekül, das zwei aktive Wasserstoffatome gebunden enthält, umsetzt. AlsSuitable polyether diols can be prepared by reacting one or more alkylene oxides with 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains two active hydrogen atoms bonded. As
Alkylenoxide seien z.B. genannt: Ethylenoxid, 1,2-Propylenoxid, Epichlorhydrin und 1 ,2-Butylenoxid und 2,3-Butylenoxid. Vorzugsweise werden Ethylenoxid, Propylen- oxid und Mischungen aus 1 ,2-Propylenoxid und Ethylenoxid eingesetzt. Die Alkylenoxide können einzeln, alternierend nacheinander oder als Mischungen verwendet werden. Als Startermoleküle kommen beispielsweise in Betracht: Wasser, Amino- alkohole, wie N-Alkyl-diethanolamine, beispielsweise N-Methyl-diethanol-amin, undExamples of alkylene oxides are: ethylene oxide, 1,2-propylene oxide, epichlorohydrin and 1, 2-butylene oxide and 2,3-butylene oxide. Ethylene oxide, propylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide are preferably used. The alkylene oxides can be used individually, alternately in succession or as mixtures. Examples of suitable starter molecules are: water, amino alcohols, such as N-alkyl-diethanolamines, for example N-methyl-diethanolamine, and
Diole, wie Ethylenglykol, 1,3-Propylenglykol, 1 ,4-Butandiol und 1,6-Hexandiol. Gegebenenfalls können auch Mischungen von Startermolekülen eingesetzt werden. Geeignete Polyether-Diole sind ferner die hydroxylgruppenhaltigen Polymerisationsprodukte des Tetrahydrofurans. Es können auch trifunktionelle Polyether in Anteilen von 0 bis 30 Gew.-%, bezogen auf die bifunktionellen Polyether, eingesetzt werden, jedoch höchstens in solcher Menge, daß ein thermoplastisch verarbeitbares Produkt entsteht. Die im wesentlichen linearen Polyether-Diole besitzen Molekulargewichte von 500 bis 5000. Sie können sowohl einzeln als auch in Form von Mischungen untereinander zur Anwendung kommen.Diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. If appropriate, mixtures of starter molecules can also be used. Suitable polyether diols are also the hydroxyl-containing polymerization products of tetrahydrofuran. Trifunctional polyethers can also be used in proportions of 0 to 30% by weight, based on the bifunctional polyethers, but at most in such an amount that a thermoplastically processable product is formed. The essentially linear polyether diols have molecular weights of 500 to 5000. They can be used both individually and in the form of mixtures with one another.
Geeignete Polyester-Diole können beispielsweise aus Dicarbonsäuren mit 2 bis 12 Kohlenstoffatomen, vorzugsweise 4 bis 6 Kohlenstoffatomen, und mehrwertigen Alkoholen hergestellt werden. Als Dicarbonsäuren kommen beispielsweise in Betracht: ali- phatische Dicarbonsäuren, wie Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Azelainsäure und Sebacinsäure und aromatische Dicarbonsäuren, wie Phthalsäure,Suitable polyester diols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols. Examples of suitable dicarboxylic acids are: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid,
Isophthalsäure und Terephthalsäure. Die Dicarbonsäuren können einzeln oder als Gemische, z.B. in Form einer Bernstein-, Glutar- und Adipinsäuremischung, verwendet werden. Zur Herstellung der Polyester-Diole kann es gegebenenfalls vorteilhaft sein, anstelle der Dicarbonsäuren die entsprechenden Dicarbonsäurederivate, wie Carbon- säurediester mit 1 bis 4 Kohlenstoffatomen im Alkoholrest, Carbonsäureanhydride oderIsophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, e.g. in the form of a mixture of succinic, glutaric and adipic acids. For the preparation of the polyester diols it may be advantageous to replace the dicarboxylic acids with the corresponding dicarboxylic acid derivatives, such as carboxylic acid diesters with 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides or
Carbonsäurechloride zu verwenden. Beispiele für mehrwertige Alkohole sind Glykole mit 2 bis 10, vorzugsweise 2 bis 6 Kohlenstoffatomen, wie Ethylenglykol, Diethylen- glykol, 1 ,4-Butandiol, 1 ,5-Pentandiol, 1,6-Hexandiol, 1,10-Decandiol, 2,2-Dimethyl- 1,3-propandiol, 1,3-Propandiol und Dipropylenglykol. Je nach den gewünschten Eigen- schaften können die mehrwertigen Alkohole allein oder gegebenenfalls in Mischung untereinander verwendet werden. Geeignet sind ferner Ester der Kohlensäure mit den genannten Diolen, insbesondere solchen mit 4 bis 6 Kohlenstoffatomen, wie 1 ,4-Butan- diol oder 1 ,6-Hexandiol, Kondensationsprodukte von Hydroxycarbonsäuren, beispielsweise Hydroxycapronsäure und Polymerisationsprodukte von Lactonen, beispielsweise gegebenenfalls substituierten Caprolactonen. Als Polyester-Diole vorzugsweise verwendet werden Ethandiol-polyadipate, 1 ,4-Butandiol-polyadipate, Ethandiol-l,4-butan- diol-polyadipate, 1 ,6-Hexandiol-neopentylglykol-polyadipate, 1 ,6-Hexandiol- 1 ,4- butandiol-polyadipate und Poly-caprolactone. Die Polyester-Diole besitzen Molekulargewichte von 500 bis 5000 und können einzeln oder in Form von Mischungen untereinander zur Anwendung kommen.To use carboxylic acid chlorides. Examples of polyhydric alcohols are glycols with 2 to 10, preferably 2 to 6, carbon atoms, such as ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2, 2-dimethyl-1,3-propanediol, 1,3-propanediol and dipropylene glycol. Depending on the desired properties, the polyhydric alcohols can be used alone or, if appropriate, as a mixture with one another. Also suitable are esters of carbonic acid with the Diols mentioned, in particular those with 4 to 6 carbon atoms, such as 1,4-butanediol or 1,6-hexanediol, condensation products of hydroxycarboxylic acids, for example hydroxycaproic acid and polymerization products of lactones, for example optionally substituted caprolactones. Preferred polyester diols are ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-1,4-butanediol-polyadipates, 1,6-hexanediol-neopentylglycol polyadipates, 1,6-hexanediol-1,4 - Butanediol polyadipate and poly-caprolactone. The polyester diols have molecular weights of 500 to 5000 and can be used individually or in the form of mixtures with one another.
Als Kettenverlängerungsmittel C) werden Diole oder Diamine mit einem Molekulargewicht von 60 bis 500 eingesetzt, vorzugsweise aliphatische Diole mit 2 bis 14 Kohlenstoffatomen, wie z.B. Ethandiol, 1,6-Hexandiol, Diethylenglykol, Dipropylen- glykol und insbesondere 1,4-Butandiol. Geeignet sind jedoch auch Diester der Tereph- thalsäure mit Glykolen mit 2 bis 4 Kohlenstoffatomen, wie z.B. Terephthalsäure-bis- ethylenglykol oder Terephthalsäure-bis-l,4-butandiol, Hydroxyalkylenether des Hydro- chinons, wie z.B. l,4-Di(-hydroxyethyl)-hydrochinon, ethoxylierte Bisphenole, (cyclo)- aliphatische Diamine, wie z.B. Isophorondiamin, Ethylendiamin, 1 ,2-Propylen-diamin, 1 ,3-Propylen-diamin, N-Methyl-propylen-1 ,3-diamin, N,N'-Dimethyl-ethylendiamin und aromatische Diamine, wie z.B. 2,4-Toluylen-diamin und 2,6-Toluylen-diamin, 3,5-Chain extenders C) used are diols or diamines with a molecular weight of 60 to 500, preferably aliphatic diols with 2 to 14 carbon atoms, such as e.g. Ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, such as e.g. Terephthalic acid bis-ethylene glycol or terephthalic acid bis-l, 4-butanediol, hydroxyalkylene ether of hydroquinone, such as e.g. 1,4-di (-hydroxyethyl) hydroquinone, ethoxylated bisphenols, (cyclo) aliphatic diamines, e.g. Isophoronediamine, ethylenediamine, 1,2-propylene-diamine, 1,3-propylene-diamine, N-methyl-propylene-1,3-diamine, N, N'-dimethyl-ethylenediamine and aromatic diamines such as e.g. 2,4-tolylene diamine and 2,6-tolylene diamine, 3,5-
Diethyl-2,4-toluylen-diamin und 3,5-Diethyl-2,6-toluylen-diamin und primäre mono-, di-, tri- oder tetraalkylsubstituierte 4,4'-Diaminodiphenylmethane. Es können auch Gemische der obengenannten Kettenverlängerer eingesetzt werden. Daneben können auch kleinere Mengen an Triolen zugesetzt werden.Diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine and primary mono-, di-, tri- or tetraalkyl-substituted 4,4'-diaminodiphenylmethanes. Mixtures of the chain extenders mentioned above can also be used. Smaller amounts of triplets can also be added.
Weiterhin können in geringen Mengen auch übliche monofunktionelle Verbindungen eingesetzt werden, z.B. als Kettenabbrecher oder Entformungshilfen. Beispielhaft genannt seien Alkohole wie Oktanol und Stearylalkohol oder Amine wie Butylamin und Stearylamin. Zur Herstellung der thermoplastischen Polyurethane können die Aufbaukomponenten, gegebenenfalls in Gegenwart von Katalysatoren, Hilfsmitteln und Zusatzstoffen, in solchen Mengen zur Reaktion gebracht werden, daß das Äquivalenzverhältnis von NCO-Gruppen zur Summe der NCO-reaktiven Gruppen, insbesondere der OH- Gruppen der niedermolekularen Diole/Triole und Polyole 0,9: 1,0 bis 1,2:1,0, vorzugsweise 0,95:1,0 bis 1,10:1,0 beträgt.In addition, conventional monofunctional compounds can also be used in small quantities, for example as chain terminators or mold release aids. Examples include alcohols such as octanol and stearyl alcohol or amines such as butylamine and stearylamine. To produce the thermoplastic polyurethanes, the structural components, if appropriate in the presence of catalysts, auxiliaries and additives, can be reacted in such amounts that the equivalence ratio of NCO groups to the sum of the NCO-reactive groups, in particular the OH groups of the low molecular weight diols / Triols and polyols 0.9: 1.0 to 1.2: 1.0, preferably 0.95: 1.0 to 1.10: 1.0.
Geeignete Katalysatoren sind die nach dem Stand der Technik bekannten und üblichen tertiären Amine, wie z.B. Triethylamin, Dimethylcyclohexylamin, N-Methylmorpho- lin, N,N'-Dimethyl-piperazin, 2-(Dimethylamino-ethoxy)-ethanol, Diazabicyclo-Suitable catalysts are the conventional tertiary amines known and known in the art, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo-
(2,2,2)-octan und ähnliche sowie insbesondere organische Metallverbindungen wie Titansäureester, Eisenverbindungen, Zinnverbindungen, z.B. Zinndiacetat, Zinndi- octoat, Zinndilaurat oder die Zinndialkylsalze aliphatischer Carbonsäuren wie Di- butylzinndiacetat, Dibutylzinndilaurat oder ähnliche. Bevorzugte Katalysatoren sind organische Metallverbindungen, insbesondere Titansäureester, Eisen- oder Zinnverbindungen.(2,2,2) octane and the like and in particular organic metal compounds such as titanium acid esters, iron compounds, tin compounds, e.g. Tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or the like. Preferred catalysts are organic metal compounds, in particular titanium acid esters, iron or tin compounds.
Es kann ein thermoplastisches Polyurethan oder ein Gemisch von thermoplastischen Polyurethanen eingesetzt werden.A thermoplastic polyurethane or a mixture of thermoplastic polyurethanes can be used.
Die TPU können kontinuierlich im sogenannten Extruderverfahren, z.B. in einem Mehrwellenextruder, hergestellt werden. Die Dosierung der TPU-Komponenten A), B) und C) kann gleichzeitig, d.h. im one-shot-V erfahren, oder nacheinander, d.h. nach einem Prepolymer- Verfahren, erfolgen. Dabei kann das Prepolymer sowohl batchweise vorgelegt, als auch kontinuierlich in einem Teil des Extruders oder in einem separaten vorgeschalteten Prepolymeraggregat hergestellt werden.The TPU can continuously in the so-called extruder process, e.g. in a multi-screw extruder. The dosage of the TPU components A), B) and C) can be carried out simultaneously, i.e. experienced in one-shot-V, or one after the other, i.e. by a prepolymer process. The prepolymer can either be introduced batchwise or else be produced continuously in part of the extruder or in a separate upstream prepolymer unit.
Polyolefine sind beispielsweise Polyethylen, Polypropylen, Poly-1 -baten und Poly- methylpenten, die noch geringe Mengen an nicht konjugierten Dienen einpoly- merisiert enthalten können. Diese Polymere sind bekannt und in Roempp's Chemie- lexikon, 8. Auflage 1987, Bd. 5, S. 3307 und in der dort zitierten Literatur beschrieben.Polyolefins are, for example, polyethylene, polypropylene, poly-1-baten and poly-methylpentene, which can still contain small amounts of non-conjugated dienes in copolymerized form. These polymers are known and are used in Roempp's chemistry Lexicon, 8th edition 1987, Vol. 5, p. 3307 and described in the literature cited therein.
Als thermoplastische Vinyl (co)polymerisate sind Polymere von mindestens einem Monomeren aus der Gruppe der Vinylaromaten, Vinylcyanide (ungesättigte Nitrile),The thermoplastic vinyl (co) polymers are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles),
(Meth)Acrylsäure-(CrC8)-Alkylester, ungesättigte Carbonsäuren sowie Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren geeignet. Vorzugsweise geeignet sind (Co)Polymerisate aus(Meth) acrylic acid (C r C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids are suitable. (Co) polymers of are preferably suitable
D.l 50 bis 99, vorzugsweise 60 bis 80 Gew.-Teilen Vinylaromaten und/oder kernsubstituierten Vinylaromaten wie beispielsweise Styrol, α-Methylstyrol, p- Methylstyrol, p-Chlorstyrol) und/oder Methacrylsäure-(C,-C4)-Alkylester wie z.B. Methylmethacrylat, Ethylmethacrylat), undDl 50 to 99, preferably 60 to 80 parts by weight of vinyl aromatics and / or nucleus-substituted vinyl aromatics such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C, -C 4 ) alkyl esters such as eg methyl methacrylate, ethyl methacrylate), and
D.2 1 bis 50, vorzugsweise 20 bis 40 Gew.-Teilen Vinylcyanide (ungesättigteD.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated
Nitrile) wie Acrylnitril und Methacrylnitril und/oder (Meth)Acrylsäure-(C,- Cg)-Alkylester (wie z.B. Methylmethacrylat, n-Butylacrylat, t-Butylacrylat) und/oder ungesättigte Carbonsäuren (wie Maleinsäure) und/oder Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren (beispielsweise Maleinsäureanhydrid und N-Phenyl-Maleinimid).Nitriles) such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (C, - C g ) alkyl esters (such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or unsaturated carboxylic acids (such as maleic acid) and / or derivatives ( such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic anhydride and N-phenyl-maleimide).
Die (Co)Polymerisate sind harzartig, thermoplastisch und kautschukfrei.The (co) polymers are resinous, thermoplastic and rubber-free.
Besonders bevorzugt sind Copolymerisate aus D.l Styrol und D.2 Acrylnitril.Copolymers of D.l styrene and D.2 acrylonitrile are particularly preferred.
Vorzugsweise sind weiterhin geeignet gegebenenfalls alkyl- und/oder halogen-kern- substituierte Polystyrole oder α-Methylpolystyrol.Also preferably suitable are optionally alkyl- and / or halogen-substituted polystyrenes or α-methylpolystyrene.
Die (Co)Polymerisate sind bekannt und lassen sich durch radikalische Polymerisa- tion, insbesondere durch Emulsions-, Suspensions-, Lösungs- oder Massepolymerisation herstellen. Die (Co)Polymerisate besitzen vorzugsweise Molekulargewichte Mw (Gewichtsmittel, ermittelt durch Lichtstreuung oder Sedimentation) zwischen 15 000 und 200 000.The (co) polymers are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymers preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
Als Pfropfpolymerisate sind geeignet ein oder mehrere Pfropfpolymerisate vonOne or more graft polymers of are suitable as graft polymers
E.l 5 bis 95, vorzugsweise 30 bis 80 Gew.-%, wenigstens eines Vinylmonomeren aufE.l 5 to 95, preferably 30 to 80 wt .-%, of at least one vinyl monomer
E.2 95 bis 5, vorzugsweise 70 bis 20 Gew.-% einer oder mehrerer Pfropfgrund- lagen mit Glasübergangstemperaturen < 10°C, vorzugsweise < 0°C, besonders bevorzugt < -20°C.E.2 95 to 5, preferably 70 to 20% by weight of one or more graft bases with glass transition temperatures <10 ° C, preferably <0 ° C, particularly preferably <-20 ° C.
Die Pfropfgrundlage E.2 hat im allgemeinen eine mittlere Teilchengröße (d50- Wert) von 0,05 bis 5 μm.The graft base E.2 generally has an average particle size (d 50 value) of 0.05 to 5 μm.
Monomere E.1 sind vorzugsweise Gemische ausMonomers E.1 are preferably mixtures of
El .l 50 bis 99 Gew.-Teilen Vinylaromaten und/oder kernsubstituierten Vinylaromaten (wie beispielsweise Styrol, α-Methylstyrol, p-Methylstyrol, p-Chlor- styrol) und/oder Methacrylsäure-(CrC4)-Alkylester (wie z.B. Methylmethacrylat, Ethylmethacrylat) undEl .l 50 to 99 parts by weight of vinyl aromatics and / or core-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C r C 4 ) alkyl esters (such as eg methyl methacrylate, ethyl methacrylate) and
El.2 1 bis 50 Gew.-Teilen Vinylcyanide (ungesättigte Nitrile wie Acrylnitril und Methacrylnitril) und/oder (Meth)Acrylsäure-(C,-C8)-Alkylester (wie z.B. Methylmethacrylat, Methylacrylat, n-Butylacrylat, t-Butylacrylat) und/oderEl.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C, -C 8 ) alkyl esters (such as methyl methacrylate, methyl acrylate, n-butyl acrylate, t-butyl acrylate ) and or
Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren (beispielsweise Maleinsäureanhydrid und N-Phenyl-Maleinimid).Derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic anhydride and N-phenyl-maleimide).
Bevorzugte Monomere E. l .l sind ausgewählt aus mindestens einem der Monomere Styrol, α-Methylstyrol und Methylmethacrylat, bevorzugte Monomere E. l .2 sind ausgewählt aus mindestens einem der Monomere Acrylnitril, Maleinsäureanhydrid, Methylacrylat und Methylmethacrylat.Preferred monomers E.1.1 are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, preferred monomers E.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride, methyl acrylate and methyl methacrylate.
Besonders bevorzugte Monomere sind E.1.1 Styrol und E.1.2 Acrylnitril.Particularly preferred monomers are E.1.1 styrene and E.1.2 acrylonitrile.
Für die Pfropfpolymerisate geeignete Pfropfgrundlagen E.2 sind beispielsweise Dienkautschuke, EP(D)M-Kautschuke, also solche auf Basis Ethylen/Propylen und gegebenenfalls Dien, Acrylat-, Polyurethan-, Silikon-, Chloropren und Ethylen/Vi- nylacetat-Kautschuke.Graft bases E.2 suitable for the graft polymers are, for example, diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and, if appropriate, diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
Bevorzugte Pfropfgrundlagen E.2 sind Dienkautschuke (z. B. auf Basis Butadien, Isopren etc.) oder Gemische von Dienkautschuken oder Copolymerisate von Dienkautschuken oder deren Gemischen mit weiteren copolymerisierbaren Monomeren (z.B. gemäß E.l .1 und E.1.2), mit der Maßgabe, daß die Glasübergangstemperatur der Komponente E.2 unterhalb <10°C, vorzugsweise <0°C, besonders bevorzugtPreferred graft bases E.2 are diene rubbers (for example based on butadiene, isoprene etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to El .1 and E.1.2), with the proviso that the glass transition temperature of component E.2 below <10 ° C, preferably <0 ° C, particularly preferred
<-10°C liegt.<-10 ° C.
Besonders bevorzugt ist reiner Polybutadienkautschuk.Pure polybutadiene rubber is particularly preferred.
Besonders bevorzugte Polymerisate sind z.B. ABS-Polymerisate (Emulsions-,Particularly preferred polymers are e.g. ABS polymers (emulsion,
Masse- und Suspensions-ABS), wie sie z. B. in der DE-OS 2 035 390 (=US-PS 3 644 574) oder in der DE-OS 2 248 242 (=GB-PS 1 409 275) bzw. in Ulimann, Enzyklopädie der Technischen Chemie, Bd. 19 (1980), S. 280 ff. beschrieben sind.Mass and suspension ABS), such as z. B. in DE-OS 2 035 390 (= US-PS 3 644 574) or in DE-OS 2 248 242 (= GB-PS 1 409 275) or in Ulimann, Encyclopedia of Chemical Engineering, Vol. 19 (1980), p. 280 ff.
Die Pfropfpolymerisate werden durch radikalische Polymerisation, z.B. durch Emulsions-, Suspensions-, Lösungs- oder Massepolymerisation, vorzugsweise durch Emulsionspolymerisation hergestellt.The graft polymers are obtained by radical polymerization, e.g. prepared by emulsion, suspension, solution or bulk polymerization, preferably by emulsion polymerization.
Geeignete Acrylatkautschuke gemäß E.2 sind vorzugsweise Polymerisate aus Acryl- säurealkylestern, gegebenenfalls mit bis zu 40 Gew.-%, bezogen auf E.2 anderen polymerisierbaren, ethylenisch ungesättigten Monomeren. Zu den bevorzugten poly- merisierbaren Acrylsäureestern gehören C,-C8-Alkylester, beispielsweise Methyl-, Ethyl-, Butyl-, n-Octyl- und 2-Ethylhexylester; Halogenalkylester, vorzugsweise Halogen-C,-C8-alkyl-ester, wie Chlorethylacrylat sowie Mischungen dieser Monomeren.Suitable acrylate rubbers according to E.2 are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on E.2, of other polymerizable, ethylenically unsaturated monomers. Among the preferred poly Merizable acrylic acid esters include C 1 -C 8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen C 1 -C 8 alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
Zur Vernetzung können Monomere mit mehr als einer polymerisierbaren Doppelbindung copolymerisiert werden. Bevorzugte Beispiele für vernetzende Monomere sind Ester ungesättigter Monocarbonsäuren mit 3 bis 8 C-Atomen und ungesättigter einwertiger Alkohole mit 3 bis 12 C-Atomen, oder gesättigter Polyole mit 2 bis 4 OH-Gruppen und 2 bis 20 C-Atomen, wie z.B. Ethylenglykoldimethacrylat, Allyl- methacrylat; mehrfach ungesättigte heterocyclische Verbindungen, wie z.B. Trivinyl- und Triallylcyanurat; polyfunktionelle Vinylverbindungen, wie Di- und Trivinylben- zole; aber auch Triallylphosphat und Diallylphthalat.Monomers with more than one polymerizable double bond can be copolymerized for crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as e.g. Ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, e.g. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
Bevorzugte vernetzende Monomere sind Allylmethacrylat, Ethylenglykoldimethacrylat, Diallylphthalat und heterocyclische Verbindungen, die mindestens 3 ethylenisch ungesättigte Gruppen aufweisen.Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.
Besonders bevorzugte vernetzende Monomere sind die cyclischen Monomere Trial- lylcyanurat, Triallylisocyanurat, Triacryloylhexahydro-s-triazin, Triallylbenzole. DieParticularly preferred crosslinking monomers are the cyclic monomers trialyll cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes. The
Menge der vernetzten Monomere beträgt vorzugsweise 0,02 bis 5, insbesondere 0,05 bis 2 Gew.-%, bezogen auf die Pfropfgrundlage E.2.The amount of crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2,% by weight, based on the graft base E.2.
Bei cyclischen vernetzenden Monomeren mit mindestens 3 ethylenisch ungesättigten Gruppen ist es vorteilhaft, die Menge auf unter 1 Gew.-% der Pfropfgrundlage E.2 zu beschränken.In the case of cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base E.2.
Bevorzugte "andere" polymerisierbare, ethylenisch ungesättigte Monomere, die neben den Acrylsäureestern gegebenenfalls zur Herstellung der Pfropfgrundlage E.2 dienen können, sind z. B. Acrylnitril, Styrol, α-Methylstyrol, Acrylamide, Vinyl-Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base E.2 are, for. B. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl
CrC6-alkylether, Methylmethacrylat, Butadien. Bevorzugte Acrylatkautschuke als Pfropfgrundlage E.2 sind Emulsionspolymerisate, die einen Gelgehalt von mindestens 60 Gew.-% aufweisen.C r C 6 alkyl ether, methyl methacrylate, butadiene. Preferred acrylate rubbers as Graft base E.2 are emulsion polymers which have a gel content of at least 60% by weight.
Weitere geeignete Pfropgrundlagen gemäß E.2 sind Silikonkautschuke mit pfropfak- tiven Stellen, wie sie in den DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 und DE-OS 3 631 539 beschrieben werden.Further suitable graft bases according to E.2 are silicone rubbers with graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
Der Gelgehalt der Pfropgrundlage E.2 wird bei 25°C in einem geeigneten Lösungsmittel bestimmt (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und II, Georg Thieme-Verlag, Stuttgart 1977).The gel content of the graft base E.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
Die mittlere Teilchengröße d50 ist der Durchmesser, oberhalb und unterhalb dessen jeweils 50 Gew.-% der Teilchen liegen. Er kann mittels Ultrazentrifugenmessung (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796) bestimmt werden.The average particle size d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).
Polyphenylenether im Sinne der vorliegenden Erfindungsind beispielsweise in EP-A 164 767 beschrieben.Polyphenylene ethers in the sense of the present invention are described, for example, in EP-A 164 767.
Füll- und Verstärkungsstoffe, insbesondere mineralische Füllstoffe, können denFillers and reinforcing materials, especially mineral fillers, can
Polyketonen bzw. Polyketon-Blends zugemischt werden. Als Füll- und Verstärkungsstoffe können z.B. Kaolin, Talkum, Wollastonit, Glasfasern (einschließlich Langglas- und Endlosglasfasern und Glasgewebe und Glasmatten), Glaskugeln, Calciumcarbonat, Kohlenstofffasern, Aramidfasern oder Glimmer, Naturfasern oder Mischungen davon eingesetzt werden.Polyketones or polyketone blends are added. As fillers and reinforcing materials e.g. Kaolin, talc, wollastonite, glass fibers (including long glass and continuous glass fibers and glass fabrics and glass mats), glass balls, calcium carbonate, carbon fibers, aramid fibers or mica, natural fibers or mixtures thereof can be used.
Die Füllstoffe werden üblicherweise in einer Menge bis zu 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-%, bezogen auf die Gesamtmischung, eingesetzt. Die Formmassen aus Polyketon und Polyketon-Blends können übliche Additive wie Gleit- und Entformungsmittel, Nukleierungsmittel, Antistatika, Stabilisatoren sowie Farbstoffe und Pigmente enthalten.The fillers are usually used in an amount of up to 50% by weight, preferably 5 to 30% by weight, based on the mixture as a whole. The molding compositions made of polyketone and polyketone blends can contain conventional additives such as lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers and dyes and pigments.
Um leitfähige Formmassen zu erhalten, können leitfähige Ruße, Carbonfibrillen,In order to obtain conductive molding compounds, conductive carbon blacks, carbon fibrils,
Graphit, leitfähige Polymere, Metallfasern sowie andere übliche Additive zur Erhöhung der Leitfähigkeit zugesetzt werden.Graphite, conductive polymers, metal fibers and other conventional additives to increase the conductivity can be added.
Die erfindungsgemäßen Kfz-Anbauteile bzw. Karosserieaußenteile aus Polyketon oder Polyketon-Blends werden durch übliche Kunststoff-Verarbeitungstechniken wie zum Beispiel Spritzguß, Extrusion, Thermoformen, Tiefziehen, Pressen, Schweißen, Prägen, Sintern, Blasformen, Gasinjektionstechnik oder einer Kombination dieser Techniken hergestellt.The motor vehicle add-on parts or exterior parts of the body made of polyketone or polyketone blends are produced by conventional plastic processing techniques such as injection molding, extrusion, thermoforming, deep drawing, pressing, welding, embossing, sintering, blow molding, gas injection technology or a combination of these techniques.
Dazu wird das Polyketon gegebenenfalls mit dem(n) Blendpartner(n) und gegebenenfalls mit üblichen Füll-, Verstärkungsstoffen und/oder Additiven in bekannter Weise vermischt und entweder direkt zur Herstellung eines Halbzeuges (zum Beispiel Platten, Folien, Profile) bzw. der erfindungsgemäßen Formteile (Kfz-Anbau- teiles) mit üblichen Kunststoff- Verarbeitungstechniken verwendet oder bei erhöhten Temperaturen, vorzugsweise 200-350°C, in üblichen Aggregaten wie zum BeispielFor this purpose, the polyketone is optionally mixed with the blend partner (s) and, if appropriate, with customary fillers, reinforcing materials and / or additives in a known manner and either directly to produce a semi-finished product (for example plates, foils, profiles) or the invention Shaped parts (automotive add-on part) used with conventional plastic processing techniques or at elevated temperatures, preferably 200-350 ° C, in conventional units such as
Extrudern, Innenknetern, Doppelwellenschnecken zu thermoplastischen Formmassen schmelzcompoundiert und anschließend zum Beispiel granuliert. Das Granulat aus Polyketon bzw. Polyketon-Blends wird mit üblichen Kunststoff-Verarbeitungstechniken wie bereits aufgezählt zu Halbzeugen (zum Beispiel Platten, Folien, Profile) bzw. den erfindungsgemäßen Formteilen (Kfz-Anbauteile) weiterverarbeitet.Extruders, internal kneaders, twin-screw extruders melt-compounded into thermoplastic molding compounds and then granulated, for example. The granulate made of polyketone or polyketone blends is processed further using conventional plastic processing techniques, as already enumerated, to give semi-finished products (for example plates, foils, profiles) or the molded parts according to the invention (vehicle attachments).
Die Halbzeuge werden durch übliche Techniken wie zum Beispiel Thermoformen zu den erfindungsgemäßen Kfz-Anbauteilen weiterverarbeitet.The semifinished products are further processed by conventional techniques such as thermoforming to the motor vehicle add-on parts according to the invention.
Die erfindungsgemäßen Kfz-Anbauteile aus Polyketon bzw. Polyketon-Blends können sich auch im Verbund mit weiteren Werkstoffen wie zum Beispiel Metall oder Kunststoff befinden. Nach der Lackierung der Kfz-Anbauteile können sich die Lackschichten direkt auf den Formmassen aus Polyketon bzw. Polyketon-Blends und/oder auf den im Verbund eingesetzten Werkstoffen befinden.The motor vehicle add-on parts made of polyketone or polyketone blends according to the invention can also be combined with other materials such as metal or plastic. After painting the vehicle attachments, the Lacquer layers are located directly on the molding compounds made of polyketone or polyketone blends and / or on the materials used in the composite.
Die Mischungen aus Polyketon, Blendpartner(n), Füll-, Verstärkungsstoffen und/oder Additiven, bzw. die erfindungsgemäßen Formmassen aus Polyketon oder Polyketon-The mixtures of polyketone, blend partner (s), fillers, reinforcing materials and / or additives, or the molding compositions according to the invention made of polyketone or polyketone
Blends bzw. die Halbzeuge aus Polyketon oder Polyketon-Blends können auch durch übliche Techniken zum Verbinden und Zusammenfügen mehrerer Komponenten oder Teile wie zum Beispiel Coextrusion, Folienhinterspritzen, Sandwich-Spritzgießen, Hinterpressen, Hinterprägen, Umspritzen von Einlegeteilen, Mehrkompo- nenten-Spritzgießen, Schweißen, Pressen, Kleben, Verschmelzen, Verschrauben oderBlends or the semi-finished products made of polyketone or polyketone blends can also be produced using conventional techniques for connecting and joining together several components or parts such as, for example, coextrusion, film injection molding, sandwich injection molding, back pressing, back embossing, overmolding of inserts, multi-component injection molding, welding , Pressing, gluing, melting, screwing or
Klammern im Verbund mit anderen Werkstoffen oder sich selbst für die Herstellung von Kfz-Anbauteile eingesetzt werden.Brackets in combination with other materials or themselves can be used for the production of automotive add-on parts.
Als Kfz-Anbauteile werden vorzugsweise genannt Kotflügel, Stoßfänger, Rück- wandtür, Kofferraumdeckel, Seitentürverkleidung, Motorhaube, Autodach, Kühlergrill, Außenspiegel. Fender, bumper, rear wall door, trunk lid, side door trim, bonnet, car roof, radiator grille, exterior mirrors are preferably mentioned as vehicle attachments.
BeispieleExamples
Die folgenden Komponenten werden in den Beispielen verwendetThe following components are used in the examples
A) Polyketon:A) Polyketone:
Linear alternierendes Terpolymer aus Kohlenmonoxid, Ethylen und Propylen, (Carilon® DP P1000, Shell International Chemicals Ltd., London, UK)Linear alternating terpolymer made of carbon monoxide, ethylene and propylene, (Carilon ® DP P1000, Shell International Chemicals Ltd., London, UK)
B) Polyketon / ABS : 95 Gew.-% Carilon® DP P 1000 und 5 % ABSB) polyketone / ABS: 95 wt .-% Carilon ® DP P 1000 and 5% ABS
Polyketon:Polyketone:
Carilon® DP P1000, Shell Int. Chem. Ltd.Carilon ® DP P1000, Shell Int. Chem. Ltd.
ABS-Pfropfkautschuk:ABS graft rubber:
Durch Kaliumpersulfat-initiierte Emulsionspolymerisation unter Verwendung eines Kautschukgemisches (50 Gew.-% eines in Latexform vorliegenden Kautschukes (Polybutadien) mit einem mittleren Teilchendurchmesser dso von 280 nm und einem Gelgehalt von 53 Gew.-% und 50 Gew-% eines in Latexform vorliegenden Kautschuks (Polybutadien) mit einem mittleremBy potassium persulfate-initiated emulsion polymerization using a rubber mixture (50% by weight of a rubber in latex form (polybutadiene) with an average particle diameter dso of 280 nm and a gel content of 53% by weight and 50% by weight of a rubber in latex form (Polybutadiene) with a medium
Teilchendurchmesser dso von 420 nm und einem Gelgehalt von 85 Gew.-%) hergestellter Propfkautschuk mit einem Kautschukgehalt von 50 Gew.-% und 50 Gew.-% einer Propfhülle aufgebaut durch Pfropfpolymerisation eines Gemischs aus 27% Gew.-Teilen Acrylnitril und 73 Gew.-Teilen Styrol.Particle diameter dso of 420 nm and a gel content of 85% by weight) produced graft rubber with a rubber content of 50% by weight and 50% by weight of a graft shell built up by graft polymerization of a mixture of 27% by weight of acrylonitrile and 73% by weight . Parts styrene.
Das Mischen des Polyketons und des Kautschukes erfolgte auf einem Extruder des Typs ZSK32 bei 220-240°C.The polyketone and the rubber were mixed in a ZSK32 extruder at 220-240 ° C.
C) Polyketon TPU: 95 Gew.-% Carilon® DP P1000 und 5 Gew.-% TPU Polyketon:C) Polyketone TPU: 95% by weight of Carilon® DP P1000 and 5% by weight of TPU Polyketone:
Carilon® DP P1000 (siehe A)Carilon ® DP P1000 (see A)
Thermoplastisches Polyurethan (TPU): Desmopan® 385, Bayer AG, Leverkusen, DeutschlandThermoplastic polyurethane (TPU): Desmopan ® 385, Bayer AG, Leverkusen, Germany
(auf Basis, Poly-butandiol-l,4-adipat, Butandiol-1 ,4, Methylendiphenyldiiso- cyanat)(based on poly-butanediol-1,4-adipate, butanediol-1,4, methylene diphenyldiisocyanate)
das Mischen des Polyketons und des TPU erfolgte auf einem Extruder des Typs ZSK 32/1 bei 220 bis 240°C.the polyketone and the TPU were mixed in a ZSK 32/1 extruder at 220 to 240 ° C.
D) PBT:D) PBT:
Pocan® B1300, Bayer AG, Leverkusen, Deutschland.Pocan® B1300, Bayer AG, Leverkusen, Germany.
E) PPO/PA (ein Polyphenylenether/Polyamid-Blend):E) PPO / PA (a polyphenylene ether / polyamide blend):
Noryl® GTX 964, General Electric Plastic, Pittsfield, USA.Noryl® GTX 964, General Electric Plastic, Pittsfield, USA.
F) schlagzäh modifiziertes BlendF) impact modified blend
Pocan KU 2-7912, Bayer AG, Leverkusen, Deutschland.Pocan KU 2-7912, Bayer AG, Leverkusen, Germany.
Die für die Prüfungen benötigten Formkörper werden auf einer Spritzgußmaschine des Typs Arburg 320-210-500 bei den von den Thermoplast-Herstellern empfohlenen Masse- und Werkzeugtemperaturen hergestellt.The moldings required for the tests are produced on an Arburg 320-210-500 injection molding machine at the melt and mold temperatures recommended by the thermoplastic manufacturers.
Die dynamisch mechanische Messung des komplexen Schubmoduls wird im Torsionsschwingversuch in Abhängigkeit von der Temperatur mit einer Meßfrequenz von 1 Hz an 80* 10*4 mm3 Prüfstäben mit einem RDS II Gerät der Fa. Rheometrics gemessen. Der Schubmodul G' macht eine Aussage über die Steifigkeit und dient als Maß für die Wärmeformbeständigkeit und Dimensionsstabilität. Ein Schubmodul G' von ca. 80 - 100 MPa bei der entsprechenden Lack-Einbrenntemperatur gilt als ausreichend, um Kfz-Anbauteile ohne Verformung lackieren zu können. Das Verhalten bei Stoßbeanspruchung im biaxialem Durchstoßversuch wird an 60 mm Rundscheiben mit 3 mm Dicke nach ISO 6603-2 untersucht.The dynamic mechanical measurement of the complex thrust module is measured in the torsional vibration test depending on the temperature with a measuring frequency of 1 Hz on 80 * 10 * 4 mm 3 test bars with an RDS II device from Rheometrics. The thrust module G 'makes a statement about the rigidity and serves as a measure of the heat resistance and dimensional stability. A thrust module G 'of approx. 80 - 100 MPa at the appropriate paint baking temperature is considered sufficient to be able to paint vehicle attachments without deformation. The behavior under impact stress in the biaxial puncture test is investigated on 60 mm round disks with a thickness of 3 mm according to ISO 6603-2.
Der Elastizitätsmodul wird im Zugversuch nach ISO 527.2 an Schulterstäben gemessen.The modulus of elasticity is measured in the tensile test according to ISO 527.2 on shoulder bars.
Die Laekierbarkeit wurde nach dem Fachmann bekannten Standardmethoden untersucht.The layability was investigated according to standard methods known to the person skilled in the art.
Die Oberfläche der Formteile wurde visuell beurteilt.The surface of the molded parts was assessed visually.
Tabelle 1Table 1
Bei Polyketon und PBT handelt es sich um teilkristalline Thermoplaste. Obwohl die Glasübergangstemperatur von Polyketon mit ca. 12°C unterhalb von Raumtemperatur liegt, ist die Steifigkeit (Schubmodul) bei hohen Temperaturen wesentlich höher als die von PBT und anderen vergleichbaren teilkristallinen Thermoplasten. Polyke- ton weist daher im Gegensatz zu anderen typischen teilkristallinen Thermoplasten eine ausreichende Wärmeformbeständigkeit für in-line und on-line lackierbare Kfz.- Anbauteile auf. Im Vergleich zu PBT und PPO/PA-Blends, zeigt Polyketon mit einem Zäh-/Sprödübergang von ca. -30°C eine deutlich bessere Tieftemperaturschlagzähigkeit. Bei dem schlagzähmodifizierten PC/PBT-Blend handelt es sich um ein typisches Blendsystem für off-line lackierbare Kfz-Anbauteile sehr guter Tieftemperaturzähigkeit aber für in-line oder on-line Lackierung völlig unzureichender Wärmeformbeständigkeit. Die Beispiele Polyketon/ABS und Polyketon/TPU zeigen, daß die günstigen Eigenschaften von Polyketonen für in-line und on-line lackierbare Anbauteile auch in Polyketon-Blends erhalten bleiben. Polyketone and PBT are semi-crystalline thermoplastics. Although the glass transition temperature of polyketone is around 12 ° C below room temperature, the stiffness (shear modulus) at high temperatures is much higher than that of PBT and other comparable semi-crystalline thermoplastics. In contrast to other typical semi-crystalline thermoplastics, polyketon therefore has sufficient heat resistance for in-line and on-line paintable automotive add-on parts. Compared to PBT and PPO / PA blends, polyketone with a toughness / brittle transition of approx. -30 ° C shows a significantly better low-temperature impact strength. The impact-modified PC / PBT blend is a typical blend system for automotive paintable parts that can be painted off-line, has very good low-temperature toughness but is completely inadequate in heat resistance for in-line or on-line painting. The examples polyketone / ABS and polyketone / TPU show that the favorable properties of polyketones for in-line and on-line paintable attachments are retained even in polyketone blends.

Claims

Patentansprüche claims
1. Kfz-Anbauteile auf Basis thermoplastischer Polyketone.1. Vehicle attachments based on thermoplastic polyketones.
2. Kfz-Anbauteile auf Basis thermoplastischer Polyketone und deren Blends mit anderen Thermoplasten ausgewählt aus mindestens einem aus der Gruppe der Polyalkylenterephthalate, thermoplastische Vinyl(co)polymere, Pfropfpoly- mere, Polyolefine und/oder thermoplastischen Elatomeren.2. Motor vehicle add-on parts based on thermoplastic polyketones and their blends with other thermoplastics selected from at least one from the group of polyalkylene terephthalates, thermoplastic vinyl (co) polymers, graft polymers, polyolefins and / or thermoplastic elatomers.
3. In-line lackierbare Kfz-Anbauteile gemäß Anspruch 1 und 2.3. In-line paintable vehicle attachments according to claim 1 and 2.
4. On-Line lackierbare Kfz-Anbauteile gemäß Anspruch 1 und 2.4. On-line paintable vehicle attachments according to claim 1 and 2.
5. Kfz-Anbauteile gemäß einem der vorhergehenden Ansprüche, wobei die thermoplastischen Polyketone und deren Blends Füll- und/oder Verstärkungsstoffe und gegebenenfalls Additive ausgewählt aus mindestens einem der Gruppe der Gleit- und Entformungsmittel, Nukleierungsmittel, Antistatika, Stabilisatoren sowie Farbstoffe und Pigmente sowie Additive zur Erhöhung der Leitfähigkeit enthalten.5. Motor vehicle attachments according to one of the preceding claims, wherein the thermoplastic polyketones and their blends fillers and / or reinforcing materials and optionally additives selected from at least one of the group of lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers and dyes and pigments and additives included to increase conductivity.
Verwendung von thermoplastischen Polyketonen, gegebenenfalls in Ab- mischung mit anderen Thermoplasten und weiteren Zusatzstoffen zur Herstellung von Kfz-Anbauteilen. Use of thermoplastic polyketones, if necessary in a mixture with other thermoplastics and other additives for the production of automotive add-on parts.
EP99948854A 1998-10-07 1999-09-24 Body add-on parts based on thermoplastic polyketones Withdrawn EP1117724A1 (en)

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DE19846051A DE19846051A1 (en) 1998-10-07 1998-10-07 Body attachments based on thermoplastic polyketones
DE19846051 1998-10-07
PCT/EP1999/007115 WO2000020486A1 (en) 1998-10-07 1999-09-24 Body add-on parts based on thermoplastic polyketones

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