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WO2000020486A1 - Elements rapportes pour carrosseries, a base de polycetones thermoplastiques - Google Patents

Elements rapportes pour carrosseries, a base de polycetones thermoplastiques Download PDF

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Publication number
WO2000020486A1
WO2000020486A1 PCT/EP1999/007115 EP9907115W WO0020486A1 WO 2000020486 A1 WO2000020486 A1 WO 2000020486A1 EP 9907115 W EP9907115 W EP 9907115W WO 0020486 A1 WO0020486 A1 WO 0020486A1
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WIPO (PCT)
Prior art keywords
thermoplastic
polyketones
parts
acid
line
Prior art date
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Ceased
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PCT/EP1999/007115
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German (de)
English (en)
Inventor
Matthias Müller
Detlef Joachimi
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Bayer AG
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Bayer AG
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Publication date
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Priority to BR9914316-0A priority Critical patent/BR9914316A/pt
Priority to AU61961/99A priority patent/AU6196199A/en
Priority to KR1020017004354A priority patent/KR20010080019A/ko
Priority to JP2000574593A priority patent/JP2002526330A/ja
Priority to EP99948854A priority patent/EP1117724A1/fr
Publication of WO2000020486A1 publication Critical patent/WO2000020486A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)

Abstract

L'invention concerne des éléments rapportés pour carrosseries à base de polycétones thermoplastiques et leurs mélanges avec d'autres polymères, ainsi que l'utilisation de polycétones thermoplastiques pour produire des éléments rapportés pour carrosseries.
PCT/EP1999/007115 1998-10-07 1999-09-24 Elements rapportes pour carrosseries, a base de polycetones thermoplastiques Ceased WO2000020486A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR9914316-0A BR9914316A (pt) 1998-10-07 1999-09-24 Peças complementares de carrocerias à base de policetonas termoplásticas.
AU61961/99A AU6196199A (en) 1998-10-07 1999-09-24 Body add-on parts based on thermoplastic polyketones
KR1020017004354A KR20010080019A (ko) 1998-10-07 1999-09-24 열가소성 폴리케톤 기재의 차체 추가 부품
JP2000574593A JP2002526330A (ja) 1998-10-07 1999-09-24 熱可塑性ポリケトンを基材とする車両装具
EP99948854A EP1117724A1 (fr) 1998-10-07 1999-09-24 Elements rapportes pour carrosseries, a base de polycetones thermoplastiques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19846051.1 1998-10-07
DE19846051A DE19846051A1 (de) 1998-10-07 1998-10-07 Karosserie-Anbauteile auf Basis thermoplastischer Polyketone

Publications (1)

Publication Number Publication Date
WO2000020486A1 true WO2000020486A1 (fr) 2000-04-13

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PCT/EP1999/007115 Ceased WO2000020486A1 (fr) 1998-10-07 1999-09-24 Elements rapportes pour carrosseries, a base de polycetones thermoplastiques

Country Status (8)

Country Link
EP (1) EP1117724A1 (fr)
JP (1) JP2002526330A (fr)
KR (1) KR20010080019A (fr)
CN (1) CN1322221A (fr)
AU (1) AU6196199A (fr)
BR (1) BR9914316A (fr)
DE (1) DE19846051A1 (fr)
WO (1) WO2000020486A1 (fr)

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DE102016013868A1 (de) 2016-11-28 2018-05-30 Carl Freudenberg Kg Polymermischung für Dichtungen

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KR100972357B1 (ko) * 2009-02-09 2010-07-26 주식회사 상신산업 확장가능한 튜브형 락 볼트
US20170166743A1 (en) * 2014-07-18 2017-06-15 Hyosung Corporation Polyketone resin composition having excellent oil resistance
KR101734888B1 (ko) * 2014-11-19 2017-05-24 주식회사 효성 파라 아라미드가 포함된 폴리케톤 조성물
KR101620568B1 (ko) * 2014-07-18 2016-05-13 주식회사 효성 폴리케톤 성형품 및 스노우 체인
KR101664926B1 (ko) * 2014-11-19 2016-10-11 주식회사 효성 폴리에스테르가 포함된 폴리케톤 조성물
ES2676498T3 (es) * 2015-11-13 2018-07-20 Ems-Patent Ag Materiales policetónicos alifáticos ignífugos, cuerpos de moldeo derivados de ellas así como procedimientos para su producción
KR101777562B1 (ko) 2015-11-27 2017-09-13 (주)휴이노베이션 친환경 및 저연 특성이 탁월한 폴리케톤계 수지 및 폴리알킬렌 카보네이트계 수지를 포함하는 난연 조성물
CN106243677A (zh) * 2016-08-24 2016-12-21 五行科技股份有限公司 一种可用于汽车燃油系统的阻燃型玻纤增强聚酮复合材料
KR101888071B1 (ko) 2017-04-20 2018-08-14 주식회사 효성 가공 안정성 및 기계적 물성이 개선된 폴리케톤 수지 조성물
CN107513263B (zh) * 2017-10-19 2020-08-04 威海联桥新材料科技股份有限公司 一种热塑性弹性体垫片材料及其生产方法
FR3077013B1 (fr) * 2018-01-24 2023-12-15 Aptar France Sas Dispositif de distribution de produit fluide.
KR101894810B1 (ko) * 2018-06-15 2018-09-04 주식회사 효성 폴리케톤 및 ａｂｓ를 포함하는 블렌드 및 그 제조방법
CN109354857B (zh) * 2018-11-09 2020-10-16 武夷学院 微发泡pok复合材料及其制备方法和用途
CN110684189B (zh) * 2019-11-11 2021-11-30 黄河三角洲京博化工研究院有限公司 一种聚酮的合成方法
CN111607077A (zh) * 2020-06-24 2020-09-01 黄河三角洲京博化工研究院有限公司 一种聚酮的制备方法

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EP3327055A1 (fr) * 2016-11-28 2018-05-30 Carl Freudenberg KG Mélange polymère pour joints d'étanchéité

Also Published As

Publication number Publication date
EP1117724A1 (fr) 2001-07-25
DE19846051A1 (de) 2000-04-13
CN1322221A (zh) 2001-11-14
AU6196199A (en) 2000-04-26
KR20010080019A (ko) 2001-08-22
BR9914316A (pt) 2001-08-07
JP2002526330A (ja) 2002-08-20

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