EP0802947A1 - Matieres de moulage polyoxymethylene stables aux agents atmospheriques - Google Patents

Matieres de moulage polyoxymethylene stables aux agents atmospheriques

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Publication number
EP0802947A1
EP0802947A1 EP95937074A EP95937074A EP0802947A1 EP 0802947 A1 EP0802947 A1 EP 0802947A1 EP 95937074 A EP95937074 A EP 95937074A EP 95937074 A EP95937074 A EP 95937074A EP 0802947 A1 EP0802947 A1 EP 0802947A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
group
molding compositions
weight
thermoplastic molding
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Withdrawn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
EP95937074A
Other languages
German (de)
English (en)
Inventor
Sabine Kielhorn-Bayer
Ulrich Eichenauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0802947A1 publication Critical patent/EP0802947A1/fr
Withdrawn legal-status Critical Current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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • R 1 , R 2 , R 3 are the same or different radicals
  • R 4 , R 5 are independently hydrogen or one
  • n is an integer from 1 to 3, or a triazine derivative of the formula II or its
  • R a is hydrogen, an aliphatic radical having 1 to 12 carbon atoms, a phenyl radical,
  • R 6 represents a C 1 -C 4 alkyl group
  • R 7 , R 8 are the same or different radicals hydrogen or
  • R 9 is hydrogen or a
  • Is methyl group and m is an integer from 0 to 20,
  • R b , R c independently of one another represent hydrogen, halogen, a cyano group or a C 1 - to C 4 -alkyl group
  • Amine compound E 0 to 2% by weight of at least one stabilizer selected from the group of benzotriazole derivatives or benzophenone derivatives or aromatic benzoate derivatives F) 0 to 80% by weight of conventional processing aids and
  • the invention relates to the use of such molding compositions for the production of moldings of any kind and the moldings thus obtained.
  • POM polymers are characterized by a large number of excellent properties, so that they are suitable for a wide variety of technical applications.
  • POM molding compositions which contain a sterically hindered phenol with triazine functionality are distinguished by improved UV stability.
  • Sterically hindered amines based on oxopiperazyltriazine are used according to EP-A 448 037 for UV stabilization of POM.
  • Combinations of sterically hindered amines and benzotriazole compounds for POM are known from EP-A 171 941 and JP-A 60/195 155 and 63/193 950.
  • DE-A 44 04 081 proposes the addition of certain types of carbon black to benzotriazole compounds and sterically hindered amines.
  • EP-A 586 988 discloses the addition of small amounts of polyamide in combination with benzotriazoles and sterically hindered amines for UV stabilization. From EP-A 293 253, EP-A 328 714 and EP-A 289 142
  • DE-A 33 15 115 also discloses the addition of polypiperidine compounds which are said to bring about increased stability against oxidation.
  • the object of the present invention was therefore to improve the weather stability of polyoxymethylene molding compositions.
  • the stabilizer combination according to the invention synergistically increases the weathering stability of the polyoxymethylene, so that cracking has been considerably minimized even for long-term use under extreme conditions.
  • the molding compositions according to the invention contain 10 to 99, preferably 40 to 99% by weight and in particular 50 to 99% by weight of a polyoxymethylene homopolymer or copolymer.
  • these polymers have at least 50 mol% of recurring units -CH 2 O- in the main polymer chain.
  • the homopolymers are generally prepared by polymerizing formaldehyde or trioxane, preferably in the presence of suitable catalysts.
  • polyoxymethylene copolymers are preferred as component A, in particular those which, in addition to the repeating units -CH 2 O-, also contain up to 50, preferably 0.1 to 20 and in particular 0.3 to 10 mol% of repeating units
  • R 1 to R 1 independently of one another are a hydrogen atom, a C 1 to C 4 alkyl group or a halogen-substituted alkyl group having 1 to 4 C atoms and R 5 is a -CH 2 -, -CH 2 O-, a C 1 - to
  • n has a value in the range from 0 to 3.
  • groups can advantageously be introduced into the copolymers by ring opening of cyclic ethers.
  • Preferred cyclic ethers are those of the formula
  • R 4 to R 5 and n have the meaning given above.
  • examples include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane and 1,3-dioxepane as cyclic ethers and linear oligo- or polyformals such as polydioxolane or polydioxepane as comonomers.
  • component A) are oxymethylene terpolymers which, for example, by reacting trioxane, one of the cyclic ethers described above, with a third monomer, preferably a bifunctional compound of the formula
  • Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in a molar ratio of 2: 1 and diether from 2 mol of glycidyl compound and 1 mol of an aliphatic diol with 2 to 8 carbon atoms, such as, for example, the diglycidyl ether of ethylene glycol, 1 , 4-butanediol, 1,3-butanediol, cyclobutane-1,3-diol, 1,2-propanediol and cyclohexane-1,4-diol, to name just a few examples.
  • the preferred polyoxymethylene copolymers have melting points of at least 150 ° C. and molecular weights (weight average) M w in the range from 5000 to 200,000, preferably from 7000 to 150,000. End group-stabilized polyoxymethylene polymers which have CC bonds at the chain ends are particularly preferred.
  • the molding compositions according to the invention contain, as component B), 0.05 to 2, preferably 0.1 to 1 and in particular 0.2 to 0.6% by weight of an isocyanurate of the formula I.
  • R 1 , R 2 , R 3 are the same or different radicals
  • R 4 , R 5 are independently hydrogen or one
  • n is an integer from 1 to 3, or a triazine derivative of the formula II or mixtures thereof
  • R a is hydrogen, an aliphatic radical having 1 to 12 carbon atoms, a phenyl radical,
  • R 6 represents a C 1 -C 4 alkyl group
  • R 7 , R 8 are the same or different radicals hydrogen or
  • R 9 is hydrogen or a
  • Is methyl group and m is an integer from 0 to 20,
  • R b , R c independently of one another represent hydrogen, halogen, a cyano group or a C 1 - to C 4 -alkyl group.
  • Preferred radicals R 4 and R 5 are hydrogen or methyl and n is preferred 1.
  • Preferred radicals R b and R c are chlorine, fluorine, tertiary butyl, methyl and hydrogen.
  • a particularly preferred compound I is triglycidyl isocyanurate:
  • Triglycidyl isocyanurate is available under the trademark Araldite ® PT 810 (Ciba Geigy) in the trade. Processes for the preparation of the isocyanurates of the formula I are known to the person skilled in the art, for which reason further details are unnecessary.
  • Triazine derivatives of formula II are under the trademark
  • Tinuvin ® (Ciba Geigy) commercially available.
  • Preferred triazine derivative as component B) is .
  • Suitable sterically hindered phenols C) are in principle all compounds with a phenolic structure which have at least one sterically demanding group, preferably at least 2 sterically hindered OH groups per molecule on the phenolic ring.
  • R 1 and R 7 are an alkyl group, a substituted alkyl group or a substituted triazole group, where the radicals R 1 and R 2 may be the same or different and
  • R 3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group. Antioxidants of the type mentioned are described for example in the
  • Another group of preferred sterically hindered phenols is derived from substituted benzene carboxylic acids, in particular substituted benzene propionic acid. Particularly preferred compounds from this class are
  • R 4 , R 5 , R 7 and R 8 independently of one another are C 1 -C 8 -alkyl groups, which in turn can be substituted (at least one of them is a sterically demanding group) and R 6 is a divalent aliphatic radical with 1 to 10 C- Atoms that can also have CO bonds in the main chain.
  • Examples include sterically hindered phenols:
  • the antioxidants (C) which can be used individually or as mixtures, are used in an amount of 0.05 to 2% by weight, preferably 0.1 to 1.0% by weight and in particular 0.2 to
  • the molding compositions according to the invention contain as component D) 0.05-2, preferably 0.1-1 and in particular 0.2-0.6% by weight of at least one sterically hindered amine compound, for example compounds of the formula preferably come
  • R is the same or different alkyl radicals
  • R ' is hydrogen or an alkyl radical
  • a ' is an optionally substituted 2- or 3-membered
  • Alkylene chain means.
  • Preferred component D are derivatives of 2,2,6,6-tetramethylpiperidine such as: 4-acetoxy-2,2,6,6-tetramethylpiperidine,
  • Tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate is suitable.
  • piperidine derivatives such as the dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol or
  • Such compounds are commercially available under the names Tinuvin ® or Chimasorb ® (registered trademark of Ciba-Geigy AG).
  • Uvinul ® 4049 H from BASF AG may be mentioned as a further particularly preferred amine compound D):
  • the molding compositions according to the invention can contain 0-2, preferably 0-1 and in particular 0-0.6% by weight of at least one stabilizer from the group of benzotriazole derivatives or benzophenone derivatives or aromatic benzoate derivatives as component E).
  • Suitable benzotriazole derivatives are:
  • Tinuvin® registered trademark of Ciba Geigy AG.
  • Preferred benzotriazole derivatives are:
  • aromatic benzoate derivatives are p-t-butylphenyl salicylate and p-octylphenyl salicylate.
  • the molding compositions according to the invention can be used as component F)
  • 0 to 80 preferably 0 to 50% by weight and in particular 0 to
  • Potassium titanate whiskers, carbon and preferably glass fibers may be mentioned as reinforcing fillers in amounts of up to 50% by weight, preferably up to 40% by weight, the glass fibers e.g. in the form of glass fabrics, mats, nonwovens and / or glass silk rovings or cut glass silk made of low-alkali E-glass with a diameter of 5 to 200 ⁇ m, preferably 8 to 50 ⁇ m, the fibrous fillers can be used according to their Incorporation preferably have an average length of 0.05 to 1 ⁇ m, in particular 0.1 to 0.5 ⁇ m.
  • Other suitable fillers are, for example, wollastonite, calcium carbonate, glass balls, quartz powder, silicon and boron nitride or mixtures of these fillers.
  • Preferred combinations of fillers are: wollastonite with glass fibers, with mixing ratios of 5: 1 to 1: 5 being preferred.
  • additives are, in amounts of up to 50, preferably 0 to 40,% by weight, impact-modifying polymers (also referred to below as rubber-elastic polymers or elastomers).
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no more double bonds, whereas EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, Hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5 -Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodie
  • Hexa-1,5-diene-5-ethylidene-norbornene and dicyclopentadiene are preferred.
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.
  • the EPDM rubbers can also be grafted with other monomers, e.g. with glycidyl (meth) acrylates, (meth) acrylic acid esters and (meth) acrylamides.
  • Another group of preferred rubbers are copolymers of ethylene with esters of (meth) acrylic acid.
  • the rubbers can also contain monomers containing epoxy groups. These epoxy group-containing monomers are preferably obtained by adding epoxy group-containing monomers of the general
  • R 6 - R 10 represent hydrogen or alkyl groups with 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.
  • the radicals R 6 to R 8 are preferably hydrogen, where m is 0 or 1 and g is 1.
  • the corresponding compounds are allyl glycidyl ether and vinyl glycidyl ether.
  • Preferred compounds of the formula II are epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate and glycidyl methacrylate.
  • the copolymers advantageously consist of 50 to 98% by weight
  • Ethylene monomers containing 0 to 20% by weight of epoxy groups and the remaining amount of (meth) acrylic acid esters. Copolymers of are particularly preferred
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • the ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.
  • Preferred elastomers are also emulsion polymers, the production of which e.g. in Blackley in the monograph "Emulsion Polymerization" is described.
  • the emulsifiers and catalysts that can be used are known per se.
  • homogeneous elastomers or those with a shell structure can be used.
  • the shell-like structure is determined by the order of addition of the individual monomers;
  • the morphology of the polymers is also influenced by this order of addition.
  • Representative here are as monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
  • monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
  • These monomers can be combined with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate,
  • the soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers can be the core, the outer shell or a middle shell (for elastomers with more than two shell structure); in the case of multi-layer elastomers, several shells can also consist of a rubber phase.
  • one or more hard components are involved in the construction of the elastomer, these are generally obtained by polymerizing styrene, acrylonitrile, methacrylonitrile,
  • emulsion polymers which have reactive groups on the surface.
  • groups are e.g. Epoxy, amino or amide groups, as well as functional groups, by using monomers of the general formula
  • R 15 is hydrogen or a C 1 to C 4 alkyl group
  • R 16 is hydrogen, a C 1 to C 8 alkyl group or an aryl group, in particular phenyl,
  • R 17 is hydrogen, a C 1 to C 10 alkyl, a C 6 to C 12 aryl group or OR 18
  • R 18 is a C 1 to C 8 alkyl or C 6 to C 12 aryl group, which may optionally be substituted by O- or N-containing groups,
  • X is a chemical bond, a C 1 to C 10 alkylene or
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide methacrylamide and substituted esters of acrylic acid or methacrylic acid such as
  • the particles of the rubber phase can also be crosslinked.
  • Monomers which act as crosslinkers are, for example
  • So-called graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds, which react at different rates during the polymerization.
  • Compounds are preferably used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerizes much slower (polymerize).
  • the different polymerization speeds result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.
  • graft-crosslinking monomers are monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate,
  • graft polymers with a core and at least one outer shell are to be mentioned, which have the following structure:
  • Buta-1,3-diene, isoprene and n-butyl acrylate or their copolymers can be used. These products can also be prepared by using crosslinking monomers or monomers with reactive groups.
  • the elastomers F) described can also be produced by other conventional methods, e.g. by suspension polymerization. Of course, mixtures of the rubber types listed above can also be used.
  • the molding compositions according to the invention can also contain other conventional additives and processing aids.
  • Additives for trapping formaldehyde (formaldehyde scavenger), plasticizers, lubricants, adhesion promoters, light stabilizers and pigments are only mentioned here as examples.
  • the proportion of such additives is generally in the range from 0.001 to 5% by weight. It goes without saying that these stabilizers should be different from B) to D) and optionally E).
  • the molding compositions according to the invention can contain a maleic-formaldehyde condensate as nucleating agent.
  • Suitable products are e.g. in the
  • thermoplastic molding compositions according to the invention are produced by mixing the components in a manner known per se, which is why detailed information is unnecessary here.
  • the components are advantageously mixed in an extruder.
  • thermoplastic molding compositions according to the invention are distinguished by a balanced spectrum of properties, in particular by the very good weather stability. Accordingly, they are suitable for the production of moldings of any kind, in particular for applications in the automotive sector, such as, for example, external handles, fuel caps or bumpers.
  • component A component A
  • component A) was compounded, each with 0.4% by weight of components B) to F), on a twin-screw extruder at 220 ° C., degassed, and extruded and pelletized as a strand.
  • the UV stability was tested as follows: Injection molded bodies (round disks, thickness 2 mm, diameter 60 mm) produced at 200 ° C. were weathered in an Atlas Weather Ometer according to the guidelines of the Society Automotive Engineers (SAE) according to J 1885 for 700 h . Every 100 h during the weathering, the surface of the round disks was examined for cracks using a light microscope at 60 ⁇ magnification.
  • SAE Society Automotive Engineers

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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)

Abstract

L'invention concerne des matières de moulage thermoplastiques qui contiennent A) entre 10 et 99 % en poids d'un homo- ou d'un copolymérisat de polyoxyméthylène, B) entre 0,05 et 2 % en poids d'un isocyanurate de la formule (I) dans laquelle R?1, R2, R3¿ désignent des restes (1) similaires ou différents et R4, R5 désignent indépendamment l'un de l'autre hydrogène ou un groupe alkyle C¿1?-C4 et n vaut un nombre entier compris entre 1 et 3, ou un dérivé triazine de la formule (II) ou leurs mélanges, dans laquelle R?a¿ désigne hydrogène, un reste aliphatique ayant entre 1 et 12 atomes de C, un reste phényle, (a), (b), où R6 désigne un groupe alkyle C¿1?-C4, (c) où R?7, R8¿ désignent des restes hydrogène ou alkyle C¿1?-C4 identiques ou différents, (d) où R?9¿ désigne hydrogène ou un groupe méthyle et m vaut un nombre entier compris entre 0 et 20, (e), (f), Rb, Rc désignent indépendamment l'un de l'autre hydrogène, halogène, groupe cyano ou un groupe alkyle C¿1?-C4, C) entre 0,05 et 2 % en poids d'au moins un composé phénol empêché stériquement, D) entre 0,05 et 2 % en poids d'au moins un composé amine empêché stériquement, E) entre 0 et 2 % en poids d'au moins un agent de stabilisation sélectionné dans le groupe des dérivés benzotriazole ou des dérivés benzophénone ou des dérivés benzoate aromatiques, F) entre 0 et 80 % en poids d'auxiliaires de traitement classiques et d'additifs, le pourcentage en poids des constituants A) à F) formant un total de 100 %.
EP95937074A 1994-11-26 1995-11-15 Matieres de moulage polyoxymethylene stables aux agents atmospheriques Withdrawn EP0802947A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4442167 1994-11-26
DE19944442167 DE4442167A1 (de) 1994-11-26 1994-11-26 Witterungsstabile Polyoxymethylenformmassen
PCT/EP1995/004484 WO1996017009A1 (fr) 1994-11-26 1995-11-15 Matieres de moulage polyoxymethylene stables aux agents atmospheriques

Publications (1)

Publication Number Publication Date
EP0802947A1 true EP0802947A1 (fr) 1997-10-29

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EP95937074A Withdrawn EP0802947A1 (fr) 1994-11-26 1995-11-15 Matieres de moulage polyoxymethylene stables aux agents atmospheriques

Country Status (4)

Country Link
EP (1) EP0802947A1 (fr)
JP (1) JPH10509995A (fr)
DE (1) DE4442167A1 (fr)
WO (1) WO1996017009A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5172094B2 (ja) * 2003-10-02 2013-03-27 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
ES2463674T3 (es) 2009-01-19 2014-05-28 Basf Se Pigmentos negros orgánicos y su preparación

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619956A (en) * 1985-05-03 1986-10-28 American Cyanamid Co. Stabilization of high solids coatings with synergistic combinations
US4996253A (en) * 1988-11-10 1991-02-26 Hoechst Celanese Corporation UV-light stabilized polyoxymethylene molding compositions
TW222292B (fr) * 1991-02-21 1994-04-11 Ciba Geigy Ag

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9617009A1 *

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WO1996017009A1 (fr) 1996-06-06
JPH10509995A (ja) 1998-09-29
DE4442167A1 (de) 1996-05-30

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