EP2760935A1 - Matières moulables stabilisées, à base de polyamide et de copolymères asa - Google Patents

Matières moulables stabilisées, à base de polyamide et de copolymères asa

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Publication number
EP2760935A1
EP2760935A1 EP12761925.2A EP12761925A EP2760935A1 EP 2760935 A1 EP2760935 A1 EP 2760935A1 EP 12761925 A EP12761925 A EP 12761925A EP 2760935 A1 EP2760935 A1 EP 2760935A1
Authority
EP
European Patent Office
Prior art keywords
component
weight
thermoplastic molding
molding composition
composition according
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Withdrawn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
EP12761925.2A
Other languages
German (de)
English (en)
Inventor
Rolf Minkwitz
Martin Weber
Marko Blinzler
Wenke WOLLNY
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.)
Ineos Styrolution Europe GmbH
Original Assignee
Styrolution GmbH
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 Styrolution GmbH filed Critical Styrolution GmbH
Priority to EP12761925.2A priority Critical patent/EP2760935A1/fr
Publication of EP2760935A1 publication Critical patent/EP2760935A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08L51/003—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 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/36—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/42—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising cyclic compounds containing one carbon-to-carbon double bond in the side chain as major constituent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2413/00—Characterised by the use of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C08J2425/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—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
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers

Definitions

  • the present invention relates to thermoplastic molding compositions comprising at least one polyamide, at least one styrene copolymer and at least one impact-modifying graft rubber without olefinic double bond in the rubber phase.
  • the invention also relates to the preparation of stabilized molding compositions of polyamide and copolymers of acrylonitrile, styrene and acrylic esters (ASA).
  • ASA acrylic esters
  • Stabilized thermoplastic molding compositions of various types have been known for years.
  • Polymer blends (blends) of polyamide and styrene polymers are widely used due to their favorable property profile for many applications, in particular their high impact strength, good flowability and chemical resistance.
  • known polymer blends of polyamide and styrenic polymer have inadequate UV light resistance for some applications.
  • EP-A 1 263 855 discloses stabilized molding compositions which, in addition to a polyethylene or polypropylene or their copolymer, also compounds of the following formulas (I), (II), (III), (IV), (V) or (VI) of the present invention in combination with an acrylate rubber-modified vinyl aromatic copolymer (ASA, acrylonitrile / styrene / acrylic ester) or polycarbonate in amounts up to 1, 5%.
  • ASA acrylate rubber-modified vinyl aromatic copolymer
  • ASA acrylonitrile / styrene / acrylic ester
  • a disadvantage of these compositions is the low heat resistance of the molding compositions.
  • US Pat. No. 4,692,486 discloses stabilizer mixtures comprising compounds of the formulas (I) and (III) of the present application for polypropylene, polyurethane and polystyrene, the amounts of the individual stabilizer components used being less than or equal to 0.1% by weight.
  • a disadvantage of these mixtures is also the low heat resistance of the molding compositions.
  • DE-A 103 16 198 discloses stabilizer mixtures for different types of thermoplastic polymers, such as polypropylene.
  • the stabilizer mixtures are ternary mixtures.
  • For the three components of this mixture a variety of possible generic and special compounds is described in each case.
  • a stabilizer mixture is described which also contains compounds of the formulas (I), (II) and (III) of the present application.
  • Each of the three stabilizer components may preferably be present in amounts of from 0.05 to 1% by weight, based on the organic material.
  • a disadvantage of these mixtures is the strong decrease of the multi-axial toughness during weathering (examination at different temperatures, humidity, etc.).
  • the present invention has for its object to provide improved molding compositions based on polyamide and acrylonitrile / styrene / acrylic ester molding compositions. Accordingly, new and improved thermoplastic molding compositions are described, containing as components (or consisting of): a) 3 to 91, 8 wt .-% of at least one polyamide as component A, b) 3 to 91, 8 wt .-% of one or more Styrene copolymers which have no units derived from maleic anhydride, as component B, c) 3 to 91, 8 wt .-% of one or more impact-modifying graft rubbers without olefinic double bond in the rubber phase as component C, d) 0.2 to 1, 5 wt .-% of a compound of formula (I) as component D. e) 0 to 0.9 wt .-% of a mixture of formula (II) as component E.
  • n 2 to 20, in particular f) 0 to 0.9 wt .-% of a compound of formula (III) as component F
  • n 2 to 20 g) 1 to 25 wt .-% of one or more styrene copolymers, based on the total component G, 0.5 to 5 wt .-% of maleic anhydride derived units, as component G, h) 1 up to 30% by weight of one or more further rubbers based on olefinic monomers without core-shell structure and with at least 0.1% by weight of functional monomers as component H,
  • component I 0 to 40% by weight of one or more additives derived from the components D, E, F, G and H are different, as component I, and j) from 0 to 50% by weight of fibrous or particulate fillers as component J, with the proviso that when the amount of component E is 0% by weight (That is, no component E is present), at least one of the components of the formulas (III), (IV), (V) or (VI) in an amount of 0.01 to 0.9 wt .-%, preferably 0.1 to 0.8 wt .-%, particularly preferably 0.2 to 0.8 wt .-%, wherein the wt .-% each based on the total weight of the components A to J, and these together 100 wt. -% result.
  • the invention also relates to thermoplastic molding compositions, characterized in that the swelling index of the component C is from 6 to 20.
  • the invention also relates to thermoplastic molding compositions, characterized in that the component B used is a copolymer of acrylonitrile, styrene and / or ⁇ -methylstyrene, phenylmaleinimide, methyl methacrylate or mixtures thereof.
  • the invention also relates to thermoplastic molding compositions, characterized in that is used as component C, a mixture of an acrylic I at-Sty ro I-Acry Ii tri I (ASA) - graft polymer, the 55 to 80 wt .-%, based on C, an elastomer-crosslinked acrylic ester polymer C1 and 45 to 25 wt .-%, based on C, a graft C2 from a vinyl aromatic monomer and one or more polar, copolymerizable, ethylenically unsaturated monomers, optionally a further copolymerizable, ethylenically unsaturated monomer in a weight ratio 80:20 to 65:35 contains.
  • ASA acrylic I at-Sty ro I-Acry Ii tri I
  • the invention also relates to thermoplastic molding compositions, characterized in that C1 to 0.01 to 20 wt .-%, preferably 0.1 to 5 wt .-%, of a crosslinking monomer, preferably Butylendiacrylat, divinylbenzene, butanediol dimethacrylate, trimethylolpropane tri ( meth) acrylate, diallyl methacrylate, diallyl maleate, dialyl fumarate, triallyl methacrylate, triallyl isocyanurate, particularly preferably diallyl phthalate, allyl methacrylate and / or dihydrodicyclopentadienyl acrylate.
  • a crosslinking monomer preferably Butylendiacrylat, divinylbenzene, butanediol dimethacrylate, trimethylolpropane tri ( meth) acrylate, diallyl methacrylate, diallyl maleate, dialyl fumarate, trially
  • the invention also relates to thermoplastic molding compositions, characterized in that the average particle diameter of component C is between 50 and 1200 nm.
  • the invention also relates to thermoplastic molding compositions, characterized in that one uses the components D to E in a weight ratio of 3: 1 to 1: 1 and the components E to F in a weight ratio of 2: 1 to 0.5: 1.
  • the invention also relates to thermoplastic molding compositions, characterized in that component C1 contains from 2 to 99% by weight of butyl acrylate.
  • the invention also relates to thermoplastic molding compositions, characterized in that is used as the vinyl aromatic component in C2 styrene or ⁇ -methylstyrene.
  • the invention also relates to thermoplastic molding compositions, characterized in that is used as the ethylenically unsaturated component in C2 acrylonitrile and / or alkyl methacrylates and / or alkyl acrylates having C 1 to C 8 alkyl radicals.
  • the invention also relates to thermoplastic molding compositions, characterized in that is used as component C is a rubber with monomodal or bimodal particle size distribution.
  • the invention also relates to thermoplastic molding compositions, characterized in that component G comprises 1, 0 to 2.5 wt .-% of maleic anhydride derived units.
  • the invention also relates to thermoplastic molding compositions, characterized in that component G comprises 1, 7 to 2.3 wt .-% of maleic anhydride derived units.
  • the invention also relates to thermoplastic molding compositions, characterized in that component A from 0.05 to 0.5 wt .-% triacetonediamine (TAD) end groups.
  • TAD triacetonediamine
  • the invention also relates to thermoplastic molding compositions, characterized in that component H is a copolymer of the following components:
  • the monomers bearing functional groups selected from carboxylic acid, carboxylic acid anhydride, carboxylic ester, carboxylic acid amide, carboxylic imide, amino, hydroxyl, epoxide, urethane or oxazoline groups or mixtures thereof.
  • the invention also provides a process for the preparation of a thermoplastic molding composition as described above, characterized in that the components A, B, C, D, G and H and optionally E, F, I and J at temperatures of 100 to 300 ° C. and a pressure of 1 to 50 bar in any order mixed together, then kneaded and extruded.
  • thermoplastic molding compositions In the process for the preparation of thermoplastic molding compositions, it is possible first to premix a part of component C with a part of component B to give a master batch in a ratio of 1: 1 to 1: 2 and then to mix it with further components A to J to form the thermoplastic molding composition ,
  • thermoplastic molding compositions as described above for the production of moldings, films or fibers.
  • the use of the thermoplastic molding compositions for the production of moldings for automotive components or parts of electronic devices is particularly preferred.
  • the invention also provides moldings, fibers or films of a thermoplastic molding composition as described.
  • the improved thermoplastic molding compositions preferably contain at least one component D and at least one component E, and optionally an additional stabilizer component F.
  • the invention relates to a process for the preparation of the molding compositions described, their use for the production of films, moldings or fibers as well as these films, moldings or fibers.
  • the molding compositions according to the invention have improved weathering resistance compared with the known, stabilized molding compositions, i. an improved heat, light and / or oxygen resistance on.
  • the novel molding materials contain, based on the total weight of the components A, B, C, D, E, F, G, H, I and J, which gives a total of 100 wt .-%,
  • the component F 0.01 to 0.9 wt .-%, preferably 0.1 to 0.8 wt .-%, particularly preferably 0.2 to 0.8 wt .-% is one of the compounds III, IV, V or VI,
  • the weight ratio of component D to component E is generally in the range from 4: 1 to 0.25: 1, preferably 4: 1 to 1: 1, more preferably 3: 1 to 1: 1.
  • the weight ratio of component E to F is generally in the range from 2: 1 to 0.5: 1.
  • Commonly used molding compositions contain (or consist of): a) 10 to 75% by weight of at least one polyamide as component A.
  • Component A is a compound having Component A:
  • thermoplastic molding compositions of one or more polyamides according to the invention preferably contain, based on the entire component A, 0.05 to 0.5 wt .-%, preferably 0.1 to 0.2 wt .-% triacetonediamine (TAD) - end groups.
  • TAD triacetonediamine
  • Component A is contained in the molding compositions in an amount of 3 to 91, 8 wt .-%, often from 10 to 75 wt .-%, often 30 to 60 wt .-%. Unless otherwise stated, the weight percent refers to the total molding composition.
  • TAD-free polyamides may be TAD-free polyamides, TAD-containing polyamides or else mixtures of polyamides with TAD end groups with polyamides without TAD end groups.
  • a polyamide is used, from whose end groups at least one of the piperidine compound TAD can be derived. It is also possible to use mixtures of two or more different polyamides as component A. For example, polyamides of different basic structure but the same end group can be used. However, it is also possible to use polyamides having the same backbone and end groups which are derived from different piperidine compounds. Furthermore, it is possible to use mixtures of polyamides having different levels of end groups derived from the piperidine compounds.
  • Polyamides are understood as meaning homopolymers or copolymers of synthetic long-chain polyamides which, as an essential constituent, have recurring amide groups in the polymer main chain.
  • Examples of such polyamides are u. a. Nylon 6 (polycaprolactam), nylon 6,6 (polyhexamethylene adipamide), nylon 4,6 (polytetra- nyladipamide), nylon 5, 10 (polypentamethylene adipamide), nylon 6, 10 (polyhexamethylene sebacamide), nylon 7 (polyene ant- holactam), nylon 1 1 (polyundexolactam), nylon 12 (polydodecanolactam). These polyamides are known to carry the generic name nylon.
  • the preparation of polyamides can be carried out in particular by two methods.
  • the amino and carboxyl end groups of the starting monomers or starting oligomers react with each other to form an amide group and water.
  • the water can then be removed from the polymer mass.
  • the amino and amide end groups of the starting monomers or starting oligomers react with one another to form an amide group and ammonia.
  • the ammonia can then be removed from the polymer mass.
  • Suitable starting monomers or starting oligomers for the preparation of polyamides are, for example:
  • C 2 - to C 2 o-, preferably C 3 - to C 8 -amino acids such as 6-aminocaproic acid, 1 1 -aminoundecanoic acid, as well as their dimers, trimers, tetramers, pentamers or hexamers
  • C 2 - to C 2 o- amino acid amides such as 6-aminocaproic acid amide, 1 1 -amino undecanoic acid amide and their dimers, trimers, tetramers, pentamers or hexamers
  • chlorides such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid, and their dimers, trimers, tetramers, pentamers or hexamers
  • TAD triacetonediamine
  • the preparation of the polyamides A is known per se or can be carried out by methods known per se.
  • the polymerization or polycondensation of the starting monomers for example in the presence of the piperdine compounds, can be carried out under customary process conditions, the reaction being able to take place continuously or discontinuously.
  • the piperidine compounds can - if present - but also with a chain regulator, as it is usually used for the production of polyamides, combined. Information on suitable processes can be found, for example, in WO 1995/28443, WO 1999/41297 or DE-A 198 12 135.
  • the TAD compound is bonded to the polyamide by reaction of at least one of the amide-forming groups R 7 .
  • the secondary amino groups of the piperidine ring systems do not react because of steric hindrance.
  • polyamides prepared by copolycondensation of two or more of the above monomers or their components e.g. Copolymers of adipic acid, isophthalic acid or terephthalic acid and hexamethylenediamine or copolymers of caprolactam, terephthalic acid and hexamethylenediamine.
  • Such partially aromatic copolyamides contain from 40 to 90% by weight of units derived from terephthalic acid and hexamethylenediamine.
  • a small proportion of the terephthalic acid, preferably not more than 10% by weight, of the total aromatic dicarboxylic acids used may be replaced by isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the carboxyl groups are in the para position.
  • a partially aromatic polyamide is nylon 9T, which is derived from nonanediamine and terephthalic acid.
  • R 1 is hydrogen or a C 1 to C 4 alkyl group
  • R 2 is a C 1 to C 4 alkyl group or hydrogen and,
  • R 3 is a Ci to C 4 alkyl group or hydrogen.
  • Particularly preferred diamines of the formula (VII) are bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) -2,2-propane or bis (4-amino-3-methylcyclohexyl) -2,2-propane.
  • 1, 3 or 1,4-cyclohexanediamine or isophoronediamine may be mentioned as further diamines.
  • the partially aromatic copolyamides contain units which are derived from ⁇ -caprolactam and / or units which are derived from adipic acid and hexamethylenediamine.
  • the proportion of units derived from ⁇ -caprolactam is up to 50% by weight, preferably 20 to 50% by weight, in particular 25 to 40% by weight, while the proportion of units derived from adipic acid and hexamethylenediamine, up to 60 wt .-%, preferably 30 to 60 wt .-% and in particular 35 to 55 wt .-% is.
  • the copolyamides may also contain both units of ⁇ -caprolactam and units of adipic acid and hexamethylenediamine; in this case, care must be taken that the proportion of units which are free of aromatic groups is at least 10% by weight, preferably at least 20% by weight.
  • the ratio of the units derived from ⁇ -caprolactam and from adipic acid and hexamethylenediamine is subject to no particular restriction.
  • Polyamides having from 50 to 80, in particular from 60 to 75,% by weight of units derived from terephthalic acid and hexamethylenediamine and from 20 to 50, preferably from 25 to 40,% by weight of units derived from ⁇ -Caprolactam derived.
  • the partially aromatic copolyamides can be prepared, for example, by the process described in EP-A 0 129 195 and EP-A 0 129 196.
  • Preferred partially aromatic polyamides are those which have a content of triamine units, in particular units of dihexamethylenediamine of less than 0.555% by weight, ie 0 to 0.554% by weight, preferably 0 to 0.45% by weight, particularly preferably 0 to 0.3% by weight.
  • polyamides having a melting point above 200 ° C Preference is given to linear polyamides having a melting point above 200 ° C.
  • Preferred polyamides are Polyhexamethylenadipinklamid, Polyhexamethylen- sebacinklamid and polycaprolactam and polyamide 6 / 6T and polyamide 66 / 6T and polyamides containing cyclic diamines as comonomers.
  • the polyamides generally have a relative viscosity of 2.0 to 5, as determined on a 1 wt.% Solution in 96 wt.% Sulfuric acid at 23 ° C, which has a number average molecular weight of about 15,000 to 45,000 equivalent.
  • Polyamides having a relative viscosity of 2.4 to 3.5, in particular 2.5 to 3.4, are preferably used.
  • polyamides which are e.g. are obtainable by condensation of 1, 4-diaminobutane with adipic acid at elevated temperature (polyamide 4.6). Manufacturing processes for polyamides of this structure are known e.g. in EP-A 038 094, EP-A 038 582 and EP-A 039 524.
  • Component B is a compound having Component B:
  • the thermoplastic molding compositions according to the invention contain one or more styrene copolymers.
  • any suitable co-monomers can be present in the copolymers in addition to styrene. It is preferably a styrene-acrylonitrile copolymer, alpha-methylstyrene-acrylonitrile copolymer or an N-phenyl-maleimide-styrene copolymer.
  • Component B is contained in the molding compositions in an amount of 3 to 91, 8 wt .-%, often 10 to 75 wt .-%. Also amounts of 10 to 20 wt .-% of component B have been proven in the molding compositions.
  • component B in principle, all styrene-acrylonitrile copolymers known to those skilled in the art and described in the literature, ⁇ -methylstyrene-acrylonitrile copolymers, N-phenylmaleimide-acrylonitrile copolymer and mixtures thereof can be used, provided that their mixtures have a viscosity number VZ (measured according to DIN 53727 at 25 ° C as 0.5% strength by weight solution in dimethylformamide, this method of measurement also applies to all viscosity numbers VZ mentioned below which are equal to or less than 85 ml / g.
  • Preferred components B are composed of 50 to 90% by weight, preferably 60 to 85% by weight, in particular 70 to 83% by weight, styrene and 10 to 50% by weight, preferably 15 to 40% by weight , in particular 17 to 30 wt .-%, acrylonitrile and 0 to 5 wt .-%, preferably 0 to 4 wt .-%, in particular 0 to 3 wt .-%, of further monomers, wherein the wt .-% in each case are based on the weight of the components in Copolymer B and together give 100% by weight.
  • Further preferred components B are composed of 50 to 90 wt .-%, preferably 60 to 80 wt.%, In particular 65 to 78 wt .-%, ⁇ -methylstyrene and 10 to 50 wt .-%, preferably 20 to 40 wt. -%, In particular 22 to 35 wt .-%, acrylonitrile and 0 to 5 wt .-%, preferably 0 to 4 wt .-%, in particular 0 to 3 wt .-%, of other monomers, wherein the wt. % each are based on the weight of the components in copolymer B and together give 100% by weight.
  • Also preferred components B are mixtures of these styrene-acrylonitrile copolymers and ⁇ -methylstyrene-acrylonitrile copolymers with N-phenylmaleimide-styrene-acrylonitrile terpolymers or N-phenylmaleimide-styrene copolymers.
  • all copolymerizable monomers can be used, for example p-methylstyrene, t-butylstyrene, vinylnaphthalene, alkylacrylates and / or alkylmethacrylates, for example those with C 1 -C 8 -alkyl radicals, N-phenylmaleimide and mixtures thereof.
  • the copolymers of component B can be prepared by known methods. They can be e.g. by free-radical polymerization, in particular by emulsion polymerization, suspension polymerization, solution polymerization or mass polymerization. They have viscosity numbers in the range of 40 to 160 ml / g, which corresponds to average molecular weights Mw (weight average) of 40,000 to 2,000,000 g / mol.
  • Component C are rubber-elastic graft copolymers of vinyl aromatic compounds, in particular of styrene, and vinyl cyanides, in particular acrylonitrile, on polyalkyl acrylate rubbers.
  • Component C is present in the molding compositions in an amount of from 3 to 91, 8 wt .-%, preferably 10 to 50 wt .-%, particularly preferably from 15 to 40 wt .-%. Also 20 to 25 wt .-% of component C are often used.
  • a method for characterizing the crosslinking state of crosslinked polymer particles is the measurement of the swelling index Q1, which according to the literature is a measure of the swellability of a more or less strongly crosslinked polymer by a solvent.
  • Typical swelling agents are, for example, methyl ethyl ketone or toluene.
  • the swelling index results from the quotient of the weights of the swollen gel and the dried gel.
  • the rubbery elastic graft copolymer C is composed of:
  • C2 99 to 1 wt .-%, preferably 45 to 20 wt .-%, in particular 45 to 35 wt .-%, of a graft C2, having a glass transition temperature above 30 ° C. based on C.
  • the component C1 is composed of: C1 1 60 to 99.98 wt .-%, preferably 80 to 99.9 wt .-%, of at least one Ci -8 - alkyl ester of acrylic acid, preferably C 4 to C 8 alkyl acrylates, in particular n-butyl acrylate and / or 2-ethylhexyl acrylate, as component C-1 1,
  • DCPA dihydrodicyclopentadienyl acrylate
  • the component C2 is composed of: C-21 40 to 100 wt .-%, preferably 65 to 85 wt .-% of a vinyl aromatic monomer, in particular of styrene, ⁇ -methyl styrene or N-phenylmalein imide, and
  • Component C is a graft copolymer comprising a graft base C1 and at least one graft C2.
  • the graft copolymer C may have a more or less perfectly pronounced core-shell structure (grafting base C1 represents the core, the grafting pad C2 the shell), but it is also possible that the grafting pad C2 encloses the grafting base C1 only incompletely ., Covered or even the Pfropfauflage C2 the Pfropfgroundlage C1 completely or partially penetrates.
  • the graft base C1 may, in one embodiment of the invention, contain a so-called core, which may be formed from a soft elastomeric polymer or a hard polymer; in the embodiments in which the graft base C1 contains a core, the core is preferably formed from a hard polymer, in particular polystyrene or a styrene copolymer.
  • a so-called core which may be formed from a soft elastomeric polymer or a hard polymer
  • the core is preferably formed from a hard polymer, in particular polystyrene or a styrene copolymer.
  • Such graft cores and their preparation are known in the art and described for example in EP-A 535 456 and EP-A 534 212.
  • grafting bases C1 which differ from each other, for example, in their composition or in particle size.
  • Such mixtures of different grafting bases can be prepared by methods known per se to the skilled person, for example by separately preparing two or more rubber latexes and mixing the appropriate dispersions, separately precipitating the wet rubbers from the corresponding dispersions and, for example, mixing them in an extruder or the corresponding dispersions are worked up completely separately and the graft bases obtained are subsequently mixed.
  • the graft copolymer C may have one or more further graft layers or shells between the graft base C1 and the graft C2, for example with other monomer compositions. Preferably, however, the graft copolymer C has no further graft or graft shells or graft shells apart from the graft C2.
  • the polymer of the graft base C1 usually has a glass transition temperature below 0 °, preferably a glass transition temperature below (-20) ° C, especially below (-30) ° C.
  • a polymer of the graft C2 forming monomers usually has a glass transition temperature of more than 30 ° C, in particular more than 50 ° C (each determined according to the standard DIN 53765).
  • the graft copolymers C usually have an average particle size d 50 of 50 to 1200 nm, preferably 50 to 800 nm, particularly preferably 50 to 600 nm. These particle sizes can be achieved if, as the graft base C1, mean particle sizes d 50 of 50 to 1000 nm, preferably 50 to 700 nm, more preferably 50 to 500 nm used.
  • the particle size distribution is monomodal.
  • the particle size distribution of component C is bimodal, wherein 60 to 90% by weight have an average particle size of 50 to 200 nm and 10 to 40% by weight have an average particle size of 200 to 800 nm on the total weight of the component C.
  • the mean particle size or particle size distribution given are the sizes determined from the integral mass distribution.
  • the graft copolymers C can be prepared by grafting the components C-21 and C-22 onto at least one of the grafting bases C1 listed above. Suitable preparation processes for graft copolymers C are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers C are preferably prepared by free-radical emulsion polymerization in the presence of latices of component C1 at temperatures of 20 to 90 ° C. using water-soluble or oil-soluble initiators such as peroxodisulfate or benzyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
  • Suitable polymerization processes are described in WO 2002/10222, DE-A 28 26 925, DE-A 31 49 358 and DE-C 12 60 135.
  • the structure of the graft is preferably carried out in the emulsion polymerization process, as described in DE-A 32 27 555, DE-A 31 49 357, DE-A 31 49 358, DE-A 34 14 1 18.
  • the defined setting The average particle sizes of 50 to 1200 nm are preferably carried out according to the methods described in DE-C 12 60 135 and DE-A 28 26 925, and Applied Polymer Science, Vol. 9 (1965), page 2929.
  • the use of polymers having different particle sizes is known, for example, from DE-A-28 26 925 and US Pat. No. 5,196,480.
  • the graft base C1 is first prepared by using the or the according to one embodiment of the Acrylic acid esters C-1 used 1 and acting as a crosslinking and / or grafting agent compound C-12, optionally together with the other monoethylenically unsaturated monomers C-13, in aqueous emulsion in a conventional manner at temperatures between 20 and 100 ° C, preferably between 50 and 90 ° C, polymerized.
  • the usual emulsifiers such as alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or resin soaps can be used.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are used.
  • the emulsifiers are used in amounts of from 0.5 to 5% by weight, in particular from 0.7 to 2% by weight, based on the monomers used in the preparation of the graft base C1. In general, a weight ratio of water to monomers of 4: 1 to 0.6: 1 is used.
  • the polymerization initiators are in particular the customary persulfates, such as potassium persulfate. However, redox systems can also be used.
  • the initiators are generally used in amounts of from 0.1 to 1% by weight, based on the monomers used in the preparation of the grafting base C1.
  • Further polymerization auxiliaries may be the customary buffer substances which are used to adjust pH values of preferably 6 to 9, such as sodium bicarbonate and sodium pyrophosphate, and 0 to 3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric ⁇ -methylstyrene be used in the polymerization.
  • the exact polymerization conditions, in particular the type, dosage and amount of the emulsifier, are determined in detail within the ranges given above such that the resulting latex of the crosslinked acrylic acid ester polymer C1 has a d 50 value in the range of 50 to 1000 nm, preferably 50 to 700 nm , more preferably 50 to 500 nm.
  • the particle size distribution of the latex should preferably be narrow with a polydispersity index ⁇ 0.75, corresponding to W. Gurchtie and L. Börger, Analytical Ultracentrifugation of Polymers and Nanoparticles, (Springer, Berlin, 2006).
  • a monomer mixture of component C-21, preferably styrene, component C-22, preferably acrylonitrile and / or a (meth) acrylic ester, and optionally further unsaturated monomers are polymerized.
  • the monomers C-21, C-22 and optionally further unsaturated monomers can be added individually or in a mixture with one another. For example, one can first graft styrene alone, and then a mixture of styrene and acrylonitrile. It is advantageous to carry out this graft copolymerization again on the graft-base crosslinked acrylic acid ester polymer in aqueous emulsion under the usual conditions described above.
  • the graft copolymerization may suitably be carried out in the same system as the emulsion polymerization for the preparation of the grafting base C1, wherein, if necessary, further emulsifier and initiator may be added.
  • the monomer mixture to be grafted in accordance with one embodiment of the invention can be added to the reaction mixture all at once, batchwise in a plurality of stages, for example to build up a plurality of grafting compositions or, preferably, continuously during the polymerization.
  • the graft copolymerization of the mixture of the components C-21, C-22 and optionally further monomers in the presence of the crosslinking acrylic acid ester polymer C1 is carried out in such a way that a degree of grafting of 10 to 70 wt.%, Preferably 20 to 60 wt. , In particular 30 to 55 wt .-%, based on the total weight of component C, resulting in the graft copolymer C. Since the graft yield in the graft copolymerization is not 100%, advantageously a slightly larger amount of the monomer mixture of C-21, C-22 and optionally further monomers should be used in the graft copolymerization than corresponds to the desired degree of grafting.
  • the control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer C is familiar to the skilled worker and can be effected, for example, by the metering rate of the monomers or by addition of a regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), pages 329 to 333).
  • a regulator Chovel, Daniel, ACS Polymer Preprints 15 (1974), pages 329 to 333.
  • In the emulsion graft copolymerization generally from 5 to 15% by weight, based on the graft copolymer, of free, ungrafted copolymer of the components C-21, C-22 and optionally of the further monomers are formed.
  • the proportion of the graft copolymer C in the polymerization product obtained in the graft copolymerization can be determined, for example, by the method described in US 2004/0006178.
  • the preparation of the graft base C1 can be carried out in the presence of seed particles and / or an agglomeration step can be carried out after the preparation of the graft base C1 and before the application of the graft C2.
  • Seed particles generally have a particle size d 50 of 10 to 200 nm, preferably 10 to 180 nm, more preferably 10 to 160 nm. It is preferred to use seed particles which have a narrow width of the particle size distribution. Of these, seed particles which have a monomodal particle size distribution are particularly preferred.
  • the seed particles may in principle be composed of monomers forming elastomeric polymers, for example 1,4-butadiene or acrylates, or of a polymer whose glass transition temperature is more than 0 ° C., preferably more than 25 ° C.
  • the preferred monomers on which these seed particles are based include vinyl aromatic monomers such as styrene, ring-substituted styrenes or ⁇ -methylstyrene, including preferably styrene, acrylonitrile, alkylacrylic acid, alkyl acrylates, including preferably n-butyl acrylate. Also suitable are mixtures of two or more, preferably two, of the monomers mentioned. Very particular preference is given to seed particles of polystyrene or n-butyl acrylate.
  • seed particles are preferably obtained by particle-forming heterogeneous polymerization processes, preferably by emulsion polymerization.
  • the seed particles are presented according to the invention, it being possible to initially produce the seed particles separately, work up and then use. However, it is also possible to prepare the seed particles and then add them without prior workup, the monomer mixture of C-1 1, C-12 and optionally C-13.
  • the agglomeration method is not limited in principle. Thus, physical processes such as freeze or pressure agglomeration processes can be used. But it can also be used chemical methods to the graft base agglomerate. The chemical methods include the addition of electrolytes or of inorganic or organic acids.
  • the agglomeration is carried out by means of an agglomeration polymer.
  • an agglomeration polymer for example, polyethylene oxide polymers, polyvinyl ethers or polyvinyl alcohols may be mentioned.
  • Other suitable agglomerating polymers include copolymers which contain C 1 -C 12 -alkyl acrylates or C 1 -C 12 -methalkyl acrylates and polar comonomers such as acrylamide, methacrylamide, ethylacrylamide, n-butylacrylamide, maleic acid amide or (meth) acrylic acid.
  • these copolymers may be composed of other monomers, including dienes such as butadiene or isoprene.
  • the Agglomerisationspolymerisate may have a multi-stage structure and, for example: have a core / shell structure.
  • Polyacrylates such as polyethyl acrylate and as a shell are particles on (meth) alkyl acrylates and said polar comonomers into consideration.
  • Particularly preferred Agglomerisationspolymerisat is a copolymer of 92 bis
  • the Agglomerisationspolymerisate are usually used in the form of a dispersion. In the agglomeration are usually from 0.1 to 5, preferably from 0.5 to 3 parts by weight of Agglomerisationspolymerisate on
  • the graft copolymers C according to the invention can be used further as they are obtained in the reaction mixture, for example as a latex emulsion or dispersion. Alternatively and as it is preferred for most applications, but they can also be worked up in a further step. Work-up measures are known to the person skilled in the art. This includes, for example, the graft copolymers C being isolated from the reaction mixture, e.g. by spray-drying, shearing or by precipitation with strong acids or by nucleating agents such as inorganic compounds e.g. Magnesium sulfate. However, the graft copolymers C present in the reaction mixture can also be worked up by dehydrating them in whole or in part. It is also possible to carry out the workup by means of a combination of the measures mentioned. The mixing of the components B and C for the preparation of the molding composition can be carried out in any manner by known methods.
  • these components have been prepared, for example, by emulsion polymerization, it is possible to mix the resulting polymer dispersions with one another, then to precipitate the polymers together and to work up the polymer mixture. Preferably, however, the mixing of these components is carried out by co-extruding, kneading or rolling the components, the components having been previously isolated, if necessary, from the solution or aqueous dispersion obtained in the polymerization.
  • the products C of the graft copolymerization obtained in aqueous dispersion can also be only partially dehydrated and mixed as a moist crumb with the hard matrix B, during which the complete drying of the graft copolymers C takes place during the mixing.
  • Component D of the molding compositions of the invention is a compound of the formula (I):
  • the component D is in the molding compositions in an amount of 0.2 to 1, 5 wt .-%, preferably from 0.2 to 1, 2 wt .-%, often from 0.3 to 1, 1 wt .-% used.
  • Component E of the molding compositions of the invention is a compound of the formula (II) or a mixture of several compounds:
  • the component E is used in the molding compositions in an amount of 0 to 0.9 wt .-%, preferably from 0.2 to 0.8 wt .-%, often from 0.2 to 0.7 wt .-%.
  • Component F of the molding compositions of the invention may be a compound of the formula (III) or a mixture:
  • This hindered amine (CAS number 101357-37-3) and its preparation are known to the person skilled in the art and described in the literature (see, for example, US Pat. No. 5,208,132 and the references cited therein). It is sold by ADEKA under the name Adeka Stab ® LA-68.
  • a compound of the formula (V) or a mixture can be used:
  • This sterically hindered amine (CAS number 192268-64-7) and its preparation are known to the person skilled in the art and described in the literature (see, for example, EP-A-782 994 and the references cited therein). It is sold by BASF SE under the name Chimassorb ® 2020.
  • the component F is used in the molding compositions in an amount of 0 to 0.9 wt .-%, preferably from 0.1 to 0.8 wt .-%, often from 0.2 to 0.8 wt .-%.
  • Component G is used in the molding compositions in an amount of 0 to 0.9 wt .-%, preferably from 0.1 to 0.8 wt .-%, often from 0.2 to 0.8 wt .-%.
  • thermoplastic molding compositions according to the invention contain styrene copolymers which, based on the entire component G, 0.5 to 5 wt .-%, preferably 1 to 2.5, in particular 1, 9 to 2.3 wt .-% have derived from maleic anhydride units. This proportion is particularly preferably 2 to 2.2% by weight, especially about 2.1% by weight.
  • component G is a styrene-acrylonitrile-maleic anhydride terpolymer or a styrene-N-phenylmaleimide-maleic anhydride terpolymer.
  • the proportion of acrylonitrile, based on the total terpolymer is preferably 10 to 30% by weight, more preferably 15 to 30% by weight, in particular 20 to 25% by weight.
  • the remainder is styrene.
  • the copolymers generally have molecular weights M w in the range from 30,000 to 500,000 g / mol, preferably from 50,000 to 250,000 g / mol, in particular from 70,000 to 200,000 g / mol, determined by GPC using tetrahydrofuran. furan (THF) as eluent and with polystyrene calibration.
  • the copolymers can be prepared by free radical polymerization of the corresponding monomers. The preparation is explained in more detail, for example, in WO 2005/040281, page 10, line 31 to page 11, line 8.
  • the component G is used in the molding compositions in an amount of 1 to 25 wt .-%, preferably from 2 to 10 wt .-%, often from 3 to 7 wt .-%.
  • the thermoplastic molding compositions according to the invention contain further rubbers.
  • the one or more other rubbers are based on olefinic monomers without core-shell structure and have at least 0.1 wt .-% of functional monomers.
  • the term "based on” means that the largest proportion of the chewing agent is derived from olefinic monomers (at least 60% by weight, preferably at least 80% by weight, in particular at least 90% by weight) 0.1% by weight of functional monomers, which are monomers which contain a functional group which are capable, in particular, of forming bonds with the polyamide of component A.
  • the functional groups contained therein selected from carboxylic acid, carboxylic acid anhydride, carboxylic ester, carboxylic acid amide, carboximide, amino, hydroxyl, epoxy, urethane or oxazoline or their mixtures Molding compounds in an amount of 1 to 30 wt .-%, preferably from 1, 5 to 10 wt .-%, often used from 2 to 5 wt .-%.
  • Component H is preferably a copolymer of the following components: h1) from 35 to 89.95% by weight of ethylene as component H1,
  • h2 from 10 to 60% by weight of 1-octene, 1-butene, propene or mixtures thereof as component H2 and
  • h3 from 0.05 to 5% by weight of functional monomers, the monomers bearing functional groups selected from carboxylic acid, carboxylic anhydride, carbonyl acid ester, carboxylic acid amide, carboximide, amino, hydroxyl, epoxy, urethane or oxazoline or mixtures thereof as component H3.
  • the proportion of the functional groups H3 is 0.1 to 5, preferably 0.2 to 4 and in particular 0.3 to 3.5 wt .-%, based on the total weight of the component H.
  • Particularly preferred components H3 are made up of an ethylenically unsaturated mono- or dicarboxylic acid or a functional derivative of such an acid.
  • esters having 1 to 12 C atoms preference is given to esters having 1 to 12 C atoms, in particular having 2 to 10 C atoms.
  • esters having 1 to 12 C atoms preference is given to esters having 1 to 12 C atoms, in particular having 2 to 10 C atoms.
  • examples of these are methyl, ethyl, propyl, n-butyl, isobutyl and tert-butyl, 2-ethylhexyl, octyl and Decylac- rylate or the corresponding esters of methacrylic acid.
  • n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • acid-functional and / or latent acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids or monomers containing epoxy groups may also be present in the olefin polymers.
  • monomers H3 are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate and dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids and their monoesters.
  • Suitable latent acid-functional monomers are those compounds which form free acid groups under the polymerization conditions or during the incorporation of the olefin polymers into the molding compositions.
  • Examples include anhydrides of dicarboxylic acids having up to 20 carbon atoms, in particular maleic anhydride and tertiary C to C 2 alkyl esters of the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.
  • the acid-functional or latent acid-functional monomers and the epoxy group-containing monomers are preferably incorporated into the olefin polymers by adding compounds of the general formulas VIII-XI to the monomer mixture.
  • R 1 C (COOR 2 ) C (COOR 3 )
  • R 1 to R 4 , R 5 to R 9 represent hydrogen or alkyl groups having 1 to 6 C atoms, and m is an integer from 0 to 20 and n is an integer from 0 to 10.
  • Preferred for R 1 to R 4 , R 5 to R 7 is hydrogen, for m the value 0 or 1 and for n the value 1.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride or alkenyl glycidyl ether or vinyl glycidyl ether.
  • Preferred compounds of the formulas VIII, IX, X and XI are maleic acid and maleic anhydride as component H3 and epoxy group-containing esters of acrylic acid and / or methacrylic acid, with glycidyl acrylate and glycidyl methacrylate (as component H3) being particularly preferred.
  • Particular preference is given to olefin polymers composed of:
  • acrylic acid or maleic acid or maleic anhydride preferably from 0.3 to 1 wt .-%, or composed of:
  • the preparation of the ethylene copolymers described above can be carried out by processes known per se, preferably by random copolymerization high pressure and elevated temperature.
  • the molecular weight of these ethylene- ⁇ -olefin copolymers is between 10,000 and 500,000 g / mol, preferably between 15,000 and 400,000 g / mol (Mn, determined by GPC in 1, 2,4-trichlorobenzene with PS calibration).
  • Mn determined by GPC in 1, 2,4-trichlorobenzene with PS calibration.
  • ethylene- ⁇ -olefin copolymers prepared by means of so-called "single site catalysts" are used Further details can be found in US 5 272 236.
  • the ethylene- ⁇ -olefin copolymers have one close to polyolefins Molecular weight distribution less than 4, preferably less than 3.5.
  • the functionalized rubbers of component H react in the melt with the component A and are finely dispersed therein. Particular preference is given to grafting EP rubbers with acrylic acid or maleic anhydride, ethylene-acrylic acid copolymers, ethylene-octene copolymers grafted with maleic anhydride, SEBS rubbers grafted with maleic anhydride, and ethylene-butene copolymers grafted with maleic anhydride or acrylic acid are.
  • additives or additives may be mentioned, for example: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve the thermal stability, to increase the resistance to hydrolysis and chemical resistance, means against the heat decomposition and in particular the lubricants / lubricants used for the production Of moldings or moldings are appropriate.
  • Heat stabilizers or oxidation inhibitors are usually metal halides (chlorides, bromides, iodides) derived from Group I metals of the Periodic Table of the Elements (such as Li, Na, K, Cu).
  • Stabilizers which are suitable as component I are the customary hindered phenols, but also "vitamin E” or compounds of analogous construction. Also suitable are benzophenones, resorcinols, salicylates, benzotriazoles and other compounds. , preferably 0.01 to 2 wt .-% (based on the total weight of the molding compositions according to the invention).) Often, the molding compositions contain no stabilizers as component I.
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms.
  • the amounts of these additives, if present, are in the range from 0.05 to 1% by weight (based on the total weight of the molding compositions according to the invention).
  • silicone oils, oligomeric isobutylene or similar substances are suitable as additives, the usual amounts are - if present - 0.05 to 5 wt .-% (based on the total weight of the molding compositions of the invention).
  • Pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid are also usable.
  • Processing aids and stabilizers, lubricants and antistatic agents are usually used in amounts of 0 to 2 wt .-%, preferably 0.01 to 2 wt .-% (based on the total weight of the molding compositions of the invention).
  • the molding compositions of the components D, E, F, G, H and I may contain various fibrous or particulate fillers or mixtures thereof. These are preferably commercially available products, for example carbon fibers and glass fibers.
  • Useful glass fibers may be of E, A or C glass and are preferably equipped with a size and a primer. Their diameter is generally between 6 and 20 ⁇ . Both continuous fibers and chopped glass fibers (staple) or rovings with a length of 1 to 10 mm, preferably 3 to 6 mm, can be used.
  • the molding compositions of the invention may contain other polymers.
  • the molding compositions of the invention can be prepared by any of the known methods. Preferably, however, the mixing of the components by melt mixing, for example, common extrusion, kneading or rolling of the components, for example at temperatures in the range of 160 to 400 ° C, preferably from 180 to 280 ° C, wherein the components, in a preferred embodiment, previously have been partially or completely isolated from the reaction mixtures obtained in the respective manufacturing steps.
  • the graft copolymers C can be mixed as moist crumbs with a granulate of the vinyl aromatic copolymer B, wherein then takes place during mixing, the complete drying to the described graft copolymers.
  • the components can be supplied in each case in pure form to suitable mixing devices, in particular extruders, preferably twin-screw extruders.
  • suitable mixing devices in particular extruders, preferably twin-screw extruders.
  • individual components, for example B and C to be premixed first and then mixed with further components B or C or other components, for example D and E.
  • the component B can be used as a pre-separately prepared component; However, it is also possible to meter the acrylate rubber and the vinyl aromatic copolymer independently of one another.
  • a concentrate for example the components C and D in component B is first prepared (so-called additive batches or masterbatches) and then mixed with the desired amounts of the remaining components.
  • the molding compositions can be processed by methods known in the art, for example, to granules, or else directly to, for example, moldings.
  • the molding compositions of the invention can be processed into films, moldings or fibers. These films, moldings or fibers are particularly suitable for outdoor use, ie under the influence of weather. These films, moldings or fibers can be prepared by the known methods of thermoplastic processing from the molding compositions of the invention. In particular, the production by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press-sintering, deep drawing or sintering, preferably by injection molding, take place. Compared with the known stabilized molding compositions, the molding compositions according to the invention have a further improved weathering resistance, ie a further improved resistance to heat, light and / or oxygen.
  • the following examples and the claims illustrate the invention.
  • the notched impact strength of the products was determined at room temperature on ISO rods according to ISO 179 1 eA.
  • the heat resistance of the samples was determined by means of the Vicat softening temperature.
  • the Vicat softening temperature was determined on standard small bars according to DIN 53 460, with a force of 49.05 N and a temperature increase of 50 K per hour.
  • the measurement of the surface gloss of all samples was carried out according to DIN 67530 at a 60 ° viewing angle.
  • As a measure of the weather resistance was on test specimens (60 x 60 x 2mm, prepared according to ISO 294 in a family tool, at a melt temperature of 260 ° C and a mold temperature of 60 ° C) weathering according to xenon test according to ISO 4892/2, method A, outside, performed.
  • the samples were not subjected to additional treatment after weathering.
  • the surface was evaluated on the basis of the gray value (5: no change, 1: massive change) according to ISO 105-A02 (1993).
  • the change in the color space ⁇ was calculated according to DIN 52 336 from ⁇ _, Aa and Ab according to DIN 6174.
  • the penetration or the multi-axial toughness on platelets (60 mm ⁇ 60 mm ⁇ 2 mm) was produced according to ISO 294 standard in a family mold at a melt temperature of 260 ° C. and a mold temperature of 60 ° C. according to ISO 6603-2 measured at room temperature.
  • the polyamide was a polyamide 6, obtained from ⁇ -caprolactam, with a
  • Viscosity number of 150 ml / g (measured 0.5 wt .-% in 96 wt .-% sulfuric acid) used, commercially available e.g. from BASF SE® under the name Ultramid® B 3.
  • the polyamide was a polyamide 6, obtained from ⁇ -caprolactam, with a
  • Viscosity number of 120 ml / g (measured 0.5 wt .-% in 96 wt .-% sulfuric acid) and a proportion of triacetonediamine of 0.16 wt .-% used.
  • V-A-ii from Lyondell Basell Industries AF S.C.A. commercially available polypropylene Moplen® HP500N.
  • V-A-iii a polystyrene marketed by BASF SE under the name Polystyrol® 158K.
  • B-i a styrene-acrylonitrile copolymer with 75% by weight of styrene and 25% by weight of acrylonitrile and a viscosity number of 80 ml / g (determined in 0.5% strength by weight DMF)
  • Ci an acrylate graft rubber whose synthesis is described in EP-A-450 485 as an example of the invention as component Bi.
  • Component Bi was replaced by 2 parts tricyclodecenyl with 2 parts Dihydodi- cyclopentadienyl acrylate (CAS number 12542-30-2) synthesized.
  • Ci 2 To a template of 2.5 parts of the latex prepared as described in Ch were after addition of 50 parts of water and 0.1 part of potassium persulfate in the course of 3 hours on the one hand a mixture of 49 parts of butyl acrylate and 2 parts Dihydrodicyclopentadienyl- acrylate and on the other hand, a solution of 0.5 part of the sodium salt of a d 2 - added to Ci 8 -Paraffinsulfonkla in 25 parts of water. The temperature of the original was 60 ° C. After the end of the addition, polymerization was continued for 2 hours. The resulting latex had a solids content of 40%. The mean particle size became too
  • Ci 3 150 parts of the latex obtained according to Ci 2 were mixed with 20 parts of styrene and 60 parts of water and heated with stirring after addition of another 0.03 parts of potassium persulfate and 0.05 parts of lauroyl peroxide for 3 hours at 65 ° C.
  • the dispersion obtained was polymerized with 20 parts of a mixture of styrene and acrylonitrile in a ratio of 75:25 for a further 4 hours, precipitated by means of calcium chloride solution, separated off, washed with water and dried in a stream of warm air.
  • the grafting degree of C-i was determined to be 35%, the average particle size to 624 nm.
  • VC-ii The preparation was carried out according to component Ci, but with 5 parts dihydrodicyclopentadienyl acrylate in Ch and Ci 2 instead of 2. This resulted in a swelling index of 4.9 for Bi in toluene.
  • VC-iii an acrylate graft rubber having a particle size of 1207 nm.
  • the preparation was carried out from component Ci 2 .
  • VC-iiii To a template of 9.4 parts of the latex prepared as described in Ci 2 after addition of 50 parts of water and 0.1 part of potassium persulfate in the course of 3 hours on the one hand a mixture of 49 parts of butyl acrylate and 2 parts Dihydrodicyclopentadienyl-acrylate and on the other hand, a solution of 0.5 part of the sodium salt of a d 2 - to Ci 8 -
  • Paraffin sulfonic acid in 25 parts of water. The temperature of the original was 60 ° C. After the end of the feed, polymerization was continued for 2 hours. The resulting latex had a solids content of 40%. The mean particle size was determined to be 1065 nm.
  • VC-iii 2 150 parts of the latex obtained according to Ci 2 were mixed with 20 parts of styrene and 60
  • VD-ii A compound of formula (XII), commercially sold by BASF under the name Tinuvin ® SE 765th
  • component F a compound of formula (III), commercialized by BASF SE under the name Chimassorb ® 944th
  • VF a high molecular weight sterically hindered amine of formula (XIII), CAS number 106990-43-6, sold commercially by SABO SpA under the name ® Sabostab 1 nineteenth
  • component G a styrene-acrylonitrile-maleic anhydride terpolymer having a composition of 74.4 wt .-% of styrene, 23.5 wt .-% of acrylonitrile and 2.1 wt .-% maleic anhydride according to infrared measurement and a viscosity number of 66 ml / g (determined in 0.5 wt .-% DMF solution at 25 ° C).
  • Hi an ethylene-1-butene copolymer functionalized with 67.9% ethylene, 31, 6 wt .-% butene and 0.5 wt .-% maleic acid, commercially available under the name Tafmer ® MH 7010.
  • the stabilized polyamide molding compositions of the invention which also contain a styrenic copolymer component, exhibit improved weathering resistance over the known molding compositions. have improved heat, light, and / or oxygen resistance.
  • the compositions are given in parts by weight, the abbreviation BWZ stands for the weathering time. Also particularly good are those compositions containing at least one component D (such as Tinuvin 770) and at least one component E (such as Cyasorb 3853).

Abstract

L'invention concerne des matières moulables thermoplastiques, contenant a) entre 3 et 91,8 % en poids d'au moins un polyamide, comme composant A, b) entre 3 et 91,8% en poids d'un ou de plusieurs copolymères styrène B qui ne comportent pas de motif dérivé d'anhydride d'acide maléique c) entre 3 et 91,8% en poids d'un ou de plusieurs caoutchoucs greffés C modifiant la résilience, d) entre 0,2 et 1,5% en poids d'un composé de formule (I), comme composant D, e) entre 0 et 0,9% en poids d'un mélange de formule (II), comme composant E, f) entre 0 et 0,9% en poids d'un autre stabilisant, comme composant F, g) entre 1 et 25% en poids d'un ou de plusieurs copolymères styrène G, h) entre 1 et 30% en poids d'un ou de plusieurs autres caoutchoucs. Lesdites matières moulables thermoplastiques présentent une meilleure résistance aux intempéries.
EP12761925.2A 2011-09-29 2012-09-03 Matières moulables stabilisées, à base de polyamide et de copolymères asa Withdrawn EP2760935A1 (fr)

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KR102396611B1 (ko) 2019-07-31 2022-05-10 롯데케미칼 주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
CN110643036B (zh) * 2019-08-23 2021-09-17 惠生(泰州)新材料科技有限公司 一种共聚耐高温尼龙及其制备方法和用途
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JP7386985B2 (ja) * 2020-07-23 2023-11-27 エルジー・ケム・リミテッド 熱可塑性樹脂組成物及びその成形品
WO2022191439A1 (fr) * 2021-03-08 2022-09-15 (주) 엘지화학 Composition de résine thermoplastique et matériau extérieur formé à partir de celle-ci

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