Classifications

• • 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
  • C08L51/04—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 rubbers
• • 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
  • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

• the invention relates to compositions containing acrylonitrile / ethylene- ⁇ -olefin / styrene resin, in particular acrylonitrile / ethylene propylene rubber / styrene (AES) resin, and other thermoplastics and molded articles containing them with improved toughness in the low-temperature range.
• AES acrylonitrile / ethylene propylene rubber / styrene
• blends containing AES rubbers and AES resins are weather-resistant, but their mechanical properties in the low-temperature range are unsatisfactory. At temperatures below 0 ° C, they become brittle and have unsatisfactory toughness, which hinders the use of these molding compositions at lower temperatures. In particular, the notched impact strength of AES blends in the low temperature range is poor, in particular in comparison to acrylic / butadiene / styrene (ABS) blends.
• ABS acrylic / butadiene / styrene
• EP-A 0 502 367 relates to the production of AES graft polymers and a copolymer, the copolymer comprising from 60 to 16% by weight of a aromatic monomer of the vinyl type and 40 to 24% of an aliphatic copolymer. Grafted on are vinyl aromatics and / or nucleus-substituted vinyl aromatics and vinyl cyanides and or (meth) acrylic acid (C 1 -Cg) alkyl esters. In addition to the desired good properties with regard to surface gloss, weather resistance and sliding properties, these thermoplastic copolymers are said to have, among other things, good impact resistance.
• JP-A 50 109 247 describes polycarbonate blends with AES which contains 0.1 to 10% by weight paraffin oil.
• JP-A 58 098 354 describes polycarbonate blends with AES and 0.5 to 20% by weight of plasticizers for vinyl polymers. It is not known that the use of special additives, which concentrate specifically in the soft phase of the blend, leads to a significant improvement in the low-temperature properties in polycarbonate AES blends.
• the object of the invention is to modify AES blends in such a way that they have an improved property profile, in particular also improved notched impact strengths, while maintaining weather resistance in the low-temperature range.
• a graft polymer composition based on acrylonitrile / ethylene- ⁇ -olefin rubber / styrene and selected thermoplastics, such as polycarbonate, polyamide or polyalkylene terephthalate or mixtures thereof, containing an additive selected from triglycerides, aliphatic saturated and / or unsaturated hydrocarbons and their mixtures, which is characterized by the fact that it concentrates in the soft phase of the blend.
• Additives which, in addition to the increase in the soft phase in the blend, have the least possible influence on the glass transition of the matrix are suitable. This can be seen in particular in the case of an improvement in the notched impact strength of moldings obtainable therefrom in the low temperature range. The improved impact strength goes hand in hand with a significantly reduced toughness / brittleness transition of the blends. The low temperature properties are improved while maintaining the essential usage properties. It is particularly advantageous and surprising that no significant increase in the melt volume flow rate (MVR) of the composition can be observed with the additives according to the invention as with known plasticizers. The MVR is essentially unchanged.
• the comparison of the MVR of a sample of a composition according to the invention with a sample which differs only in the absence of the plasticizer used according to the invention shows that the MVR of the sample according to the invention by at most 9, preferably at most 6 and most preferably at most three units of one Sample deviates without this plasticizer. Units in the sense of the invention are integer MVR values.
• the change in the soft phase can be defined according to the formulas (IV) and (V) by the ratio of the storage module G 'at room temperature to the storage module G' at -125 ° C, standardized to the level for ABS (1650 MPa)
• G orr G ' (23 ° C) * 1650 R (IV) G' (- 125 ° C)
• the additives effective according to the invention include all oils and additives which, in the manner described above, increase the soft phase of the blends.
• Triglycerides, aliphatic saturated and / or unsaturated hydrocarbons and mixtures thereof are particularly suitable.
• Triglycerides to be used according to the invention are preferably those of higher fatty acids with 12 to 35, preferably 14 to 30
• the triglycerides can be vegetable, animal and synthetic fats and oils. Suitable vegetable oils are, for example, linseed oil, castor oil, rapeseed oil, corn oil and wheat germ oil.
• Aliphatic saturated and / or unsaturated hydrocarbons suitable according to the invention are those with molecular weights of at least about 400 and mixtures thereof.
• the hydrocarbons can, for example and preferably have molecular weights of 300 to 50,000, particularly preferably 500 to 30,000, in particular 600 to 10,000.
• Particularly effective oils have one branched structure, with short-chain branched hydrocarbon oils being particularly effective.
• Polybutenes or polyisobutenes are particularly suitable, in particular if they are notable for a high content, preferably> 50%, in particular> 60%, based on the end groups, of vinylidene end groups.
• Low molecular weight EPDM oils are also suitable according to the invention.
• Low molecular weight EPDM oils are in particular those with molecular weights of 1,000 to 30,000, preferably 5,000 to 10,000, and mixtures thereof.
• EPDM oils with molecular weights of approximately 5,600 to 8,800 are particularly preferred.
• the additives to be used according to the invention can be used in amounts of 0.1 to about 25% by weight, for example about 1 to 10% by weight, based on the mass of the blends.
• the graft polymers used according to the invention are those with EP (D) M rubbers as the graft base.
• the glass transition temperature of such rubbers can be -40 to -60 ° C, they have only a small number of double bonds, for example less than 20 per 1000 carbon atoms.
• Examples include at least one copolymer or terpolymer containing ethylene and an ⁇ -olefin, preferably with only a small number of double bonds; in this respect reference is made to EP-A 163 411 and 244 857. Those which are preferred by polymerization of at least 30% by weight are preferred.
• Propylene, 1-butene, octene, hexene, and optionally 0.5 to 15 parts by weight of a non-conjugated diolefinic component can be produced, the sum of the parts by weight giving 100.
• Diolefins with at least five carbon atoms such as 5-ethylidene norbornene, dicyclopentadiene, 2,2,1-dicyclopentadiene and 1,4-hexadiene are generally used as the ter component.
• polyethylenes such as polypentamers, polyoctenamers, polydodecanamers or their mixtures. mix.
• partially hydrogenated polybutadiene rubbers are also suitable, in which at least 70% of the residual double bonds are hydrogenated.
• EP (D) M rubbers have a Mooney viscosity L W (100 ° C) of 25 to 120. They are commercially available. Furthermore, the polyolefin elastomers or ethene / octene polyolefins offered under the trade name Engage can also be used analogously.
• Vinylaromatics and / or nucleus-substituted vinylaromatics and vinylcyanides and / or (meth) acrylic acid (C 1 -C 8 ) alkyl esters are grafted on.
• the graft base 2 generally has an average particle size (dso value) of 0.05 to 5 ⁇ m, preferably 0.10 to 2 ⁇ m, particularly preferably 0.15 to 1 ⁇ m.
• Monomers 1) are preferably mixtures of
• Nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid- (C 1 -
• C 8 C 8 ) -alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and or derivatives, such as anhydrides and imides of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide.
• Preferred monomers 1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
• preferred monomers 1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
• the EP (D) M-based graft polymer can be prepared, for example, by preparing a solution of the EP (D) M elastomer in the monomer mixture and, if appropriate, indifferent solvents, and by radical initiators such as azo compounds or peroxides at higher temperatures
• the graft polymer compositions according to the invention can be aromatic
• Aromatic polycarbonates can be prepared by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalo- geniden, according to the phase interface method, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols.
• Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
• R5 and R6 can be selected individually for each ⁇ , independently of one another hydrogen or Ci-Cg-alkyl, preferably hydrogen, methyl or ethyl,
• n is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom ⁇ , R ⁇ and R ⁇ are simultaneously alkyl.
• Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis- (hydroxyphenyl) -C ⁇ -C5-alkanes, bis- (hydroxyphenyl) -C5-C6-cycloalkanes, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl) sulfoxides, bis- (hydroxyphenyl) -ketones,
• diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, l, l-bis (4-hydroxyphenyl) cyclohexane, 1,1-
• 4,4'-dihydroxydiphenyl sulfone and its di- and tetrabrominated or chlorinated Derivatives such as 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3, 5-dibromo-4-hydroxyphenyl) propane.
• 2,2-Bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.
• the diphenols can be used individually or as any mixtures.
• Diphenols are known from the literature or can be obtained by processes known from the literature.
• Suitable chain terminators for the production of the thermoplastic, aromatic polycarbonates or polyester carbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) - phenol according to DE-A 2 842 005 or monoalkylphenol.
• the amount of chain terminator is generally 0.5 to 10 mol%, based on the molar sum of the diphenols used in each case.
• thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M w ), measured by ultracentrifuge or scattered light measurement, of 10,000 to 200,000, preferably 15,000 to 80,000. Mixtures of polycarbonates with different molecular weights can also be used.
• thermoplastic, aromatic polycarbonates or polyester carbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example sol - Chen with three and more phenolic groups.
• 3- or polyfunctional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, or 3- or polyfunctional phenols such as phloroglycine can be used as branching agents in amounts of 0.01 to 1.0 mol%, based on the diphenols used.
• Phenolic branching agents can be introduced with the diphenols
• acid chloride branching agents can be introduced together with the acid dichlorides.
• homopolycarbonates and copolycarbonates are suitable.
• preferred polycarbonates are the copolycarbonates of bisphenol-A with up to 15 mol%, based on the molar sums of diphenols, of other diphenols, in particular 2,2-bis (3, 5-dibromo-4-hydroxyphenyl) propane.
• Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
• Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
• a carbonic acid halide preferably phosgene, is additionally used as a bifunctional acid derivative in the production of polyester carbonates.
• the aromatic polyester carbonates can also contain built-in aromatic hydroxycarboxylic acids.
• the proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
• the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and carbonate content of the aromatic
• Polyester carbonates can be in the form of blocks or randomly distributed in the polycondensate.
• the relative solution viscosity ( ⁇ re ⁇ ) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably 1.20 to 1.32, measured on solutions of 0.5 g polycarbonate or polyester carbonate in 100 ml methylene chloride solution at 25 ° C.
• thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture.
• the blend compositions according to the invention can also include polyalkylene terephthalates, as described, for example, in WO 0 029 476, and / or vinyl (co) polymers, as described in EP-A 640 655, in particular styrene / acrylonitrile ( Co) polymers.
• Preferred polyalkylene terephthalates are polyethylene or polybutylene terephthalates or mixtures thereof.
• blend compositions according to the invention can contain further additives known for blends and aromatic polycarbonates, such as at least one of the customary additives, such as lubricants and mold release agents, for example pentaerythritol tetrastearate, nucleating agents, flame retardants, antistatic agents, stabilizers, fillers and reinforcing materials, and also dyes and pigments, and also electrically conductive additives, e.g. Polyaniline or nanotubes.
• customary additives such as lubricants and mold release agents, for example pentaerythritol tetrastearate, nucleating agents, flame retardants, antistatic agents, stabilizers, fillers and reinforcing materials, and also dyes and pigments, and also electrically conductive additives, e.g. Polyaniline or nanotubes.
• Phosphorus-containing flame retardants in the sense of the invention are particularly preferably selected from the groups of the mono- and oligomeric phosphorus and phosphonic acid esters, phosphonatamines and phosphazenes, mixtures of several components selected from one or different of these groups also being able to be used as flame retardants.
• Other halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other halogen-free phosphorus compounds.
• the filled or reinforced molding compositions can contain up to 60% by weight, preferably
• Preferred reinforcing materials are glass fibers.
• Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite.
• the molding compositions according to the invention can contain up to 35% by weight, based on the
• Composition contain another, optionally synergistic flame retardant.
• Organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide and nitrogen compounds such as melamine are mentioned as examples of further flame retardants.
• compositions according to the invention can be prepared by mixing the constituents in a known manner and melt-compounding or melt-extruding them at elevated temperatures, preferably at from 200 to 350 ° C., in the customary devices, such as internal kneaders, extruders or twin-screw screws.
• the individual components can be mixed in one after the other or simultaneously.
• the moldings according to the invention can be produced by extrusion or injection molding.
• Moldings according to the invention are, for example, outdoor applications, e.g. Window parts, air conditioners, water tanks, automotive exterior parts, garden equipment, housing parts for household appliances, such as juicers, coffee machines, mixers, for office machines, such as monitors, printers, copiers or cover plates for the construction sector and automotive parts. They can also be used in the field of electrical engineering because they have very good electrical properties.
• Molding compositions are also suitable for the production of moldings by deep drawing from previously produced sheets or foils.
• telecommunication devices such as telephone devices and faxes, computers, printers, scanners, plotters, monitors, keyboards, typewriters, dictation devices, etc.
• garden tools garden furniture, lawn mower housings, pipes and housings for garden irrigation, garden houses, leaf vacuums, shredders, shredders, sprayers etc.,
• sports / play equipment toy vehicles, seats, pedals, sports equipment, bicycles,
• Polycarbonate / AES or polyamide / AES blends of the following composition are produced as the base material for carrying out tests:
• AES blend (Blendex® WX 270patentede Cycon Ltd, Tokyo, Japan or Royaltuf® 372, Uniroyal, Great Britain or AES 665, Techno Polymers, Tokyo, Japan) 0.9 parts by weight of common additives , such as B. mold release agents, antioxidants
• PA / AES blends base material B
• Samples of the base material A or B are 1, 5 or 10 parts by weight of corn oil, 5 parts by weight of Napvis® D2, D5 or D07 (BP Amoco Chemicals Lavera,
• the components are mixed on a 3-1 kneader.
• the moldings are produced on an Arburg 270 E injection molding machine at 260 ° C.
• Step drop and the melt volume rate.
• the memory module G ' is determined by a dynamic mechanical analysis in a manner known to the person skilled in the art. From the ratio of the storage module at room temperature to the storage module at -125 ° C normalized to the level for ABS (1650 MPa), a measure for the change in the soft phase can be defined according to formula (IV) and (V):
• G orr G ' (23 ° C) * 1650 R ⁇ (IN) G' (- 125 ° C)
• the notched impact strength a k is determined in accordance with ISO 180 / 1A.
• the critical temperature the temperature below which a brittle fracture behavior occurs instead of a tough fracture behavior, is determined accordingly.
• the melt volume rate indicates the volume of the blends that flow through a nozzle of a specified size in 10 minutes at a certain temperature and under a certain load.
• the melt volume flow rate (MVR) is determined according to ISO 1133 at 260 ° C and 5kg coating weight.
• Tables 1 to 3 and 5 contain the base material A, which

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