DE4114589A1 - Moulding materials with high impact strength and solvent resistance - Google Patents

Abstract

Thermoplastic moulding materials (I) are claimed, contg.(A) 10-70 pts. wt. thermoplastic aromatic polycarbonate, (B) 5-70pts. wt. thermoplastic, partly crystalline or amorphous polyamideor a mixt. thereof, (C) 5-50 pts. wt. graft copolymer. (D) 1-20pts. wt. imidised polyacrylate contg. 0.5-10 wt.% imide andanhydride structures of formula (II) and (E) 0-40 pts. wt.thermoplastic copolymer of (E1) 50-95 wt.% styrene and/oralpha-methylstyrene and (E2) 50-5 wt.% acrylonitrile (C) is agraft copolymer of (C1) 15-80 wt.% of a mixt. of (C.1.) 50-95wt.% styrene and/or alpha-methylstyrene and (C.1.2) 50-5 wt.%acrylonitrile with (C2) 85-20 wt.% crosslinked elastomerparticles with d50 .05- microns and Tg below 10 deg.C; In (II)R1, R2 = H or Me; X = O or NR3 (with R3 = H or 1-4C alkyl).

Description

The invention relates to thermoplastic molding compositions made from aromatic poly carbonates, polyamides, graft polymers with rubber core and with styrene and acrylonitrile in the shell, imidized polyacrylates containing acid anhydride functions, and optionally additional thermoplastic copoly Merisaten from styrene and acrylonitrile. The molding compounds have high impact strength and good solvent resistance. In particular, the invention characterized by the use of imidated anhydride groups Polyacrylates.

Polyamides are due to their good wear resistance, chemical and Stress crack resistance and flowability as materials for molded parts with high demands used. Aromatic polycarbonates, especially those of Bisphenol A, are characterized by good toughness and high heat resistance as well as high transparency. Molding compounds made from polyamides and aromatic In contrast, polycarbonates have unsatisfactory technological properties. The reason for this are the strong intolerance of the polymers and a Possible molecular weight reduction of the polycarbonate through the polyamide Component considered in the production of mixtures, being known for a long time is that in particular free amino groups in polyamide have a degrading effect.

US 47 88 248 describes thermoplastic mixtures of polyamide and poly carbonate or polyester carbonate or polyarylate to improve the Properties of a polyamide-polyarylate block copolymer as compatibility intermediaries included. Modifiers are another component of the mixture  Impact resistance called improvement. In US 47 88 249 is considered a contract keitsvermittler a polyester-polyamide block copolymer used.

US 47 82 114 describes polyamide / polycarbonate molding compositions that are compatible keitsvermittler contain a polymer that has functional groups that a Compatibility to manufacture polyamide component, and other functional group has pen that produce a compatibility with the polycarbonate component.

EP O 3 32 454 describes molding compositions with improved impact resistance compared to the respective individual blend components made of polyamide and / or polycarbo nat, graft polymer and a copolymer of six-ring imide and / or Six-ring anhydride units, methyl methacrylate, (meth) acrylic acid and opp if necessary, another vinyl monomer. As impact modifiers are only graft polymers with a rubber component as the graft base layer and a themoplastic graft shell, built up from an aromatic Vinyl compound (e.g. styrenes) and a methacrylic acid ester, or one aromatic vinyl compound, acrylonitrile and a methacrylic acid ester. Modifiers such as SB block copolymers, HIPS (impact-resistant polystyrene) and ABS are not suitable for impact modification.

It has now been found that technologically high-quality molding compositions are based of mixtures of aromatic polycarbonates (A), polyamides (B) and optionally copolymers (E) of styrene and acrylonitrile with graft polymers saten (C), which has a rubber core and a grafted shell made of styrenes and Wear acrylonitrile (without the use of alkyl methacrylates), and one Modify imidized polyacrylate (D) with acid anhydride functions advantageously to let. The mixtures are characterized by significantly improved impact strength even at lower temperatures compared to binary mixtures from Polycar bonat / polyamide and a comparison to ternary blends of polycarbonate / Polyamide / graft polymer and polycarbonate / polyamide / imidized polyacrylate out. The mixtures continue to have high solvent resistance.  

The finding is irrespective of whether polycarbonate or polyamide is the quantity predominant matrix component in the molding compositions. The polycarbonate Component in the blend is not as usual due to the amino end groups of the polyamide degraded, but by the addition of the anhydride imidized polyacrylate stabilized against molecular weight reduction.

The invention thus relates to thermoplastic molding compositions containing

• A. 10 to 70 parts by weight, preferably 10 to 60 parts by weight, of a thermoplastic aromatic polycarbonate,
• B. 5 to 70 parts by weight, preferably 10 to 60 parts by weight, of a thermoplastic , partially crystalline or amorphous polyamide or a mixture of a partially crystalline and an amorphous polyamide,
• C. 5 to 50 parts by weight, preferably 12.5 to 40 parts by weight, of a graft polymer
  • C.1. 15 to 80 wt .-%, preferably 20 to 70 wt .-%, based on C) of a mixture of
    • C.1.1. 50 to 95 wt .-%, preferably 60 to 80 wt .-%, based on C.1, styrene, α-methylstyrene or mixtures of these compounds and
    • C.1.2. 50 to 5% by weight, preferably 40 to 20% by weight, based on C), of acrylonitrile
  • C.2. 85 to 20 wt .-%, preferably 80 to 30 wt .-%, based on C), a crosslinked, particulate, elastomeric graft base with an average particle diameter d₅₀ of 0.05 to 5, preferably 0.09 to 1 μm and one Glass temperature <10 ° C, preferably -20 ° C,
• D. 1 to 20 parts by weight, preferably 2 to 17.5 parts by weight, of an imidized polyacrylate containing 0.05 to 10% by weight, preferably 0.1 to 5% by weight, of anhydride structures of the formula (I) in C) in addition to imide structures of the formula (II), wherein
  R¹, R² independently of one another are hydrogen or methyl,
  R³ is hydrogen or C₁-C₄ alkyl, and
• E. 0 to 40 parts by weight, preferably 0 to 20 parts by weight, in particular 2 to 20 parts by weight, of a thermoplastic vinyl copolymer
  • E.1. 50 to 95% by weight, preferably 60 to 85% by weight, based on E), styrene, α-methylstyrene or mixtures thereof, and
  • E.2. 50 to 5 wt .-%, preferably 40 to 15 wt .-%, based on E), acrylonitrile.

If the content of aromatic polycarbonate (A) compared to the content of Polyamides (B) predominate (polycarbonate component as matrix), contain the thermoplastic molding compositions 30 to 70 parts by weight, preferably 35 to 60 parts by weight Parts of component (A), 5 to 29 parts by weight, preferably 10 to 25 parts by weight, component (B), 5 to 50 parts by weight, preferably 12.5 to 40 parts by weight, of Component (C), 1 to 20 parts by weight, preferably 2.5 to 17.5 parts by weight, of the Component (D) and 0 to 40 parts by weight, preferably 0 to 20 parts by weight, of Component (E).

If the content of polyamides (B) compared to the content of aromatic polycar Bonaten (A) predominates (polyamide component as matrix), contain the thermopla tical molding compositions 10 to 29 parts by weight, preferably 10 to 25 parts by weight, the Component (A), 30 to 70 parts by weight, preferably 35 to 60 parts by weight, the com component (B), 5 to 40 parts by weight, preferably 12.5 to 40 parts by weight, of Component (C), 1 to 20 parts by weight, preferably 2.5 to 17.5 parts by weight, of the Component (D) and 0 to 40 parts by weight, preferably 0 to 25 parts by weight, of Component (E).

The components A) -E) are in the ratio of the specified, respective Weight limits mixed.  

Aromatic polycarbonates A

The aromatic polycarbonates A. and their starting materials are known from the literature or can be produced by processes known from the literature (see for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, DE-AS 14 95 626, DE-OS 22 32 877, DE-OS 27 03 376, DE-OS 30 00 610, DE-OS 27 14 544, DE-OS 29 40 024 and DE-OS 30 07 934. Especially the preferred manufacturing process is the phase interface process.

The polycarbonates are prepared in a known manner, for. B. by Reaction of diphenols with carbonic acid halides, preferably phosgene, according to the phase interface method, if necessary using ket tenabbruchern, for example monophenols, and optionally with Mitver use of trifunctional or more than trifunctional branches, at for example triphenols or tetraphenols. For the production of aromatic Polycarbonates are referred to Schnell, loc.cit., P. 33 ff.

Diphenols for the production of polycarbonates A. are preferably those of Formula (III)

wherein

A is a single bond, a C₁-C₅ alkylene, a C₂-C₅ alkylidene, e.g. B.

an optionally mono-, bis- or tris-substituted C₅-C₆-cycloalkylidene, e.g. B.

B chlorine, bromine, methyl,
x is 0, 1 or 2 and n is 1 or 0.

Preferred diphenols of the formula (III) are e.g. B. hydroquinone, resorcinol, bis (hy droxyphenyl) -C ₁ -C ₅ alkanes, bis (hydroxyphenyl) -C ₅ -C ₆ cycloalkanes, bis (hydroxy phenyl) ether, bis (hydroxyphenyl) - sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, α, α-bis (hydroxyphenyl) diisopropylbenzenes and their core-brominated and / or core-chlorinated derivatives.

The most important diphenols of the formula (III) are bisphenol A (2,2-bis (4-hydroxy phenyl) propane), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-di hydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-di bromo-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The diphenols can be used individually or as any mixture.

For the production of thermoplastic, aromatic polycarbonates suitable chain terminators z. B. phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethyl butyl) phenol according to DE-OS 28 42 005 (Le A 19 006) or monoalkylphenol or Dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol. The amount chain terminators to be used is generally between 0.5 and 10 mol%, based on the sum of the diphenols used in each case.

The thermoplastic, aromatic polycarbonates A. have weight average molecular weights (M _w , measured, for example, by ultracentrifugation or scattered light measurement) of 10,000 to 20,000, preferably 20,000 to 80,000 g / mol.

The thermoplastic, aromatic polycarbonates A. can in a known manner be branched, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, three or more than tri-functional compounds, e.g. B. those with three or more than three phenolic groups.  

Both homocarbonates and copolycarbonates are suitable. For the production Copolycarbonate A. according to the invention can also be 1 to 25% by weight, preferably as 2.5 to 25 wt .-% (based on the total amount to be used Diphenols), diphenols of the formula (V) can be used.

wherein

A has the meaning given for formula (III),
n is 1 or zero,
R⁴ the same or different and a linear C₁-C₂₀ alkyl, branched C₃-C₂₀ alkyl or C₆-C₂₀ aryl, preferably CH₃, and
m is an integer between 5 and 100, preferably between 20 and 80.

Polydiorganosiloxanes with hydroxy-aryloxy end groups according to formula (V) are known (see for example US Patent 34 19 634) or according to the literature Process can be produced. The production of such polydiorganosiloxane Copolycarbonate is e.g. B. described in DE-OS 33 34 782.  

Preferred polycarbonates A. in addition to the bisphenol A homopolycarbonates Copolycarbonates of bisphenol A with up to 80 mol%, based on the molsum of diphenols, of 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Polyamides B

All are suitable as polyamide component B. of the molding compositions according to the invention Semi-crystalline polyamides, especially polyamide-6, polyamide-6,6, mixtures of these polyamides or partially crystalline copolyamides based on these two Components. Furthermore, partially crystalline polyamides can be considered, the Acid components, in particular in whole or in part (in addition to adipic acid or Caprolactam) from other dicarboxylic acids, preferably from terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or Azelaic acid and / or adipic acid and / or a cyclohexanedicarboxylic acid and other diamine components, preferably wholly or partly, in particular made of m and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine and / or isophorone diamine, and there Composition and manufacture are known from the prior art.

Also to be mentioned are partially crystalline polyamides, which are made up entirely or in part Lactams or ω-aminocarboxylic acids with 6 to 12 carbon atoms, optionally under Using one or more of the above-mentioned starting components, getting produced.

Particularly preferred partially crystalline polyamides B. are polyamide 6 and poly amide-6,6 or their mixtures or copolyamides with only minor Proportions (up to about 10% by weight) of the co-components.

B. Amorphous polyamides can also be used as the polyamide component. They are obtained by polycondensation of diamines, for example Tetramethylene diamine, hexamethylene diamine, decamethylene diamine, 2,2,4- and / or Trimethylhexamethylene diamine, m- and / or p-xylylenediamine, bis- (4-amino cyclohexyl) methane or mixtures of 4,4'-, 2,4'- and / or 2,2'-diaminodicyclo  hexylmethanes, 2,2-bis (4-aminocyclohexyl) propane, 3,3'-dimethyl-4,4'-diamino- dicyclohexylmethane, 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine, 2,5- and / or 2,6-bis (aminomethyl) norbornane and / or 1,4-diamino-methylcyclohexane, with Dicarboxylic acids, for example oxalic acid, adipic acid, azelaic acid, decanedioic acid, Heptadecanedicarboxylic acid, 2,2,4- and / or 2,4,4-trimethyladipic acid, Isophthalic acid or small amounts of terephthalic acid, at least one Component has an asymmetrical structure (e.g. by alkyl substitution). Of course are also amorphous copolymers made by several polycondensation Monomers obtained are suitable, furthermore such copolymers which are added of aminocarboxylic acids, such as ε-aminocaproic acid, ω-aminoundecanoic acid or ω-aminolauric acid or its lactams.

Particularly suitable amorphous polyamides are those made from isophthalic acid, Hexamethylene diamine and other diamines such as 4,4′-diaminodicyclohexyl methane, Isophoronediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine, 2,5- and / or 2,6-bis (aminomethyl) norbornane; or from isophthalic acid, 4,4′-diamino dicyclohexylmethane and ε-caprolactam; or from isophthalic acid, 3,3'-dimethyl 4,4'-diamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine.

Instead of the pure 4,4'-diaminodicyclohexylmethane, mixtures of positionally isomeric diaminodicyclohexylmethanes are used, which composed of 70 to 99 mol% of the 4,4'-diamino isomer, 1 to 30 mol% of 2,4'-diamino isomer, 0 to 2 mol% of 2,2'-diamino isomer and optionally correspond to higher condensed diamines by hydrogenation of Technical quality diaminodiphenylmethane can be obtained. Isophthalic acid up to 30 mol% can be replaced by terephthalic acid.

The thermoplastic polyamides B. can also be in the form of mixtures before added by semi-crystalline and amorphous polyamides.  

The polyamides B. should have a relative viscosity (measured on a 1% by weight Solution in m-cresol at 25 ° C) from 2.0 to 5.0, preferably from 2.0 to 4.0 exhibit.

Graft polymers C

Suitable particulate, crosslinked rubbers C.2. as a graft base to Her position of the graft polymers C. are in particular polybutadiene rubbers, Butadiene / styrene copolymers (both also copolymerized with up to 30% by weight, based on the weight of rubber, a lower alkyl ester of acrylic or Methacrylic acid such as methyl methacrylate, ethyl acrylate, methyl acrylate or ethyl methacrylate). The alkyl acrylate rubbers can optionally contain up to 30% by weight, based on the rubber weight, monomers such as vinyl acetate, acrylonitrile, styrene, Contains copolymerized methyl methacrylate and / or vinyl ether as well as smaller ones Amounts, preferably up to 5 wt .-%, based on the weight of rubber, ver wetting ethylenically unsaturated monomers. Such crosslinkers are e.g. B. alkylenediol di (meth) acrylates, polyester di (meth) acrylates, divinylbenzene, Trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene or isoprene. As Acrylate rubbers are also suitable for those with a networked dienkau Tschuk from one or more conjugated dienes and possibly less Amounts of an ethylenically unsaturated monomer such as styrene and / or acrylic nitrile, contained as core. Other suitable rubbers are, for example EPDM rubbers, i.e. rubbers made of ethylene, propylene and an unconjugated ten dien; silicone rubbers are also suitable.

Preferred rubbers C.2. for the preparation of the graft polymers C. are diene and Alkyl acrylate rubbers.

The rubbers C.2. are in the graft polymers C. at least in the form partially cross-linked particles with an average particle size of 0.09 to 5 µm, in particular 0.1 to 1 ul, and thus form the core in the Graft polymers C. which have a hard shell from C.1.1. and C.1.2. exhibit.  

The graft polymers C. can be obtained by radical graft polymerization be put.

To prepare the graft polymer C., the graft monomers C.1.1. and C.1.2. in the presence of the particulate rubber base C.2. radi graft-polymerized, especially at 40 to 90 ° C. The graft polymerization can be carried out in suspension, dispersion or emulsion. Is preferred the continuous or discontinuous emulsion graft polymer ion. These Graft polymerization is carried out using radical initiators (from the group of peroxides, azo compounds, hydroperoxides, persulfates, per phosphates) and optionally also using anionic emulsifiers, e.g. B. carboxonium salts, sulfonic acid salts or organic sulfates. Make it up graft polymers with high graft yields, d. H. a large proportion of the poly merisates of the monomers C.1. is attached to the rubber C.2. chemically bound and result in particulate graft products with a core / shell structure (next to them form Usually and practically unavoidable smaller amounts of not grafted polymers).

The graft polymers C. are those which can be obtained by graft polymerizing 15 up to 80, preferably 20 to 70% by weight of a vinyl monomer mixture C.1. on 20 to 85, preferably 30 to 80 wt .-%, one of the aforementioned Rubber basics C.2. receives.

Vinyl monomer mixtures C.1. consist of 50 to 95 wt .-% styrene, o-methyl styrene or mixtures thereof (C.1.1.) on the one hand and from 5 to 50% by weight of acrylic nitrile (C.1.2.) on the other hand. A mixture of 60 to 60 is particularly preferred 80% by weight styrene and 40 to 20% by weight acrylonitrile.

The graft polymers C. prepared in this way can be prepared by known processes be worked up, e.g. B. by coagulation of the latices with electrolytes (salts, Acids or mixtures thereof) and subsequent cleaning and drying.  

In the manufacture of the graft polymers C. form by graft copolymerization generally in addition to the actual graft copolymer in a small amount The extent also of free copolymers of the graft monomers forming the graft shell.

Graft polymers C. are therefore by polymerization of the graft monomers C.1. in the presence of the rubber C.2. obtained particulate products, exactly taken generally a mixture of graft copolymer with core / shell structure and inevitably resulting free copolymer of Graft Monomers C.1.

The molding compounds have optimal properties if C. in the graft polymer. the amount of free copolymer C.1. 50% by weight, preferably 30, in particular not exceeding 20% by weight, based on component C.

Imidized polyacrylates D. with 0.05 to 10% by weight of anhydride structures

Imidized polyacrylates D. having anhydride functions in the polymer chain can generally be prepared by reacting polymers of esters of acrylic acid or methacrylic acid and acrylic acid or methacrylic acid with ammonia or primary amines R ³ -NH ₂ according to US Pat. No. 4,246,374. Esters of methacrylic acid and methacrylic acid are preferably used as monomers (see also ME Fowler et al., J. Appl. Polym. Sci. 37, 513 (1989)). The resulting imidized polyacrylates also contain anhydride groups of the formula (I)

in addition to the predominant imide groups of the formula (II)

wherein

R¹, R² independently of one another are hydrogen or methyl,
R³ is hydrogen or C₁-C₄ alkyl.

Depending on the degree of imidization, the imidized, anhydride-containing polyacrylates can furthermore contain esters of acrylic acid and methacrylic acid as well as acrylic acid or methacrylic acid in polymerized form. Examples of imidized polyacrylates and their chemical composition are described in ME Fowler et al., J. Appl. Polym. Sci. 37, 513 (1989). The polymers are resinous, thermoplastic and rubber-free and preferably uncrosslinked and z. B. soluble in dimethylformamide. The average molecular weights (weight average _w ) are 20,000 to 2,000,000 g / mol. The glass transition temperatures of the imidized polyacrylates D. are determined by the degree of imidization and increase with an increasing degree of imidization.

Vinyl copolymers E

The vinyl copolymers E. are those from the monomers styrene, α-methyl styrene or mixtures thereof (E.1.) and acrylonitrile (E.2.), preferably styrene and Acrylonitrile. They are resinous, thermoplastic and rubber-free.

Preferred weight ratios in the thermoplastic copolymer E. are 60 up to 85% by weight of styrene (E.1.) and 40 to 15% by weight of acrylonitrile (E.2.).

The copolymers E. are known and can be polymerized by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The copolymers E. preferably have molecular weights _w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000 g / mol.

Copolymers E. often arise during graft polymerization for production component C. as by-products, especially when large amounts of mono gers are grafted onto small amounts of rubber. The invention The amount of copolymer E. to be used is inevitably obtained By-products of the graft polymerization in the production of C. not included.

The molding compositions according to the invention can further, for polycarbonate / ABS-Mi known conventional additives, such as stabilizers, UV absorbers, pigments, Lubricants and removers, flame retardants, anti-dripping agents and Antistatic agents in the effective amounts for their known application contain.  

Production of molding compounds

The molding compositions according to the invention can be produced by the Components A to C (optionally E) with those to be used according to the invention anhydride-containing, imidized polyacrylates (D) mixed in a known manner and at elevated temperatures, preferably at 200 to 300 ° C, in usual Vorrich such as internal kneaders, extruders or twin-screw extruders, schmelzcom pounded or melt extruded. The individual components can be consecutively or mixed at the same time. Individual components can also be used as masterbatches in polyamide and / or polycarbonate can be added.

The compounded molding compositions according to the invention can be used to produce Shaped bodies of any kind, e.g. B. by injection molding and extrusion. Examples of molded articles are housing parts for electrical appliances or molded parts for the Automotive interior and exterior.

Examples Polymers used A.-100

Linear polycarbonate based on bisphenol A with a relative viscosity of 1.26, measured in CH ₂ Cl ₂ at 25 ° C and in a concentration of 0.5 g / 100 mol.

A.-200

Linear polycarbonate based on bisphenol A / 1,1-bis- (4-hydroxy-phenyl) -3,3,5-trimethylcyclohexane (molar ratio 66:34) with a relative viscosity of 1.3, measured in CH ₂ Cl ₂ at 25 ° C and in a concentration of 0.5 g / 100 ml.

B.-100

Polyamide-6 with a relative viscosity of 3.0, measured on a 1 wt .-% Solution in m-cresol at 25 ° C.

C.-100

Graft polymer of 25 parts by weight of a monomer mixture of styrene and acrylonitrile in a ratio of 72:28 to 75 parts by weight of particulate crosslinked polybutadiene rubber (average particle diameter d ₅₀ = 0.4 μm), produced by emulsion polymerization.

D.-100

Imidized polyacrylate with anhydride functions (Paraloid EXL 4151, from Röhm & Haas).
IR analysis: anhydride absorption at 1850 and 1760 cm⁻¹
DSC analysis: glass transition temperature T _g = 147 ° C
Viscosity number [η] = 40 ml / g, dimethylformamide, 20 ° C.

Compounding

The components were on a continuously working double shaft extruder melted at a melt temperature of 270 ° C, homogenized, cooled and granulated.

processing

The mixtures obtained after compounding were sprayed Casting machine for test specimens measuring 80 · 10 · 4 mm at a mass of 270 ° C temperature processed.

Notched impact strength according to Izod

The Izod impact strength was determined on test specimens of the dimension 80 · 10 · 4 mm, melt temperature 270 ° C, at those given in the tables Temperatures determined according to ISO 180 1A.

Heat resistance

The heat resistance according to Vicat (method B) was in accordance with DIN 53 460 certainly.  

Flowability

The flowability was assessed over that of the injection molding machine used (Melt temperature: 270 ° C) necessary filling pressure (see Johannaber, plastics 74, 1-5, (1984)) for the production of rods measuring 80 × 10 × 4 mm.

Resistance to petrol (ESC behavior)

The gasoline resistance was tested on bars measuring 80 · 10 × 4 mm (mass temperature 270 ° C). A mixture of 50 vol.% Toluene / 50 vol.% Isooctane was used as fuel simulant. The test specimens were pre-stretched using an arc template and stored in the fuel simulator for 5 minutes at room temperature. The pre-stretch ε _x was 0.4 to 2.4%. The stress crack behavior was assessed via the fracture as a function of the pre-stretch.

The compositions of the mixtures and the test results are summarized.  

Table 1

Composition of the mixtures

Table 2

Composition of the mixtures

Claims (9)

1. Thermoplastic molding compositions containing

• A. 10 to 70 parts by weight of a thermoplastic, aromatic polycarbonate and
• B. 5 to 70 parts by weight of a thermoplastic, partially crystalline or amorphous polyamide or a mixture of a partially crystalline and an amorphous polyamide and
• C. 5 to 50 parts by weight of a graft polymer composed of:
  • C.1. 15 to 80 wt .-%, based on C, a mixture of
    • C.1.1. 50 to 95 wt .-%, based on C.1, styrene, α-methylstyrene or mixtures of these compounds, and
    • C.1.2. 50 to 5 wt .-%, based on C.1, acrylonitrile
  • C.2. 85 to 20% by weight, based on C. of a crosslinked, particulate, elastomeric graft base (rubbers) with an average particle diameter d₅₀ of 0.05 to 5 μm and a glass transition temperature <10 ° C., and
• D. 1 to 20 parts by weight of an imidized polyacrylate which in D. 0.05 to 10% by weight of anhydride structures of the formula (I) in addition to imide structures of the formula (II), wherein
  R¹, R² independently of one another are hydrogen or methyl,
  R³ is hydrogen or C₁-C₄ alkyl, and
• E. 0 to 40 parts by weight of a thermoplastic vinyl copolymer from:
  • E.1. 50 to 95 wt .-%, based on E) styrene, α-methylstyrene or mixtures thereof and
  • E.2. 50 to 5 wt .-%, based on E) acrylonitrile.

2. Thermoplastic molding compositions according to claim 1, characterized in that they

• A. 10 to 70 parts by weight of a thermoplastic, aromatic polycarbonate and
• B. 10 to 60 parts by weight of a thermoplastic, partially crystalline or amorphous polyamide or a mixture of a partially crystalline and an amorphous polyamide and
• C. 12.5 to 40 parts by weight of a graft polymer
  • C.1. 20 to 70 wt .-%, based on C., a mixture of
    • C.1.1. 60 to 80 wt .-%, based on C.1, styrene, α-methylstyrene or mixtures of these compounds, and
    • C.1.2. 40 to 20% by weight, based on C., acrylonitrile,
  • C.2. 80 to 30 parts by weight of a crosslinked, particulate, elastomeric graft base (rubbers) with an average particle diameter d₅₀ of 0.09 to 1 µm and a glass transition temperature <-20 ° C and
• D. 2.5 to 17.5 parts by weight of an imidized polyacrylate which contains in D. 0.1 to 10% by weight of anhydride structures of the formula (I) in addition to imide structures of the formula (II), wherein
  R¹, R² independently of one another are hydrogen or methyl,
  R³ is hydrogen or C₁-C₄ alkyl, and
• E. 0 to 20 parts by weight of a thermoplastic vinyl copolymer
  • E.1. 60 to 85 wt .-%, based on E., styrene, α-methylstyrene or mixtures thereof, and
  • E.2. 40 to 15 wt .-%, based on E., acrylonitrile.

3. Thermoplastic molding compositions according to claim 1, characterized in that they

• A. 30 to 70 parts by weight of a thermoplastic, aromatic polycarbonate and
• B. 5 to 29 parts by weight of a thermoplastic, partially crystalline or amorphous polyamide or a mixture of a partially crystalline and an amorphous polyamide and
• C. 5 to 50 parts by weight of a graft polymer
  • C.1. 15 to 80 wt .-%, based on C., of a mixture of
    • C.1.1. 50 to 95 wt .-%, based on C.1, styrene, α-methylstyrene or mixtures of these compounds and
    • C.1.2. 50 to 5 wt .-%, based on C.1, acrylonitrile
  • C.2. 85 to 20% by weight, based on C., of a crosslinked, particulate, elastomeric graft base (rubbers) with an average particle diameter d₅₀ of 0.05 to 5 μm and a glass transition temperature <10 ° C. and
• D. 1 to 20 parts by weight of an imidized polyacrylate which contains 0.05 to 10% by weight of anhydride structures of the formula (I) in addition to imide structures of the formula (II).
• E. 0 to 40 parts by weight of a thermoplastic vinyl copolymer
  • E.1. 50 to 95 wt .-%, based on E., styrene, α-methylstyrene or mixtures thereof and
  • E.2. 50 to 5 wt .-%, based on E., acrylonitrile.

4. Thermoplastic molding compositions according to claims 1, 2 and 3, characterized in that they

• A. 35 to 60 parts by weight of a thermoplastic, aromatic polycarbonate and
• B. 10 to 25 parts by weight of a thermoplastic, partially crystalline or amorphous polyamide or a mixture of a partially crystalline and an amorphous polyamide and
• C. 12.5 to 40 parts by weight of a graft polymer
  • C.1. 20 to 70 wt .-%, based on C., a mixture of
    • C.1.1. 60 to 80 wt .-%, based on C.1, styrene, α-methylstyrene or mixtures of these compounds and
    • C.1.2. 40 to 20 wt .-%, based on C., acrylonitrile
  • C.2. 80 to 30 parts by weight of a crosslinked, particulate, elastomeric graft base (rubber) with an average particle diameter d₅₀ of 0.09 to 1 µm and a glass transition temperature <-20 ° C and
• D. 2.5 to 17.5 parts by weight of an imidized polyacrylate which contains in D. 0.1 to 10% by weight of anhydride structures of the formula (I) and imid structures of the formula (II),
  wherein
  R¹, R² independently of one another are hydrogen or methyl,
  R³ is hydrogen or C₁-C₄ alkyl, and
• E. 0 to 20 parts by weight of a thermoplastic vinyl copolymer
  • E.1. 60 to 85 wt .-%, based on E., styrene, α-methylstyrene or mixtures thereof and
  • E.2. 40 to 15 wt .-%, based on E., acrylonitrile.

5. Thermoplastic molding compositions according to claim 1, characterized in that they

• A. 10 to 29 parts by weight of a thermoplastic, aromatic polycarbonate and
• B. 30 to 70 parts by weight of a thermoplastic, partially crystalline or amorphous polyamide or a mixture of a partially crystalline and an amorphous polyamide and
• C. 5 to 40 parts by weight of a graft polymer
  • C.1. 15 to 80 wt .-%, based on E., a mixture of
    • C.1.1. 50 to 95 wt .-%, based on C.1, styrene, α-methylstyrene or mixtures of these compounds and
    • C.1.2. 50 to 5 wt .-%, based on C.1. Acrylonitrile
  • C.2. 85 to 20% by weight, based on C., of a crosslinked, particulate, elastomeric graft base (rubbers) with an average particle diameter d₅₀ of 0.05 to 5 μm and a glass transition temperature <10 ° C. and
• D. 1 to 20 parts by weight of an imidized polyacrylate which contains 0.05 to 10% by weight of anhydride structures of the formula (I) in addition to imide structures of the formula (II),
• E. 0 to 40 parts by weight of a thermoplastic vinyl copolymer
  • E.1. 50 to 95 wt .-%, based on E., styrene, α-methylstyrene or mixtures thereof and
  • E.2. 50 to 5 wt .-%, based on E., acrylonitrile.

6. Thermoplastic molding compositions according to claims 1, 2 and 5, characterized in that they

• A. 10 to 25 parts by weight of a thermoplastic, aromatic polycarbonate and
• B. 35 to 60 parts by weight of a thermoplastic, partially crystalline or amorphous polyamide or a mixture of a partially crystalline and an amorphous polyamide and
• C. 12.5 to 40 parts by weight of a graft polymer
  • C.1. 20 to 70 wt .-%, based on C., a mixture of
    • C.1.1. 60 to 80 wt .-%, based on C.1, styrene, α-methylstyrene or mixtures of these compounds and
    • C.1.2. 40 to 20 wt .-%, based on C.1, acrylonitrile
  • C.2. 80 to 30% by weight, based on C., of a crosslinked, particulate, elastomeric graft base (rubbers) with an average particle diameter d₅₀ of 0.09 to 1 μm and a glass transition temperature <-20 ° C. and
• D. 2.5 to 17.5 parts by weight of an imidized polyacrylate which contains D. 0.1 to 10% by weight of anhydride structures of the formula (I) and imide structures of the formula (II),
  wherein
  R¹, R² independently of one another are hydrogen or methyl,
  R³ is hydrogen or C₁-C₄ alkyl, and
• E. 0 to 25 parts by weight of a thermoplastic vinyl copolymer
  • E.1. 60 to 85 wt .-%, based on E., styrene, α-methylstyrene or mixtures thereof and
  • E.2. 40 to 15 wt .-%, based on E., acrylonitrile.

7. Thermoplastic molding compositions according to claim 1 and 2, characterized in that as component A) the polycarbonate of 2,2-bis (4- contain hydroxyphenyl) propane (bisphenol A). 8. Thermoplastic molding compositions according to claim 1 and 2, characterized in that as component A) a copolycarbonate of 2,2-bis (4- hydroxyphenyl) propane (bisphenol A) with up to 80 mol%, based on the Molar sums of diphenols, of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane contain. 9. Thermoplastic molding compositions according to claim 1 and 2, characterized in that they are component B) polyamide-6, polyamide-6,6 or mixtures contain from these polyamides.