DD298129A5 - POLYURETHANE AND ABS THERMOPLASTIC POLYMER MIXTURE AND A METHOD OF MANUFACTURING THEM - Google Patents

Abstract

Improved thermoplastic polymer blends include a blend of a thermoplastic polyurethane A, at least one component B comprising a grafted polybutadiene, and optionally at least one further thermoplastic component C, wherein the weight ratio of AB: C is between 95: 5 and 5:95 and in polyurethane A 5 to 25 * of a compound having a molecular weight of 600 to 6,000 containing hydroxyl or amino groups.

Description

The invention relates to thermoplastic polymer mixtures consisting essentially of a mixture of a thermoplastic polyurethane A, at least one component B, which has a grafted polybutadiene and optionally a further thermoplastic component C, excipients D and fillers odor fibers E.

EP-A 0131714 discloses polymer blends of polyurethane glass liners and impact modifiers, e.g. Butyl acrylate described.

Blends of such high tear propagation resistance are not specified there. The addition of ABS and butadiene-containing graft rubbers is not mentioned there.

In US-A 4179479 blends of thermoplastic polyurethane with thermoplastics such. As ABS, polycarbonate in combination with Acrylatzusätzen known. The mixtures given in the examples have a hardness of 32 to 72 Shore D (E-ModuKIOOOMPa).

DE-A 2854409 discloses a process for the production of thermoplastic chemical materials by feeding a preformed thermoplastic polymer into an extruder and adding polyisocyanates and chain extenders in a second feed point. Tearing resistance and processability of the so obtained Werks-FFe meet in part not the increased demands of practice.

In DE-A 2405a 31 the Zuoatz of ABS is given to thermoplastic polyurethanes in certain molecular weight ranges. The modulus of elasticity and the tear propagation resistance likewise do not correspond to the increased requirements.

In "Rubber World", Vol. 199, No. 6 (1989), pages 30-35, various "impact modifiers", such as polymethyl methacrylate, are described as additives to pure hard segment. However, the wear resistance (tear propagation resistance) of these polymers is poor and the ABS used therein has poor Notched Izod Impact Strength.

The object of the invention was therefore to provide thermoplastic polymer blends having an improved tear propagation resistance and increased hardness, which can be processed well.

The invention relates to thermoplastic polymer blends of at least one thermoplastic polyurethane A and at least one other thermoplastic B, consisting essentially of a mixture of

A) a thermoplastic polyurethane obtainable by reaction of

a) a diisocyanate Aa)

b) at least one preferably short-chain chain lengthener Ab), in particular a diol, preferably having a maximum molecular weight of 399

c) a hydroxyl group or amino group-containing relatively high molecular weight compound Ac), preferably having a molecular weight of 600 to 6000

B) at least one graft rubber and / or ABS thermoplastic B, wherein the weight ratio of A: B may range from 96: 4 to 4:96, preferably 90:10 to 70:30,

C) optionally with at least one further thermoplastic component C, wherein the weight ratio of (A + B): C95; 5 to 5: 95,

D) optionally the usual excipients and

E) optionally fillers and / or fibers

with the proviso that, based on the sum of Aa) to Ac) the proportion by weight of Ac) is 5 to 25 wt .-% and that the ratio of NCO groups of component Aa) to the Zerewitinoff-active groups of components Ab) and Ac) 0.9 to 1.15, preferably 0.9 to 1.1 and used as C) terephthalic acid esters are used to less than 20%. In a preferred embodiment, component B is used without the addition of component C). In another embodiment, based on the sum of components B and C, at least 20, in particular at least 50 parts by weight of B are used.

The polymer blends according to the invention have a Shore hardness of 73 to 90 Shore D, preferably 80 to 90 Shore D and a Ε-modulus of more than 1000 MPa, preferably from 1900 to 3000 MPa, particularly preferably from 2200 to 3003 MPa. Surprisingly, the mixtures according to the invention optimally combine the required properties. The strengths, in particular wear resistance and tear propagation resistance are extremely high. The further processing is possible in contrast to the further processing of other mixtures without vacuum drying of the granules. With the mixtures according to the invention constructed moldings show no segregation phenomena such. B. opaque appearance. Despite the high Ε-modulus of preferably more than 1900MPa or the high Shore D hardness (> 72D), the mixtures according to the invention still exhibit high elongation at break values and a pronounced cold-impact behavior. The mixtures continue to show unity. improvement in terms of expansion coefficient, gasoline resistance, swelling in polar solvents and hydrolysis resistance. It is surprising that such hard polymer blends still show such a favorable wear behavior.

Diisocyanates Aa) to be used according to the invention are the aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates known per se of the prior art. Preferred diisocyanates according to the invention are aromatic diisocyanates, naphthylene-1-S-diisocyanate, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), 1,4-diisocyanatobenzene and the corresponding hydrogenated product, toluene diisocyanates and in particular the diphenylmethane diisocyanate isomers. Particularly preferred is the 4,4'-diisocyanatodiphenylmethane or its mixture of isomers with up to 5 mol%. preferably 1 to 4 mol%, of 2,4'-diisocyanatodiphenylmethane, usually accompanied by very small amounts of the 2,2'-DiisoΓ.yanato-diphenylmethane isomers.

The said diisocyanates may optionally be used together to about 15 mol% (based on diisocyanate) of a higher functional polyisocyanate; However, the amount of the higher-functional polyisocyanates must be limited so that a still fusible or thermoplastic polyurethane elastomer is obtained. A larger amount of higher-functional isocyanates must generally be eusgegleichen by the concomitant use of on average less than difunctional hydroxyl or amino compounds or monoisocyanates or so that excessive chemical crosslinking of the product is avoided.

Examples of higher functional isocyanates and monofunctional compounds can also be found in the prior art cited above. For example, mention may be made of monoamines such as butylamine or dibutylamine, hydroxylamine, stearylamine, N-methylstearylamine, and also monoalcohols such as butanediol-1,2-ethylhexanol-1, dodecanol-1, isobutanol or tert-butanol, cyclohexanol or ethylene glycol monomethyl ether and stearyl alcohol.

Preferred chain extenders Ab) are e.g. the compounds described in DE-A-2302564,2423764,2549372,2402840,2457387 and 2854384. These are, in particular, low molecular weight polyalcohols, preferably diols, diamines, in particular aliphatic diamines, hydrazines and hydrazide derivatives. As diamines are diethyl-toluylenediamines, or called isophoronediamine. Also, amino alcohols such as ethanolamine, diethanolamine, n-methyldiethanolamine, 3-aminopropanol or compounds such as hydrazine (hydrate) or carbodihydrazide according to the invention in question. Preferred chain extenders are diols, e.g. Ethylene glycol, di- and triethylene glycol, 1,6-hexanediol and hydroquinone di-ßhydroxyethylether, and more preferably the 1,4-butanediol, optionally in mixtures with other diols, especially 1,6-hexanediol. Preference is given to mixtures of from 96 to 80 mol% of 1,4-butanediol with 4 to 20 mol% of 1,6-hexanediol.

The molecular weight of the chain extenders is 32 to 399, preferably 62 to 220.

Furthermore, monofunctional compounds in minor proportions, for example. B. from 0.01 to 4Gew .-%, based on PU solid, be used as so-called chain terminators. Examples are monoalcohols such as butanol, 2-ethylene hexanol, isobutyl alcohol, octanol-1, stearyl alcohol or monoamines such as aniline, dibutylamine, N-meth> isearylamine or piperidine.

Preferred hydroxyl-containing higher molecular weight compounds Ac) are polyester, polyester carbonate and polyether oils, for. B. polyester diols of geradkettigon or branched aliphatic and / or cycloaliphatic diols and aliphatic dicarboxylic acids, in particular adipic acid. However, they may also contain minor amounts of aromatic dicarboxylic acids, in particular phthalic acid and optionally also terephthalic acid, as well as their hydrogenation products.

Also suitable are hydroxyl polycarbonate, hydroxypolycaprolactones. In a particularly preferred embodiment, butane diol 1,4-adipate of molecular weight 1500 to 3000 is used.

Also preferred are hydroxyethordiols based on ethylene oxide, propylene oxide or mixed polyethers of propylene oxide and / or ethylene oxide and / or tetrahydrofuran, e.g. Hydroxyether diols based on tetrahydrofuran having a molecular weight of 1000 to 3000. Suitable polyols are e.g. in the German Offunlegungsschriften 2302564,2423764,2549372 (US-PS 3963679), DE-OS 2402840 (US-PS 3984607), DE-AS 245738 / (US-PS 4035213) and in DE-OS 2854384, 2920501 and 3405531 detail described.

Optionally, also höhenmopolekulare Polyaminoverbindui conditions, preferably be used with primary aromatic amino groups. Preferred representatives are prepared, for example, by hydrolysis of corresponding NCO prepolymers based on relatively high molecular weight polyhydroxy compounds and excess aromatic diisocyanates by (preferably basic) hydrolysis. Examples of these methods are given in DE-A-2948419, DE-A-3039600, DE-A-3112118, EP-A-61627, EP-A-71132 and EP-A-97869. In the former patent also other methods of the prior art for the preparation of aromatic amino compounds of higher molecular structure, called Amlnopolyether called, as are suitable for the inventive method. Further production processes are described in DE-AS 1694152, FR-PS 1415317 or DE-AS 1155907.

The proportion by weight of component A "is based on the sum of A. Ac 5-25%, preferably 8-15%.

Before and / or during and / or after the polyurethane reaction, it is of course possible to use the customary auxiliaries D, such as catalysts, release agents, antistatic agents, flame retardants and colorants according to the prior art (see, for example, US Pat.

DE-A-2854409, DE-OS 2920501 and DE-PS 3329775) are added. Antioxidants and UV absorbers (light stabilizers) are also possible according to the prior art (see DE-A-3405531).

As catalysts can be such. As tertiary amines, organic metal compounds, in particular organic tin, lead and titanium compounds are used, for. Tin acetate, stannous ethylhexanoate, dibutyltin dilaurate or lead acetate.

As a release agent waxes or oils are preferably used, also z. As long-chain compounds with carboxyl, ester, amide, urethane or urea groups and silicones, as they are listed as release agents, for example in DE-OS 2204470.

The amounts of reaction components Aa) to Ac) for the polyurethanes are in the process of the invention in the rule

chosen so that the NCO / OH equivalent ratio of isocyanate to OH-Verblndungen between 0.9 and 1.15, preferably 0.95 and 1.03.

Preferred graft rubbers B and / or ABS thermoplastics B are elastic-thermoplastic products which are composed essentially of the monomers acrylonitrile, butadiene and styrene or α-methylstyrene. Butadiene may be partially replaced by another rubber component, e.g. B. by an ethylene-propylene-1,5-diene methylene rubber (EPDM rubber) or acrylic rubbers, but is preferably present at least 20 wt .-%, in particular 25-40Gew .-%, based on component B.

These polymers are prepared in a conventional manner by emulsion, suspension, bulk and solution polymerization or combinations of these methods, as z. From CH. Basdekis in "ABS-Plastics" Reinhold Publishing Corporation, New York, 1964.

ABS polymers B preferred according to the invention are mixtures of

Ba) 5-70% by weight of one or more elastomeric graft products and Bb) 95-30% by weight of one or more thermoplastic non-elastomeric resins.

Graft products Ba) are preferably polymers which are obtained by polymerization of graft monomers in the presence of a rubber as graft base. The rubber content is about 5 to 80% by weight and is determined by the polymerization process.

In particular polybutadiene, butadiene / acrylonitrile and butadiene / styrene polymers and butadiene-styrene block polymers are suitable as the graft base. Graft monomers are mainly styrene, mixtures of styrene and acrylonitrile, preferably in a weight ratio of 90:10 to 50:50, mixtures of styrene and methyl methacrylate, preferably in a weight ratio 5:95 to 95: 5, and styrene-acrylonitrile-methyl methacrylate mixtures.

The second component of the ABS polymers forming thermoplastic resin Bb) forms the continuous phase (matrix) and z. Example, a polymer or copolymer of styrene, α-methyl styrene, acrylonitrile, methyl methacrylate and maleic anhydride.

Preference is given to polystyrene, styrene-acrylonitrile copolymers having an acrylonitrile content of from 20 to 35% by weight and also α-methylstyrene-acrylonitrile copolymers having an acrylonitrile content of from 20 to 31% by weight. The weight average molecular weight of these resins is usually 50,000 to 55,000. The molecular nonuniformity expressed by the value (M _w / M _n ) -1 = U _n is 1.0 to 3.5.

Preferred polyesters C can be prepared from terephthalic acid (or its reactive derivatives) and alkanediols having 2 to 10C atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695ff., Carl Hanser Verlag, Munich 1973).

However, terephthalic acid esters B are used at less than 20% by weight, based on the sum of B + C.

Preferred polyalkylene terephthalates C contain at least 80, preferably at least 90 mol%, based on the dicarboxylic acid, terephthalic and at least 80, preferably at least 90 mol%, based on the diol component, ethylene glycol and / or 1,4-butanediol radicals.

In addition to terephthalic acid residues, the preferred polyalkylene terephthalates C may contain up to 20 mol% of residues of other aromatic dicarboxylic acids having 8 to 14 C atoms, aliphatic dicarboxylic acids having 4 to 12 C atoms, such as. As residues of phthalic acid, isophthalic acid, naphtha, in-2,6-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, succinic, adipic, sebacic, azelaic and cyclohexanediacetic.

The preferred polyalkylene terephthalates C may contain, in addition to ethylene glycol or butane-1,4-diol residues, up to 20 mol% of other aliphatic diol having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, eg. B. residues of propanediol-1,3,2-ethylpropane-1,3-diol, neopentyl glycol, pentane-dioi->, 5, 1,6-hexanediol, cyclohexane-dimethanol-i ^, 3-methylpentanediol-2,4,2 -Methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,3 and -1,6,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3, hexanediol-2,5,1, 4-di (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis ( 3-.beta.hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 2715932).

The polyalkylene terephthalates C can be prepared by incorporation of relatively small amounts of 3 or 4-valent alcohols or 3 or 4basic carboxylic acids, as described, for. 0. are described in DE-OS 1900270 and US Patent 2692744 are branched. Examples of preferred branching agents are t imesinsäure, trimellitic acid, trimethylolethane u, .J-propane and pentaerythritol. It is advisable to use not more than 1 mol% of the Ve branching agent, based on the acid component.

Particularly preferred are polyalkylene terephthalates C which have been prepared solely from terephthalic acid or its reactive derivatives (e.g., its dialkyl esters) and ethylene glycol or butane-1,4-diol.

The polyothylene terephthalates preferably used as component C generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, in particular 0.6 to 1.2 dl / g, and the Polybutylene terephthalates used as component B generally have an intrinsic viscosity of 0.7 to 1.5 dl / g, preferably 0.8 to 1.3 dl / g, in particular 0.8 to 1.05 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C in 0.5% solution.

Instead of the homo- or copolyesters and the mixtures of these polyesters can be used. Preferred mixtures consist of

a) 1-99, preferably 10-80, in particular 30-60Gew .-% polyethylene terephthalate and

b) 99-1, preferably 90-20, in particular 70-40Gew .-% poly (1,4-butylene terephthalate). Particularly preferred is poly (1,4-butylene terephthalate).

The novel polyester molding compositions may contain conventional additives, such as lubricants and mold release agents, nucleating agents, stabilizers, fillers and reinforcing agents, flame retardants and dyes.

The filled clay or reinforced molding compositions may contain up to 60, preferably 10 to 50,% by weight, based on the molding composition, of a filler and / or reinforcing material. Preferred reinforcing materials are glass fibers. Preferred fillers which may also have reinforcing properties are glass beads, mica, silicates, quartz, talc, titanium dioxide, wollastonite.

The flameproofing agent-treated polyester molding compositions contain flame retardants in a concentration of generally less than 30% by weight, based on the molding compositions.

Particularly preferred polycarbonates C are the polycondensates obtainable by reacting dihydroxydiarylalkanes with phosgene or diesters of carbonic acid, suitable in addition to the unsubstituted dihydroxydiarylalkanes also those whose aryl radicals in the o- and / or m-position to the hydroxyl group carry methyl groups or halogen atoms.

Likewise, branched polycarbonates are suitable. These polycarbonates generally have average molecular weights between 10,000 and 100,000, preferably between 20,000 and 40,000.

Suitable aromatic dihydroxy compounds are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis- (hydroxyphenyO-alkanes such as, for example, C 1 -C ₈ -alkylene or C 1 -C -alkylidenebisphenols, bis (hydroxyphenyl) -cycloalkanes, such as for example, Cj-C ^ -Cycloalkylen- or Cg-C ^ -Cycloalkylidenbisphenole, bis (hydroxyphenyl) sulfides, ethers, ketones, sulfoxides or sulfones.

Further, α, α'-bis (hydroxyphenyl) diisopropylbenzene and the corresponding nuclear alkylated or nuclear halogenated compounds. Preference is given to polycarbonates based on bis (4-hydroxy-phenyl) -propane-2,2 (bisphenol A), bis (4-hydroxy-3,5-dichloro-phenyl) -propane-2,2 (tetrachlorobisphenol A ), Bis (4-hydroxy-3,5-dibromo-phenyl) -propane-2,2 (tetrabromobisphenol A), bis (4-hydroxy-3,5-dimethyl-phenyl) -propane-2,2 ( Tetramethylbisphenol A), bis (4-hydroxy-phenyl) -cyclohexane-1,1 (bisphenol Z) and based on Dreikernbisphenolen such as a, a'-bis (4-hydroxyphenyl) -p-diisopropylbenzene.

Other bisphenols suitable for the preparation of polycarbonates are described in US Pat. Nos. 3,028,365, 2,998,335, 3,148,172, 3,271,368, 299,137,291, 273,327,136, 3,230,078, 3,014,891 and 2,999,846.

In principle, preferred polycarbonates can be defined as those which contain recurring carbonate groups

O-O-C-O-

and units of the formula linked to these carbonate groups

own (see US Patent 3,070,563).

Particularly preferred aromatic polycarbonates have repeating structural units of the formula

in which

Z is a single bond, an alkylene or alkylidene radical having 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical

with 6 to 12 C atoms, an oxygen atom, a sulfur atom, a -CO-.SO-or-SOj group, preferably methylene or isopropylidene,

R ¹ and R ^{2 are} a hydrogen atom, a halogen atom or an alkylene or alkylidene radical having 1 to 7 C atoms and η is an integer of Obis 4.

Preferred aromatic polycarbonates have a melt index of about 1 to 24g per 10 minutes at 3OU ⁰ C, measured according to ASTM D-1238.

The most important aromatic polycarbonate because of its availability is the bis- (4-hydroxyphenyl) -2,2-propane-based polycarbonate known as bisphenol A polycarbonate; commercially available for. 4, commercially available from Mobay Chemical Corporation, USA, as Merlon M39 (melt index about 12 to 24), M40 (melt index about 6 to 12), M50 (melt indox about 3 to 6) and M60 (melt index <3 [g / 10 minutes) at 300 ° C). The tensile modulus of elasticity of these types is about 2 300 MPa (DIN 53457).

Other thermoplastics C which are suitable according to the invention are polystyrene (in particular impact-modified polystyrene), aromatic polyethers (for example polyphenylene oxide) and polybutylene glycol terephthalate containing soft-segment polyethers. Polymers of this type are z. By Vieweg et al. in the "Kunststoff-Handbuch", Vol. II, IV-VII, IX and Xl, Carl Hanser Verlag, Munich, 1963-1971, and by Hans-Jürgen Saechtling in the "Kunststofftaschenbuch", 20, edition, Carl Hanser Verlag, Munich Vienna, 1977.

In addition, as component E fillers or fibers may be included.

In particular, up to 50% by weight of inorganic or organic fibers and / or other inorganic fillers such as mica or talcum can be added to the claimed polymer mixtures.

As fibrous reinforcers, inorganic fibers are particularly preferred because of the reinforcing effect and their heat resistance. Preferred inorganic fibers for the present invention are sized glass fibers having a thickness of 8-30, especially 10-18μηη and having a length of 0.3mm to about 100 mm, in particular 1-10 mm, which are prepared according to the prior art , An addition of 10 to 40% by weight is particularly favorable.

The glass fiber sizes preferably consist essentially of 2 components; a film-forming component (generally polyvinyl acetate, polyester, polyurethanes or epoxy resins) and as adhesion promoter in general an organosilicon compound. Sizing agents are based on polyurethane and have an amino group-containing adhesion promoter.

In addition, the glass fiber sizes may optionally also contain known antistatic agents and lubricants.

Processes for the preparation of polyurethane-based glass fiber sizes are described e.g. in DE-Auslegeschriften 2426657 (GB-PS 1456628), 2426654 and DE-A 2854406 described. Fillers such as mica, other silicates, chalk and dyes may also be added to the inorganic fiber.

The polymer blends according to the invention are particularly suitable, for example, for the following applications: semi-finished products, profiles, toys, seat shells, protective helmets, pump housings, pump seals, pipes, tennis rackets, housings for tools and drills, pump parts, shell cases and automotive exterior parts such as bumpers, wheel covers, spoilers, grille and headlamp housing , They are particularly suitable for articles with high wear resistance, very high tear propagation resistance and high elongation at break, such as bumpers, shoe parts, sieve elements, dowels and door fittings.

The polymer mixtures may preferably with metal parts, for. B. made of steel, iron and aluminum screwed flat, glued, sprayed or otherwise connected. So composite materials of various types such. B. bumpers, bumpers etc. are produced.

The use of appropriate moldings or composites thereof is also the subject of the invention.

The molded articles of the polymer blends may be injection molded, extruded, calendered, extrusion blown, i. obtained by the usual thermoplastic molding processes.

The thermoplastic polymer blends of this invention can be prepared in a variety of ways. In a preferred embodiment, the polyurethane thermoplastic is prepared by the ribbon or screw process (see Becker / Braun, Kunststoff Handbuch, Volume 7, Polyurethane, Capital 8.2.1 page 428 ff, Carl Hanser Verlag Munich, Vienna 1983).

The thermoplastic polyurethane can then be mixed in a second step with the component B and optionally the other thermoplastics C and processed into moldings. In a preferred embodiment, a twin-screw kneader is used, wherein the components required for polyurethane formation are fed into a first feed point and then preferably component B and optionally C are metered in during the polyurethane formation in the middle part of the twin-screw kneader. Reference is made in this connection to US Pat DE-PS 2302564 described method.

The said polyurethane-forming components Aa) to Ac) can be introduced into the extruder via a single or else several feed points. The components can be introduced both separately and premixed into the screw machine, see DE-A-2842806. In particular, when using amino-functional chain extenders, it is recommended, however, first to produce a Unuetzungsprodukt of the polyisocyanate and the higher molecular weight polyhydroxyl compound. As isocyanate component Aa) in this case, therefore, a relatively high molecular weight, NCO-containing Voraddukt is used.

Examples

Preparation of Thermoplastic Polymer Blends of the Invention on a Two-Kneaded Kneading Machine In the examples, a two-wool kneading machine is used. .- kneading machine e.g. The type ZSK53V of the company Werner & Pfleiderer, Stuttgart, with self-cleaning shaft stocking and a kneading element content of about 20% used. The process part consists of 12 separately heatable housings, the length of the process part corresponds to about 20 times the shaft diameter.

The residence times of the reaction melt in the screw machine are generally 0.3 to 30, preferably 0.5 to 4 minutes.

The temperatures of the Schneckengehäuso are between about 60 and 300 ° C (about 80 to 280 ° C) in the feed zone; about 100 to 300 ⁰ C in the middle of the extruder and about 120 to 27O ⁰ C in the discharge zone. The melt emerging from the extruder is quenched and comminuted by methods known per se. The preparation of the thermoplastic polymer mixtures is carried out with the starting materials of Tables 2, 4 and 6 in the stated parts by weight.

Table 1 shows the composition of the TPU components used (component A).

TABLE 1 Composition of component A (PU content)

Aa) 4,4'-diisocyanatodiphenylmethane containing about 2.5% by weight of 2,4'-isomer TPU1 65.7 TPU 2 65.2 TPU 3 66.0 TPU 4 64.8 TPU 5 74,1 Ab) Butanediol-1,4 Hexanediol-1,6 Octadecanol 20,9 2,1 20,6 2,1 1,3 20.8 2.1 20,6 2,1 1,5 25.9 Ac) Butanediol-1,4-adipate, molecular weight 2 250 10.5 10.3 - - - Polytetramethylene ether diol Molecular weight 1000 Polytetramethylene ether diol Molecular weight 2,000 - - 5.2 5.2 5.2 5.2 -

2,2'-6,6'-tetraisopropyl-diphenylcarbodiimide 0.1 0.1 -

Pentaerythrityl tetrakis-3- (3,5-di-t-

butyl-4-hydroxyphenyl) propionate 0.3 0.3 0.3 0.3

2,6-di-t-butyl-4-methylphenol 0.2. 0.2 0.2 0.2

Poly (N-hydroxyethyl-2,2,6,6-tetra

methyl-4-hydroxypiperidinosuccinic acid ester) 0.2 0.2 0.2 0.2

The component Ac) (with additives) is metered from the 120 ° C hot pot via a gear pump in the housing 1 of a Zweiwellenknetmaschine. Also in the housing 1, the Diolgemisch Ab) is metered with a temperature of 6O ⁰ C via a gear pump. The component Aa) is also pumped into the housing 1 with 6O ⁰ C via a gear pump. The non-polyurethane-containing thermoplastics or mixtures thereof (components B and optionally CE of the claims) are introduced via a vibrating channel in the screw center. The following housing temperatures were set on the screw machine:

casing 1 2.3 4.5 6.7 8.9 11/12 head temperature 80 ⁰ C 200 ⁰ C 200 ⁰ C 200 ⁰ C 220 ° C 200 ⁰ C 24O ⁰ C

Examples 1-7

In these examples according to the invention thermoplastic polyurethanes are used with a polyester as component A ₀ ). The second component used is a graft rubber (ABS 1) with about 30% by weight of polybutadiene as elastomer component and about 70% by weight of resin component of styrene and acrylonitrile. The proportions A: B are shown in Table 2.

Table 2 Formulations of Examples 1-7

example 1 2 3 4 5 6 7 TPU1 95 90 85 80 TPU 2 95 85 80 ABS1 5 10 15 20 5 15 20

The TPU-ABS blonds have nt.cn three days of storage, injection to standard injection molding machines and Temperur.g the sample of 15h at 110 ° C the mechanical properties described in Table 3 on. The materials "allow me to process well thermoplastics and give homogeneous transparent injection molded parts at low ABS contents, they become translucent at higher ABS contents, they show bending moduli of more than 2000 MPa, very high resistance to fouling and very high values in the penetration test -20 ⁰ C very high impact resistance at the fracture pattern, non-splitter products. the linear expansion coefficient of these blends is cheap (low). Since the same modulus, and impact resistance of polyurethane thermoplastics are very high, these new materials can even be used in combination with metals.

Table 3 Properties of the products of the invention according to Example 1 to 7

exam DIN measure 1 55.2 2 55.2 3 54.2 4 58.2 5 53.9 6 52.7 7 68.6 standard unit 13 15 47 19 107 30 tensile strenght 53504 MPa 253.6 296 293 305 230 309 elongation 53504 % 2437 2382 2422 2352 2416 2367 2310 Tear strength 53515 KN / m Flexural modulus 53452 MPa 123 122 118 115 120 116 113 bending stress SBB (RT) 53452 MPa 57 61 85 106 93 130 131 Penetration Test (-20 C ^c) 53443 J 3 3 4 4 3-4 4 4 Fracture picture at 82 83 81 82 83 84 83 Penetration test " Shore HärteD 53505 113 125 113 123 115 119 119 Linear expansion coefficient α 53752 10 " ⁸ K- '

1 rating 1 = brittle, splinter break

2 = partly brittle, big cracks

3 = partly tough, some small cracks

4 = tough, without cracks.

Examples 8-11

In these examples of the invention thermoplastic polyurethanes are used with a polyether diol as component AJ. Component B is identical to that of Examples 1-7. The proportions are shown in Table 3.

Table 4 Recipes of Beis <* j8-12

example 8th 9 10 11 12 TPU 3 95 90 8'j 80 TPU 4 80 ABS1 5 10 15 20 ABS 2 20

These blends have slightly lower flex moduli and tear strengths than Examples 1-7, but also show excellent cold properties (Table 5).

Example 12

In this example, component A _{b) is} slightly modified from Example 11 by the addition of octadecanol. As graft rubber (ABS 2), a type with 50% by weight of butadiene is used here. This product is softer and more brittle in the cold (Table 5).

-8- 298 129 Table 5 Properties of the products according to the invention according to Example 8 to 12

Test DIN dimension 8 9 10 11 12

Standard unit

tensile strenght 53504 MPa elongation 53504 % Tear resistance 53 515 KN / m Flexural modulus 53452 MPa bending stress SBB (RT) 53442 MPa Penetration Test (-2O ⁰ C) 53443 J Fracture picture at Puncture attempt ¹¹ Shore HärteD 53505 Linear expansion coefficient α 53752 ΙΟ ' "·

63.0 146 62.3 156 56.8 160 56.46 1704 241 2033 248 2022 237 1950 268 2027 78 106 102 98 103 20 79 99 91 113 2-3 79 4 80 4 82 4 80 4 81

109 117 114 120

1 rating 1 = brittle, splinter break

2 = partly brittle, big cracks

3 = toils tough, some small cracks

4 = tough, without riose.

Examples 13-16

The materials of these noninventive examples were prepared in the same manner as those of Examples 1-12.

Table 6 indicates the composition.

Examples 13 and 14

These are the thermoplastic polyurethanes of Examples 1-4 and 5-7 (TPU 1 and TPU 2). These are very stiff products (bending modulus above 2400 MPa, Table 7), which show low values and a brittle fracture pattern at -2O ⁰ C during the penetration test.

Example 15

Here, TPU1 is blended with 10% by weight of a medium viscosity thermoplastic polybutylene terephthalate ester. Also, this material shows worse cold properties than the inventive examples.

Example 16

The TPU component consists in this blend only of 4,4'-diisocyanatodiphenylmethane and butanediol, component B is ABS 1. This material has a significantly lower bending modulus and worse cold properties (Table 7).

Table 6 Recipes of Example «13-16

13 14 15

TPU1 100

TPU2 - 100 - -

TPU4 -

TPU 5 - 43.6 ABS 1 56.4 PBJ - 10

Table 7 Characteristics of the non-inventive products according to Example 13 to 16

Test DIN standard Unit of measure 13 14 15 16

MPa

KN / m

MPa

MPa

tensile strenght 53504 elongation 53504 Tear strength 53515 Flexural modulus 53452 Bending stress SbB (RT) 53452 Puncture attempt (-2O ⁰ C) 53443 Fracture picture at Penetration test " Shore HärteD 53505 1 rating 1 = brittle, splinter break 2 = partly brittle, big cracks 3 = partly tough, some small cracks 4 = tough, without cracks

57.8 50.2 60.9 45.7 10 100 20 174 350 249 2482 2459 2 573 1773 124 125 120 68 85 19 11 20 3 3 1 2-3 82 81 82 79

Claims (12)

1. thermoplastic polymer mixtures, consisting essentially of a Misdung A) a thermoplastic polyurethane obtainable by reaction of a) a diisocyanate Aa) b) at least one short-chain chain extender Ab), c) a hydroxyl or amino group-containing relatively high molecular weight compound Ac), preferably having a molecular weight of 600 to 6000 B) at least one graft rubber and / or ABS thermoplastic B, wherein the weight ratio of A: B may be from 96: 4 to 4:96, C) optionally with at least one further thermoplastic component C, wherein the weight ratio of (A + B): C95: 5 to 5:95 can be, D) optionally the usual excipients and E) optionally fillers and / or fibers characterized in that, based on the sum of Aa) to Ac), the proportion by weight of Ac) of from 5 to 25% by weight and of the ratio of NCO groups of component Aa) to the Zerewitinoff-active groups of components Ab) and Ac) 0.9 to 1.1 and used as C) terephthalic acid esters are used to less than 20%. 2. Polymer mixture according to claim 1, characterized in that the diisocyanate Aa) is 4,4'-diisocyanatodiphenylmethane with a maximum of 5 wt .-% 2,4'-diisocyanatodiphenylmethane. 3. Polymer mixture according to at least one of the preceding claims, characterized in that the chain extender Ab) is a polyhydric alcohol, a polyamine or an aminoalcohol having a maximum molecular weight of 399. 4. A polymer mixture according to at least one of the preceding claims, characterized in that the hydroxyl group h hltige relatively high molecular weight compound Ac) is a polyester diol having a molecular weight of 600 to 6000. 5. Polymer mixture according to at least one of the preceding claims, characterized in that component B is an ABS thermoplastic with 25-40 wt .-% butadiene. 6. Polymer mixture according to at least one of the preceding claims, characterized in that a terephthalic acid ester, in particular polybutylene terephthalate, is contained as component C. 7. Polymer mixture according to at least one of the preceding claims, characterized in that component C is a polycarbonate or a mixture of a polybutylene terephthalate and a polycarbonate. 8. Polymer mixture according to at least one of the preceding claims, characterized in that the Shore hardness D of the mixture is 73 to 90 and the E modulus> 1000MPa. 9. Polymer mixture according to at least one of the preceding claims, characterized in that they contain up to 50 wt .-% of inorganic or organic fibers and / or other inorganic fillers such as mica or talcum as component E. 10. Polymer mixture, according to at least one of the preceding claims, characterized in that it contains 10-40Gew .-% glass fibers, with a polyurethane-based sizing. 11. A process for the preparation of thermoplastic polymer mixtures according to claim 1, characterized in that the components Aa) to Ac) and in a subsequently arranged feed the components B) and optionally C) and E) feeds in a Zweinneckenknetrnaschine in a first feed. 12. Thermoplastic molded bodies and composites thereof comprising a polymer mixture, characterized in that the polymer mixture corresponds to at least one of the preceding claims.