EP1274792A1

EP1274792A1 - Impact resistant thermoplastic molding materials comprised of syndiotactic polystyrene, glass fibers and acrylate impact modifiers

Info

Publication number: EP1274792A1
Application number: EP01927820A
Authority: EP
Inventors: Michael GEPRÄGS; Graham Edmund Mc Kee; Konrad Knoll
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2000-04-03
Filing date: 2001-03-28
Publication date: 2003-01-15
Also published as: AU2001254748A1; WO2001074943A1; US20030130403A1; US6727297B2; JP2003529656A; DE10016280A1

Abstract

The invention relates to thermoplastic molding materials containing, as essential constituents: A) 5 to 95 wt. % of a vinyl aromatic polymer having a syndiotactic structure; B) 2 to 50 wt. % of an inorganic filler; C) 1 to 45 wt. % of a rubber-elastic particle-shaped graft polymer; D) 1 to 10 wt. % of a compatibility mediator, optionally; E) 1 to 45 wt. % of a rubber-elastic particle-shaped styrene/diene block copolymer whose portion of diene can be completely or partially hydrogenated, optionally; F) 1 to 35 wt. % of a thermoplastic elastomer based on copolymers comprised of vinyl aromatic monomers, dienes and, optionally, 1,1-diphenylethylene, and optionally; additives, whereby the weight percentages from A) to G) total 100.

Description

Impact-resistant thermoplastic molding compositions made of syndiotactic polystyrene, glass fibers and acrylate impact modifier

description

The invention relates to thermoplastic molding compositions containing

A) 5 to 95% by weight of a vinyl aromatic polymer with a syndiotactic structure

B) 2 to 50% by weight of an inorganic filler

C) 1 to 45% by weight of a rubber-elastic, particulate graft polymer

D) 1 to 10% by weight of a compatibility agent and, if appropriate

E) 1 to 45% by weight of a rubber-elastic particulate

Styrene-diene block copolymers whose diene part can be fully or partially hydrogenated and, if appropriate

F) 1 to 35% by weight of a thermoplastic elastomer based on copolymers of vinylaromatic monomers, dienes and, if appropriate, 1, 1-diphenylethylene and, if appropriate

G) additives

as essential components, the sum of the weight percentages from A) to G) being 100.

Furthermore, it relates to the use of the thermoplastic molding compositions for the production of fibers, films and moldings, and to the fibers, films and moldings obtainable therefrom.

Owing to its syndiotactic polystyrene

Crystallinity has a very high melting point of approx. 270 ° C, high rigidity and tensile strength, dimensional stability, a low dielectric constant and high chemical resistance. The mechanical property profile is maintained even at temperatures above the glass temperature. The production of syndiotactic polystyrene in the presence of metallocene catalyst systems is known and z. B. described in detail in EP-A 0 535 582.

Because of the brittleness of syndiotactic polystyrene, its area of application is very limited.

There was therefore a desire to reduce the brittleness of syndiotactic polystyrene, hereinafter also referred to as SPS, and at the same time to improve its impact resistance, breaking stress and rigidity.

Polymer blends made from syndiotactive polystyrene, inorganic fillers, polyphenylene ether and a rubber component are known from EP-A 0 779 329 (Idemitsen Kosan) and WO-A 941 24 206 (Dow). However, the blends still have insufficient properties, e.g. low fluidity, complex manufacture, on.

EP-A 755 972 describes SPS, which is impact modified with a mixture of a block copolymer of styrene and hydrogenated butadiene on the one hand and a core shell polymer with a butadiene polymer core on the other. Molding compositions with inorganic fillers are not disclosed.

The object of the present invention was therefore to produce a thermoplastic molding composition based on vinylaromatic polymers with a syniodotactive structure, which combines high impact strength, high rigidity (modulus of elasticity), good flowability (MVR, processability) and tensile strength.

We have found that this object is achieved by the thermoplastic molding compositions defined at the outset.

Furthermore, the use of the thermoplastic molding compositions for the production of fibers, films and moldings and the fibers, films and moldings obtainable therefrom were found.

The thermoplastic molding compositions according to the invention contain, as component A), 5 to 95% by weight, preferably 20 to 80% by weight, in particular 40 to 70% by weight, of a vinylaromatic polymer with a syndiotactic structure. The term “with a syndiotactic structure” means here that the polymers are essentially syndiotactic, ie the syndiotactic fraction determined according to ¹³ C-NMR is greater than 50%, preferably greater than 60% mmmm pentads. Component A) is preferably composed of compounds of the general formula I.

in which the substituents have the following meaning:

R ^{1 is} hydrogen or C ¹ -C ₄ -alkyl,

R ² to R ⁶ independently of one another hydrogen, Ci- to -C-alkyl _# CQ - to Ciβ-aryl, halogen or where two adjacent radicals together for 4 to 15 carbon atoms having cyclic groups, for example C ₄ -C ₈ cycloalkyl or fused ring systems.

Vinylaromatic compounds of the formula I are preferably used, in which

Ri means hydrogen.

Suitable substituents R ² to R ⁶ are in particular hydrogen, C 1 -C ₄ -alkyl, chlorine, phenyl, biphenyl, naphthalene or anthracene. Two adjacent radicals can also together represent cyclic groups having 4 to 12 carbon atoms, so that naphthalene derivatives or anthracene derivatives, for example, result as the compound of the general formula I.

Examples of such preferred compounds are:

Styrene, p-methylstyrene, p-chlorostyrene, 2, 4-dimethylstyrene, 4-vinylbiphenyl, vinylnaphthalene or vinylanthracene.

Mixtures of different vinyl aromatic compounds can also be used, but preferably only one vinyl aromatic compound is used.

Particularly preferred vinyl aromatic compounds are styrene and p-methylstyrene. Mixtures of various vinyl aromatic polymers with a syndiotactic structure can also be used as component A), but preferably only one vinyl aromatic polymer is used, in particular syndiotactic polystyrene (SPS).

Vinylaromatic polymers (A) with a syndiotactic structure and processes for their preparation are known per se and are described, for example, in EP-A 535 582. The preparation is preferably carried out by reacting compounds of the general formula I in the presence of a metallocene complex and a cocatalyst. In particular pentamethylcyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltitanium trimethyl and pentamethylcyclopentadienyltitanium trimethylate are used as metallocene complexes.

The vinyl aromatic polymers with a syndiotactic structure generally have a molecular weight M (weight average) of 5,000 to 10,000,000, in particular 10,000 to 2,000,000 g / mol. The molecular weight distributions M _w / M _n are generally in the range from 1.1 to 30, preferably from 1.4 to 10.

Also suitable as vinyl aromatic polymers with syndiotactic structure A) are syntiotactic star polymers based on vinyl aromatic monomers. These star polymers are described, for example, in the older German patent application 196 34 375.5-44, in particular on pages 2, line 21 to page 6, line 25, and in the examples.

The molding compositions according to the invention contain as component B) 2 to 50% by weight, preferably 5 to 45% by weight, in particular 15 to 42% by weight, of fibrous or particulate inorganic fillers or mixtures thereof.

These are, for example, carbon or glass fibers, glass mats, glass silk rovings or glass balls and potassium titana whiskers, preferably glass fibers. Glass fibers can be equipped with a size and an adhesion promoter. These glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings). Preferred glass fibers contain an aminosilane size and typically have a diameter D of 1 to 30 μm, preferably 3 to 20 μm, in particular 5 to 15 μm. In the extruded molding composition according to the invention, the glass fibers then have a length to diameter ratio of 5 to 100, preferably 10 to 80, in particular 15 to 50. Furthermore, as component B), for example, amorphous silica, magnesium carbonate, powdered quartz, mica, talc, feldspar or calcium silicates can be used.

The rubber-elastic, particulate graft copolymer C) is composed of

cl) 30 to 100% by weight, preferably 40 to 85% by weight, particularly preferably 45 to 80% by weight of a phase produced by emulsion polymerization of

cl.l) 70 to 100% by weight, preferably 70 to 99.8% by weight, particularly preferably 75 to 99.5% by weight of an acrylate and

cl.2) 0 to 10% by weight, preferably 0.2 to 6% by weight, particularly preferably 0.5 to 5% by weight, of a further monomer with two or more polymerizable double bonds and

cl.3) 0 to 30% by weight, preferably 0 to 29.8% by weight, particularly preferably 0 to 24.5% by weight of further polymerizable monomers and

c2) 10 to 70% by weight, preferably 30 to 60% by weight, particularly preferably 30 to 55% by weight, of at least one further phase, prepared by polymerization in the presence of the first phase cl) of

c2.1) 80 to 100% by weight, preferably 90 to 100% by weight of styrene and

c2.2) 0 to 20% by weight, preferably 0 to 10% by weight, of further monomers

The phase cl) of the crosslinked rubber c), which preferably has a glass transition temperature of <0 ° C, preferably <-10 ° C, particularly preferably <-15 ° C, is predominantly composed of acrylates (cl.l), in particular butyl acrylate and / or ethylhexyl acrylate. This rubber phase cl) can contain further monomers cl.3), in particular methacrylates, styrene and / or acrylonitrile, and cl.2) polyfunctional crosslinking monomers, which are preferably selected from the following group: dinvinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate , Allyl methacrylate, triallyl isocyanurate, butadiene, isoprene, dihydrocyclopentadienyl acrylate, particularly preferably dihydrocyclopentadienyl acrylate.

The rubber phase cl) is produced by emulsion polymerization of the monomers or by mini-emulsion polymerization. The rubber c) has at least one further phase, produced by polymerization of

c2.1) 80 to 100% by weight, preferably 90 to 100% by weight of styrene,

c2.2) 0 to 20% by weight - further monomers in the presence of the first phase.

The same substances are suitable as further monomers as listed for cl.l) and cl.3) as further monomers for the first phase. The second phase c2) is usually the outer phase of the rubber c), i.e. The rubber c) is usually present as a core / shell polymer, although this structure is not mandatory.

In addition, the rubber C) can have further polymer phases, in particular of polystyrene and its copolymers, preferably of polystyrene and crosslinking agents and / or graft-active monomers. These phases can be formed on outer shells or can also form the cores of the multiphase rubber particles c).

The amount of component C) in the molding compositions according to the invention is 1 to 45% by weight, preferably 1 to 35% by weight and in particular 1 to 20% by weight.

The average particle size LD ₅₀ is 50 to 160 nm, preferably 70 to 150 nm.

The thermoplastic molding compositions according to the invention contain, as component D), 1 to 10% by weight, preferably 1 to 8% by weight, in particular 2.5 to 5% by weight, of a compatibilizer which, based on the current state of knowledge, binds to the inorganic filler B. ) causes. There are substances known from the literature, in particular polyarylene ethers.

Polyarylene ethers and processes for their preparation are known per se and are described, for example, in DE-A 42 19 438. Of the polyarylene ethers, polyphenylene ethers are particularly suitable, in particular polyphenylene ethers modified with polar groups. Such polyphenylene ethers modified with polar groups and processes for their preparation are likewise known per se and are described, for example, in DE-A 41 29 499.

Polyphenylene ethers modified with polar groups and composed of are preferably used as component D) di) 70 to 99.95% by weight of a polyphenylene ether,

d) 0 to 25% by weight of a vinyl aromatic polymer,

d ₃ ) 0.05 to 5% by weight of at least one compound which contains at least one double or triple bond and at least one functional group selected from the group of carboxylic acids, carboxylic acid esters, carboxylic acid anhydrides, carboxylic acid amides, epoxides, oxazolines or urethanes.

Examples of polyphenylene ethers di) are poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) e, poly (2,6-imethoxy-1,4) -phenylene) ether, poly (2,6-die hoxi-l, 4 -phenylene) ether,

Poly (2-methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-ethyl-6-stearyloxy-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2-methyl-6-phenyl-1,4-phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2-ethoxy-1,4-phenylene) ether, Poly (2-chloro-1,4-phenylene) ether, poly (2,5-dibromo-1,4-phenylene) ether.

Polyphenylene ethers are preferably used in which the

Substituents are alkyl radicals with 1 to 4 carbon atoms, such as

Poly (2,6-dimethyl-1,4-phenylene) ether,

Poly (2,6-diethyl-1,4-phenylene) ether,

Poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether,

Poly (2,6-dipropyl-1,4-phenylene) ether and

Poly (2-thyl -6-propyl-1,4-phenylene) ether.

Examples of preferred vinylaromatic polymers d ₂ ) can be found in the monograph by Olabisi, pp. 224 to 230 and 245. Vinyl aromatic polymers made from styrene, chlorostyrene, α-methylstyrene and p-methylstyrene are only representative here; in minor amounts (preferably not more than 20, especially not more than 8 wt -.% to as (meth) acrylonitrile or (meth) acrylate to be involved in the formation of comonomers is particularly preferred vinylaromatic polymers are polystyrene and impact-modified ^{'polystyrene.} It goes without saying that mixtures of these polymers can also be used and are preferably prepared by the process described in EP-A 302 485. Suitable modifiers d ₃ ) are, for example, maleic acid, methylmaleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the mono- and diesters of these acids, for example from Ci- and C- to Ca-alkanols, the mono- or diamides of these acids such as N-phenyl maleimide, maleic hydrazide. N-vinylpyrrolidone and (meth) acryloylcaprolactam may also be mentioned, for example.

The rubber-elastic component E) from a styrene-diene block copolymer, the diene portion of which can be completely or partially hydrogenated, is known, for example, from EP-A 755 972 and can be purchased, for example, from Shell under the name Kraton® G 1651, further examples are Cariflex ® "TR types (Shell), Finaprene® types (Fina) and Europrene® types (Enichen).

As component F), the thermoplastic molding compositions according to the invention optionally contain 1 to 35% by weight, preferably 1 to 20% by weight, in particular 1 to 15% by weight, of copolymers of vinylaromatic monomers, 1, 1-diphenylethylene and optionally dienes. This component F) can also be referred to as a thermoplastic elastomer (TPE).

Component F) is preferably produced by anionic polymerization.

Three-block copolymers are particularly preferred as component F), in particular those which are hydrogenated. Such copolymers are preferably used as component F) which are prepared from styrene, 1,1-diphenylethylene and butadiene, in particular styrene (S) /1.1-diphenylethylene (DPE) -butadiene -S / DPE-three-block copolymers, the .butadiene block being hydrogenated is (EB), i.e. (S / DPE) -EB- (S / DPE).

Also suitable are copolymers or block copolymers with at least one block A composed of vinyl aromatic monomers a1) and

1, 1-Diphenylethylene or its derivatives a2) optionally substituted with alkyl groups with up to 22 C atoms on the aromatic rings, obtainable by anionic polymerization, with a starter solution consisting of the reaction product being formed to form the copolymer or the block A. an anionic polymerization initiator and at least the equimolar amount of monomers a2) used.

Block copolymers with at least one block A and at least one, optionally hydrogenated block B from dienes b) are preferably produced by sequential anionic polymerization. The following process steps are carried out one after the other:

I) Formation of a block A by

1.1) Preparation of a starter solution consisting of the reaction product of an anionic polymerization initiator and at least the equimolar amount of monomers a2),

1.2) adding the remaining amount of monomers a2) and 60 to 100% of the total amount of monomers al),

1.3) adding the remaining amount of monomers a1) after conversion of at least 80% of the monomers added in the preceding process steps,

the concentration of the polymerization solution after the last monomer addition being at least 35% by weight,

II) subsequent formation of a block B by

II.1) addition of an additive influencing the polymerization parameters,

II.2) addition of dienes b) and

if necessary, the subsequent steps

III) adding a chain terminating or coupling agent,

IV) hydrogenation of the block copolymer,

V) isolation and processing of the block copolymers in a manner known per se,

VI) addition of stabilizers.

The copolymers or blocks A consist of vinyl aromatic monomers a1) and 1,1-diphenylethylene or its aromatic rings, optionally with alkyl groups having up to 22 carbon atoms, preferably having 1 to 4 carbon atoms, such as methyl, ethyl , i- and n-propyl and n-, i- or tert-butyl substituted derivatives a2). Preferred vinyl aromatic monomers a1) are styrene and its derivatives substituted in the α-position or on the aromatic ring with 1 to 4 carbon atoms, for example α-methylstyrene, p-methylstyrene, ethylstyrene, tert. -Butylstyrene, vinyl toluene used. The unsubstituted is particularly preferred as monomer a2) 1,1-diphenylethylene used itself. The molar ratio of the units derived from 1,1-diphenylethylene or its derivatives a2) to units derived from the vinylaromatic monomer al) is generally in the range from 1: 1 to 1:25, preferably from 1: 1.05 to 1:10 and particularly preferably in the range from 1: 1.1 to 1: 3.

The copolymers or the blocks A are preferably randomly structured and have a molecular weight Mw of generally 1,000 to 500,000, preferably 3,000 to 100,000, particularly preferably 4,000 to 30,000.

In principle, all dienes are suitable as diene b) for block B, but preference is given to those with conjugated double bonds such as 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadienes, phenylbutadiene, Piperylene or mixtures thereof. 1,3-Butadiene and isoprene are particularly preferably used. The diene block can be partially or completely hydrogenated or unhydrated. Hydrogenation of polyisoprene blocks leads to ethylene-propylene blocks or from polybutadiene blocks to polyethylene or polyethylene-butylene blocks corresponding to the 1,2-vinyl portion of the unhydrogenated butadiene block. The hydrogenation makes the block copolymers more thermostable and, above all, more resistant to aging and weathering. The molecular weights Mw of blocks B are generally in the range from 10,000 to 500,000, preferably from 20,000 to 350,000 and particularly preferably from 20,000 to 200,000. The glass transition temperatures of blocks B are generally below -30 ° C., preferably below -50 ° C.

The proportion by weight of the sum of all blocks A to the total block copolymer is generally 5 to 95% by weight, preferably 5 to 50% by weight, particularly preferably 25 to 35% by weight.

The anionic polymerization is initiated using organometallic compounds. The usual alkali metal alkyls or aryls can be used as initiators. Organic lithium compounds are expediently used, such as ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, hexyldiphenyl, hexamethylene di, butadienyl, isoprenyl or polystyryllithium. 1, 1-Diphenylhexyl lithium is particularly preferably used, which is easily obtainable from the reaction of 1, 1-diphenyl ethylene with n- or sec-butyllithium. The amount of initiator required results from the desired molecular weight and is generally in the range from 0.002 to 5 mol percent, based on the amount of monomer to be polymerized. Suitable solvents are solvents which are inert towards the organometallic initiator. Aliphatic, cycloaliphatic or aromatic hydrocarbons having 4 to 12 carbon atoms such as pentane, hexane, heptane, cyclopentane, cyclohexane, methylcyclohexane, decalin, iso-octane, benzene, alkylbenzenes such as toluene, xylene or ethylbenzene or suitable mixtures are advantageously used.

After the molecular weight has been built up, the “living” polymer ends can, if appropriate, be reacted with customary chain terminators or coupling agents in amounts which usually depend on the amount of initiator used.

Suitable chain terminators are proton-active substances or Lewis acids such as water, alcohols, aliphatic and aromatic carboxylic acids and inorganic acids such as carbonic acid, phosphoric acid or boric acid.

To couple the block copolymers, bi- or multifunctional compounds, for example halides of aliphatic or araliphatic hydrocarbons such as 1,2-dibromoethane, bischloromethylbenzene, silicon tetrachloride, dialkyl- or diarylsilicon dichloride, alkyl- or arylsilicon trichloride, tin-polytetrachloride, tin-tetrachloride, tin-tetrachloride, tin-tetrachloride, such as tin tetra-chloride, can be used Terephthalic acid dialdehyde, ketones, esters, anhydrides or epoxides can be used. Carboxylic acid esters such as ethyl acetate are preferably used as coupling agents if the block copolymer is not hydrogenated. In the case of hydrogenated block copolymers, preference is given to using 1,2-dibromoethane or diepoxides, in particular diglycidyl ethers, such as 1,4-butanediol diglycidyl ether.

Lewis bases such as polar, aprotic solvents or hydrocarbon-soluble metal salts, for example, can be used as an additive influencing the polymerization parameters (randomizer). Lewis bases which can be used are, for example, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, tetrahydrofurfuryl ether such as tetrahydrofurfuryl methyl ether or tertiary amines such as pyridine, trimethylamine, triethylamine and tributylamine or peralkylated bisamethylamine or oligoamine. These are usually used in concentrations of 0.1 to 5 percent by volume based on the solvent. Among the hydrocarbon-soluble metal salts, preference is given to using alkali or alkaline earth metal salts of primary, secondary and above all tertiary alcohols, particularly preferably the potassium salts such as potassium triethyl carbinolate or potassium tetrahydrolinaloolate. The molar ratio of metal salt to initiator is usually 1: 5 to 1: 200, preferably 1: 30 to 1: 100.

The selection and quantity of the randomizer are selected depending on the desired end product. For polymers which are not intended for hydrogenation and if, for example, a high 1,4-vinyl content is desired when using butadiene, a hydrocarbon-soluble potassium salt is preferably used. Tetrahydrofuran is preferably used for polymers which are subsequently to be hydrogenated. The amount is chosen so that, for example, a 1,2-vinyl content of about 20 to 50% results when using butadiene.

In this process, the total amount of monomers a2) is preferably placed in a solvent and the polymerization initiator is added. However, it is also possible to add parts of the monomers a2) or the solvent only at a later point in time. The amount of polymerization initiator results from any protic impurities in monomers and solvents which can be removed by titration, plus the amount which is calculated from the desired molecular weight and the total amount of monomer to be polymerized. N- or sec-Butyllithiu is preferably used, which within a few hours, generally in the range from 0.5 to 40 hours at 20 to 70 ° C. with the monomers a2), completely to 1, 1-diphenylhexyllithium or the corresponding substituted derivatives. 60 to 100%, preferably 70 to 90% of the total amount of monomers a1) required to form block A are metered into the template, which is preferably at a temperature of 40 to 70 ° C. The feed time depends on the reactivity of the monomers used and the concentration and is generally between 0.5 and 10 hours at a temperature of 40 to 70 ° C. The remaining amount of the monomers a1) is generally added after a conversion of more than 80%, preferably more than 95%, of the monomers presented or previously added. Block A is polymerized at a high monomer concentration, it being possible to reduce the residual monomers a2). In general, the concentration of the polymerization solution after the last monomer addition is at least 35% by weight, particularly preferably above 50% by weight.

In the production of the block copolymers with at least one block B, first a block A as described above, then a block B is formed by sequential anionic polymerization. After formation of the A block, before addition of dienes b), the addition of the polymerization solution which influences the polymerization parameters is added. Block B is then polymerized by adding dienes b). Before or during the addition of the diene, it is advisable to dilute the reaction mixture with an inert solvent in order to ensure adequate mixing and heat dissipation. The polymerization temperature for block B is preferably 50 to 90 ° C., particularly preferably 50 to 70 ° C. if polar, aprotic solvents are used as randomizers.

The A-B block copolymers obtained can be terminated by chain termination or coupling agents or, in the case of bifunctional coupling agents, linked to form linear three-block copolymers or in the case of more functional coupling agents to form star-shaped block copolymers.

The process is not limited to solution polymerization. For example, the process can also be easily applied to dispersion polymerization. For this purpose, it is expedient to use a dispersion medium which is inert to the anionic polymerization initiators and in which the A block is not soluble, such as propane, butane, isobutane, pentane or its branched isomers, hexane, heptane, octane or isooctane. In order to obtain a small particle size, 0.1 to 2% by weight of a dispersant is generally added. Suitable dispersants are e.g. Styrene / butadiene two-block copolymers with the highest possible molecular weight of, for example, over 100,000 g / mol.

Also suitable as component E) are thermoplastic elastomers styrene-butadiene-styrene, as described, for example, in WO-A 97/40079 (BASF) and e.g. Styroflex® BX 6105 from BASF. Additives or processing aids or mixtures thereof can be added to the thermoplastic molding compositions according to the invention in customary amounts.

• These are, for example, nucleating agents such as salts of carbon or organic sulfonic or. Phosphoric acids, preferably sodium benzoate, aluminum tris (p-tert-butyl benzoate), aluminum trisbenzoate, aluminum tris (p-carboxymethyl benzoate) and aluminum triscaproate; Antioxidants such as phenolic antioxidants, phosphites or phoshonites, especially trisnornylphenylphosph.it; Stabilizers such as sterically hindered phenols and hydroquinones. Lubricants and mold release agents, dyes, pigments and plasticizers can also be used. Organophosphorus compounds, such as phosphates or phosphine oxides, can be used as flame retardants.

Examples of phosphine oxides are triphenylphosphine oxide, tritolylphosphine oxide, trisnonylphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, tris (n-octyl) phosphine oxide, tris (cyanoethyl) ) -phosphine oxide, benzylbis (cyclohexyl) -phosphine oxide, benzylbisphenylphosphine oxide, phenylbis- (n-hexyl) -phosphine oxide. Triphenylphosphine oxide, tricyclohexylphosphine oxide are particularly preferably used,

Tris (n-octyl) phosphine oxide or tris (cyanoethyl) phosphine oxide.

Particularly suitable phosphates are alkyl and aryl-substituted phosphates. Examples are phenyl bisdodecyl phosphate, phenyl bis neopentyl phosphate, phenyl ethyl hydrogen phosphate, phenyl bis (3, 5, 5-trimethyl hexyl phosphate), ethyl diphenyl phosphate, bis - (2-ethyl hexyl) p-tolyl phosphate, tritolyl phosphate, trixylyl bis (phosphate) ) -phenyl phosphate, tris- (nonylphenyl) phosphate, bis- (dodecyl) -p- (tolyl) phosphate, tricresyl phosphate, triphenyl phosphate, di-butylphenyl phosphate, p-tolyl-bis- (2,5, 5-trimethylhexyl) - phosphate, 2-ethylhexyl diphenyl phosphate. Phosphorus compounds in which each R is an aryl radical are particularly suitable. Triphenyl phosphate, trixylyl phosphate and trimesityl phosphate are very particularly suitable. Cyclic phosphates can also be used. Diphenylpentaerythritol diphosphate is particularly suitable. Resorcinol diphosphate is also preferred.

Mixtures of different phosphorus compounds can also be used.

The thermoplastic molding compositions according to the invention can generally be obtained by mixing the individual components at temperatures of from 270 to 330 ° C. in customary mixing devices, such as kneaders, Banbury mixers and single-screw extruders, but preferably using a twin-screw extruder. Intensive mixing is necessary to obtain the most homogeneous molding compound possible. The mixing order of the components can be varied, so two or, if necessary, several components can be premixed, but all components can also be mixed together.

The sum of components A) to G) is 100%.

The thermoplastic molding compositions according to the invention can also be mixed with other polymers, such as atactic or isotactic homopolystyrene, styrene copolymers with, for example, acrylonitrile, Methacrylates and / or diphenylethylene as comonomers, or with polyamides, polyesters or polyphenylene ethers or mixtures of the polymers, are generally mixed as described above.

The thermoplastic molding compositions according to the invention are notable for high impact strength, high rigidity and good flowability (processability). They are suitable for the production of fibers, foils or molded articles.

Examples

Manufacture of PLC

Manufacture of syndiotactic polystyrene (SPS)

9.2 ol styrene (1000 g) was placed in a round-bottom flask inertized with nitrogen, the solution was heated to 60 ° C. and mixed with 78.3 ml methylaluminoxane (MAO) from Witco (1.53 M in toluene) and 20 ml diisobuthyaluminum hydrite DIBAH (1.0 M in cyclohexane) from Aldrich. The mixture was then mixed with 91.2 mg of [C ₅ (CH ₃ ) ₅ ] TiMe ₃ . The internal temperature was adjusted to 60 ° C and allowed to polymerize for 2 hours. After 2 hours, the polymerization was stopped by adding methanol. The polymer obtained was washed with methanol and dried at 50 ° C. in vacuo. The molar masses and their distribution were determined by high-temperature GPC with 1,2-trichlorobenzene as solvent at 135 ° C. The calibration was carried out using narrowly distributed polystyrene standards. The molar mass was M _w = 322 100 with a distribution width of M _w / Mn = 2.1. The syndiotactic fraction determined by ¹³ C-NMR was> 96 ^. The conversion was 84% based on the monomer styrene used.

Try 1 to 5

Fillers: Glass fibers with a length of 4.5 mm, an L / D ratio of 450 and an aminosilane size (PPG 3544 from PPG).

Kraton: Kraton G 1651 from Shell. Block copolymer with styrene-hydrogenated butadiene-styrene blocks. Styrene content 32% by weight, butandiene content: 68% by weight.

Styroflex: styrene-butadiene-styrene thermoplastic elastomer, e.g. Styrolflex® BX 6105 from BASF AG. D-Styroflex: styrene / 1,1-diphenylethene (DPE) -butadiene-styrene / 1,1-diphenylethene block copolymer with 15% by weight 1,1-diphenylethene in styrene / 1,1 -DPE- Block and 65% by weight of butadiene.

Core / shell rubber: 60% by weight core (consisting of 98% n-butyl acrylate and 2% DCPA), 40% by weight shell (consisting of 100% PS). Particle size 0.079 μm, made with the emulsion method.

Nucleating agents: sodium benzoate, talc IT Extra

Antioxidants: Irganox 1076

Mixtures: extruder ZSK 30, 290-310 ° C melt temperature. The strand was first cooled in air, then in a water bath and then granulated. PPE, sPS were melted, then rubbers and glass fiber were added.

Test specimen production: Production by injection molding at 310 ° C melt temperature and 100 ° C mold surface temperature.

Experiment 1-5:

* Experiments 1 and 2 are comparative experiments, not ¹ sPS according to the invention: syndiotactic polystyrene with molecular weight M _w = 246,000, D = 2.4

² sPS with molecular weight M _w = 300,000 g / mol, D = 2.7 ³ glass fiber: chaines chops PPG 3544, 10 μm

⁴ Kraton G 1652: SEBS, 29% styrene, 71% butandiene hydrogenated

Experiments 6 to 12 fillers: glass fibers (chopped glass fibers) with a length of 4.5 mm, an LD ratio of 450 and an aminosilane size

(PPG 3544 from PPG)

Styroflex: styrene-butanediene-styrene-thermoplastic elastomer, e.g. Styroflex® BX 6105 from BASF AG rubber 1: core 60% by weight from 98% butyl acrylate (BA) with 2%

Dicyclopentadiene acrylate (DCPA) with PS graft shell (40% by weight).

Rubber 2: core (60% by weight) made of 98% BA and 2% DCPA, graft cover made of 40% by weight (99.95% styrene and 0.05% butylene diacrylate)

Kraton: Kraton G 1652 from Shell. Block copolymer with styrene - hydrogenated butandiene-styrene blocks. Styrene content: 29% wt.%,

Butandiene content: 71% by weight

Nucleating agents: sodium benzoate, talc IT Extra

Antioxidants: Irganox 1076

blends:

Extruder ZSK 30, 290-310 ° C melt temperature, strand was only started

Air, then cooled in a water bath and then granulated.

PPE, sPS and additives were melted, then rubbers and

Glass fiber added.

Test specimen production:

Manufactured by injection molding at 310 ° C melt temperature and 100 ° C

Mold surface temperature.

Trial 6-12:

* Experiments 6 to 8 are comparative experiments, not according to the invention _Q is S: syndiotactic polystyrene with molecular weight M _w = 246,000, D = 2.4 ² sPS with molecular weight M _w = 300,000 g / mol, D = 2.7

Experiments 13 to 17 5 fillers: glass fibers with a length of 4.5 mm, an L / D ratio of 450 and an aminosilane size (PPG 3544 from Fa.

PPG)

Kraton: Kraton G 1651 from Shell. Block copolymer with styrene - hydrogenated butadiene-styrene blocks. Styrene content: 32% by weight, 0 butandiene content: 68% by weight

Core-shell rubber: 60% by weight core (consisting of 98% n-butyl acrylate and 2% DCPA), 40% by weight shell (consisting of 200%

PS). Particle size 0.079 μm, produced with the emulsion method. 5 nucleating agents: sodium benzonate, talc IT Extra

Antioxidants: Irganox 1076

blends:

ZSK 30 extruder, 290-310 ° C Melt Temperature, strand was only on _Q air, then cooled in a water bath and then granulated.

PPE, sPS were melted, then cardboard and glass fiber were added and finally core-shell rubber was assembled.

Test specimen production: ₅ Production by injection molding at 310 ° C melt temperature and 100 ° C mold surface temperature.

0

5 10

15

20

* Experiment 13 (ZK 169/60/1) and 14 are comparative experiments, not according to the invention

¹ sPS: Syndiotactic polystyrene with molecular weight M _w =

25 246,000, D = 2.4

² glass fiber: chained chops PPG 3544, 10 μm ³ PPE-modif. Polyphenylene ether with 0.35% by weight fumaric acid ⁴ core / shell rubber with particle size LD ₅₀ 680 nm (ZK 1831/17/7)

30

35

40

5

Claims

claims

1. Containing thermoplastic molding compositions

H) 5 to 95% by weight of a vinyl aromatic polymer with a syndiotactic structure

I) 2 to 50% by weight of an inorganic filler

J) 1 to 45% by weight of a rubber-elastic, particulate graft polymer

K) 1 to 10% by weight of a compatibility agent and, if appropriate

L) 1 to 45 wt .-% of a rubber-elastic particulate styrene-diene block copolymer whose diene part can be completely or partially hydrogenated and, if appropriate

M) 1 to 35 wt .-% of a thermoplastic elastomer based on copolymers of vinyl aromatic monomers, dienes and optionally 1, 1-diphenylethylene and optionally

N) additives

2. Thermoplastic molding compositions according to claim 1; wherein component C) has an average particle size of 50 to 160 nm.

3. Thermoplastic molding compositions according to claim 1 to 2, from components A) to F) and optionally G).

4. Thermoplastic molding compositions according to claim 1 to 2, from components A), B), C), D), and E) and optionally G).

5. Thermoplastic molding compositions according to claim 1 to 2, from components A), B), C), D), and F) and optionally G).

6. Thermoplastic molding compositions according to claim 1 to 5, wherein component B) is glass fibers.

7. Thermoplastic molding compositions according to claim 1 to 6, with 15 to 42% by weight of component B).

8. Use of the thermoplastic molding compositions according to claims 1 to 7 for the production of fibers, films or moldings.

9. Fibers, films and moldings obtainable from thermoplastic molding compositions according to claims 1 to 7 as an essential component.

Summary

Containing thermoplastic molding compounds

A) 5 to 95% by weight of a vinyl aromatic polymer with a syndiotactic structure

B) 2 to 50% by weight of an inorganic filler

C) 1 to 45% by weight of a rubber-elastic, particulate graft polymer

D) 1 to 10% by weight of a compatibility agent and, if appropriate

Ξ) 1 to 45% by weight of a rubber-elastic particulate styrene / diene block copolymer whose diene part can be completely or partially hydrogenated and, if appropriate

G) additives

as essential components, the sum of the percentages by weight from A) to G) being 100.