WO1999041312A1

WO1999041312A1 - Transparent, thermoplastic moulding materials on the basis of styrene/diphenylethylene copolymers

Info

Publication number: WO1999041312A1
Application number: PCT/EP1999/000714
Authority: WO
Inventors: Michael Schneider; Norbert Niessner; Hermann Gausepohl
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-02-12
Filing date: 1999-02-03
Publication date: 1999-08-19
Also published as: AU3027099A; DE19805587A1

Abstract

The invention relates to thermoplastic moulding materials containing A) between 5 and 95 weight % of a copolymer of styrene and 1,1-diphenylethene with a diphenylethene content of between 1 and 15 weight %, B) between 5 and 95 weight % of crystal-clear or impact-resistant polystyrene or polyphenylether and C) between 0 and 90 weight % other additives, where the sum of A), B) and C) is 100 weight %.

Description

Transparent thermoplastic molding compounds based on styrene / diphenylethylene copolymers

description

The invention relates to thermoplastic molding compositions containing

A) 5 to 95 wt .-% of a copolymer of styrene and 1,1-diphenylethene with a content of diphenylethene in the range of

1 to 15% by weight,

B) 5 to 95 wt .-% crystal-clear or impact-resistant polystyrene or polyphenylene ether and

C) 0 to 90% by weight of further additives

the sum of A), B) and C) being 100% by weight.

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

Thermoplastic molding compositions based on styrene / l, 1-diphenyl-ethene copolymers are known, for example, from WO 95/34586. They have high glass transition temperatures. As a rule, the compatibility of these copolymers with other polymer components is low, so that the molding compositions are not transparent.

It is an object of the present invention to provide thermoplastic molding compositions based on styrene / 1, 1 '-Diphenylethen copolymers are available which do not exhibit the aforementioned disadvantages ^¬, in particular a good heat resistance, high Stei- stiffness and transparency, or translucent have .

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

As component A), the thermoplastic molding compositions 5 containing up to 95 wt .-%, preferably 25 to 90 wt .-%, of a copolymer of a vinyl aromatic monomer and 1, 1-diphenylethylene or ^¬ sen on the aromatic rings optionally having alkyl groups with up to 22 C-substituted derivatives. A stati ^¬ stisches copolymer of styrene and 1, 1-diphenylethylene is preferably used. The content of 1,1-diphenylethene is expediently from 1 to 15% by weight, preferably from 5 to 15% by weight, in the copolymer or the corresponding molar amount of one of the 1,1-diphenylethene derived derivatives. The weight average molecular weight M _w of component A is 10,000 to 2,000,000 g / mol, preferably 20,000 to 1,000,000 and very particularly preferably 50,000 to 500,000 g / mol.

The copolymers which can be used as component A) are known per se. Their production is described in detail in WO 95/34586.

As component B), the molding compositions according to the invention contain 5 to 95% by weight, preferably 10 to 75% by weight, of crystal-clear or impact-resistant polystyrene or polyphenylene ether. The production of crystal-clear or impact-resistant polystyrene is known and is described, for example, in A. Echte, Handbuch der Technischen Polymer-Chemie, Verlag VCH Weinheim, 1993, chapter 8.3, page 475 ff. Mixtures with radically produced standard polystyrene and with impact-modified polystyrene are particularly preferred. All rubber-modified polystyrenes, in particular modified by polybutadiene or styrene-butadiene block copolymers, can be used as impact-modified polystyrene. Standard polystyrene 158 K or 168 N from BASF Aktiengesellschaft is suitable as crystal-clear polystyrene. The impact-resistant polystyrene is preferably translucent, such as polystyrene 585 K from BASF Aktiengesellschaft. In order to obtain a transparent molding compound, it is expedient to use transparent standard polystyrene or polyphenylene ether.

To modify the properties and processability, the thermoplastic molding compositions can be used as component C)

0 to 90 wt .-%, preferably 0 to 65 wt .-% of other additives. Examples of these are impact-modifying polymers, fibrous or particulate fillers, halogen-containing or halogen-free flame retardants, or processing aids, which are added in customary amounts. Antioxidants or UV stabilizers are also often added to achieve better durability under the influence of the weather.

The impact-modifying polymers (also called impact modifiers, elastomers or rubbers) used to improve the toughness are used in amounts of 0 to 30, preferably 3 to 20 and in particular 5 to 15% by weight.

The following may be mentioned as rubbers which increase the toughness of the copolymers A): Polyoctenylenes, graft rubbers with a cross-linked, elastomeric core, which is derived, for example, from butadiene, isoprene or alkyl acrylates and a graft shell made from polystyrene, further copolymers from ethylene and acrylates or methacrylates, and the so-called ethylene propylene (EP) - And ethylene propylene diene (EPDM) rubbers, as well as the EP or EPDM rubbers grafted with styrene.

Furthermore, block copolymers with up to six, preferably with up to four identical or different blocks, which can be connected both linearly and in a star shape (so-called radial block copolymers), can be used. Block copolymers are preferred which have at least one block of vinyl aromatic monomers, which is preferably located at the end of the polymer chain.

Mixtures of block copolymers of various structures, e.g. Mixtures of two- and three-block copolymers or of wholly or partly hydrogenated and unhydrogenated block copolymers can also be used.

Such impact modifying polymers are known per se and are described in the literature. For example, reference is made here to US-A-4,085,163, US-A-4,041,103, US-A-3,149,182, US-A-3,231,635 and US-A-3,462,162.

Also commercially Corresponding products are available, for example a polyoctylene the name Vestenamer ^® (Hüls AG), metallocene catalytic polyethylenes such Affinity ^® (DOW) or Luflexen ^® (BASF), and a variety of suitable block copolymers with at least one vinyl aromatic and an elastomeric block. Examples include the Cariflex ^® TR types (Shell), the Kraton ^® G types (Shell), the Finaprene ^® types (Fina), the Europrene ^® SOL TR types (Enichem) and Styroflex ^® and Styrolux ^® (BASF) called.

As further additives, the molding compositions according to the invention can contain 0 to 50, preferably 5 to 40 and in particular 10 to 35% by weight of a fibrous or particulate filler or mixtures thereof.

Preferred fibrous reinforcing materials are fibers carbon fibers, potassium, aramid fibers and particularly preferably glass ^¬. If glass fibers are used, they can be equipped with a size and an adhesion promoter for better compatibility with the thermoplastic polyamide (A). In general, the glass fibers used have a diameter in the range from 6 to 20 μm.

These glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings). In the finished injection molded part, the average length of the glass fibers is preferably in the range from 0.08 to 0.5 mm.

Amorphous silica, asbestos, magnesium carbonate (chalk), powdered quartz, mica, talc, feldspar and in particular calcium silicates such as wollastonite and kaolin (in particular calcined kaolin) are suitable as particulate fillers.

The molding compositions according to the invention can furthermore contain flame retardants in a concentration of 0 to 20% by weight, preferably 1 to 15% by weight, in particular 3 to 10% by weight, based on the total weight of the molding composition.

Suitable flame retardants are e.g. Polyhalodiphenyl, polyhalodiphenyl ether, polyhalophthalic acid and its derivatives, polyhalogen oligo- and polycarbonates, the corresponding bromine compounds being particularly effective.

Examples include polymers of 2, 6, 2 ', 6' tetrabromobisphenol A, tetrabromophthalic acid, 2, 6-dibromophenol and 2,4,6-tribromophenol and their derivatives.

The preferred flame retardant is elemental phosphorus. As a rule, the elementary phosphorus can e.g. Polyurethanes or aminoplasts are desensitized or coated. In addition, concentrates of red phosphorus are e.g. in a polyamide, elastomer or polyolefin.

Combinations of elemental phosphorus with 1, 2, 3, 4, 7, 8, 9, 10, 13, 13, 14, 14-dodecachloro-1, 4, 4a, 5, 6, 6a, 7, - 10 are particularly preferred , 10a, 11, 12, 12a-dodecahydro-l, 4: 7, 10-dimethanodibenzo (a, e) -Cy- clooctan (Dechlorane Plus ^®, Occidental Chemical Corp.) and, optionally, a synergist such as antimony trioxide.

Phosphorus compounds such as organic phosphates, phosphonates,

Phosphinates, phosphine oxides, phosphines or phosphites are also preferred. Triphenylphosphine oxide and triphenylphosphate may be mentioned as examples. This can be used alone or mixed with hexabromobenzene or a chlorinated biphenyl and, optionally, antimony oxide. Typical of the preferred phosphorus compounds that can be used in accordance with the present invention are those of the following general formula

0

OQ OQ

OQ

wherein Q represents the same or different radicals hydrocarbon radicals, such as alkyl, cycloalkyl, aryl, alkyl-substituted aryl and aryl-substituted alkyl, furthermore halogen, hydrogen and combinations thereof, provided that at least one of the radicals representing Q is an aryl radical.

Examples of such suitable phosphates are e.g. the following: phenyl bisdodecyl phosphate, phenyl bis neopentyl phosphate, phenyl ethylene hydrogen phosphate, phenyl bis (3-5, 5'-trimethyl hexyl phosphate), ethyl diphenyl phosphate, 2-ethyl hexyl di (p-tolyl) phosphate, bis (2-ethyl hexyl) phenyl , Tri (nonylphenyl) phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate, tri-cresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate and diphenyl hydrogen phosphate. The preferred phosphates are those where each Q is aryl. The most preferred phosphate is triphenyl phosphate. The combination of triphenyl phosphate with hexabromobenzene and antimony trioxide is also preferred.

Compounds which contain phosphorus-nitrogen bonds, such as phosphoronitrile chloride, phosphoric acid ester amides, phosphoric acid ester amines, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, tris (azidinyl) phosphine oxide or tetrakis (hydroxymethyl) phosphonium chloride, are also suitable as flame retardants. Most of these flame retardant additives are commercially available.

Other halogen-containing flame retardants are tetrabromobenzene, hexachlorobenzene and hexabromobenzene as well as halogenated polystyrenes and polyphenylene ethers.

The halogenated phthalimides described in DE-A-19 46 924 can also be used. Of these, N, N'-ethylene bistetrabromophthalimide in particular has gained importance. Other additives are, for example, stabilizers and oxidation inhibitors, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes, pigments and plasticizers.

Oxidation retarders and heat stabilizers which can be added to the thermoplastic compositions according to the invention are e.g. Group I metals of the Periodic Table, e.g. Sodium, potassium, lithium halides, optionally in combination with copper (I) halides, e.g. Chlorides, bromides or iodides. Zinc fluoride and zinc chloride can also be used. Sterically hindered phenols, hydroquinones, substituted representatives of this group and mixtures of these compounds, preferably in concentrations of up to 1% by weight, based on the weight of the mixture, can be used.

Examples of UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2% by weight.

Materials for increasing the shielding against electromagnetic waves such as metal flakes, powders, fibers, metal-coated fillers can also be used.

Lubricants and mold release agents, which are generally added in amounts of up to 1% by weight to the thermoplastic composition, are stearic acid, stearyl alcohol, alkyl stearates and amides, and esters of pentaerythritol with long-chain fatty acids.

The additives also include stabilizers that prevent the decomposition of the red phosphorus in the presence of moisture and atmospheric oxygen. Compounds of cadmium, zinc, aluminum, silver, iron, copper, antimony, tin, magnesium, manganese, vanadium, boron, aluminum and titanium may be mentioned as examples. Particularly suitable connections are e.g. Oxides of the metals mentioned, also carbonates or oxicarbonates, hydroxides and salts of organic or inorganic acids such as acetates or phosphates or hydrogen phosphates and sulfates.

The thermoplastic molding compositions according to the invention can be prepared by processes known per se, by mixing the starting components A), B) and, if appropriate, further additives C) in conventional mixing devices, such as screw extruders, preferably twin-screw extruders, Brabender mills or Barbury mills, and then extruding them. After the extrusion, the extrudate is cooled and crushed. In order to obtain a molding material that is as homogeneous as possible, intensive mixing is advantageous. This generally requires average mixing times of 0.2 to 30 minutes at temperatures of 160 to 320 ° C. The mixing order of the components can be varied, so two or possibly three components can be premixed, but all components can also be mixed together.

Compositions according to the invention can also be produced by a pultrusion process as described in EP-A-56 703. The glass fiber strand is impregnated with the polymer mass and then cooled and crushed. In this case, the glass fiber length is identical to the granulate length and is between 3 and 20 mm.

The thermoplastic molding compositions according to the invention are notable for high rigidity and heat resistance. They are translucent or transparent.

They are suitable for the production of films, fibers and moldings, in particular for the production of transparent films and moldings, for example) in the food, automotive, electrical, electronics, construction, construction and leisure sectors, for the examples listed below are:

a) Food sector:

Drinking cups for hot or cold drinks, disposable tableware such as cups, plates, cutlery; Bowls for salads, microwave dishes for single use or for reusable use. Jam container. Containers for dairy products such as yogurt, curd cheese, cream, cream, cheese. Blister packs for technical parts such as nails, tools, toys; Tablet blister packs, blister packs for toothbrushes, bottles, packaging films, household films, roasting films;

b) Automotive, electrical and electronics sector:

For Kf for interior parts, air ducting installation parts, stereo speakers, audio and video cassette casing, hot air jets, Tastaturabdek- fluctuations, Cable TV, busbars, electrical distribution, Stek ^¬ kerleisten, fluctuations bobbin plates, hubcaps, car steering wheel Abdek-, heating fan controller , switch cabinets, automotive exterior mirror body, the air inlet grille, car racks in the interior, housings of electric appliances such as measuring instruments (volt-ampere, ohmmeter), Küchenge ^¬ boards such as a kitchen machine, a stirrer, mixer, blender, toaster, egg ^¬ cooker, coffee maker , Coffee grinder, fan heater, air conditioners, Electric cutting machine, electric knife, vacuum cleaner, fans. Cover of stove, microwave oven, dishwasher, washing machine, dryer. Housings for audio, video systems, televisions, irons, computers, copiers, faxes, telephones, teleprinters, cameras, printers, plotters, typewriters, control units, time switches, chargers, batteries, capacitors, pumps. Electrical functional parts such as switches, electrical installation housings for transformers, deflection coil bodies for TV sets;

Decorative strips for motor vehicles, spiral cables, ball joint seals, bushings, slide bearings, stabilizers, torsion bars, gear knobs, impact zones for motor vehicles, bumpers, spoilers, sills, wheel trims. Guide, rain strips. Components in the engine block and in the engine lubrication, e.g. Camshaft sprockets, chain guide rails, toothed belt covers, intake pipes, engine covers, oil pan, oil filter housing, clutch pressure bearing. Components in the fuel supply system, e.g. Fuel filter housing. Components in gearboxes, gears; Tachometer drive. Components on the chassis Chip carriers, isolators, connectors, parts of infusion sets, sterilizable medical or diagnostic parts such as beakers, dishes, scales, housings for dialyzers, forceps, surgeons. Instruments; Valves, battery cases, grilles, rear panels, parts for antennas, CD packaging, compact discs;

c) Construction, construction and leisure area:

Window profiles, pipes, tubes, cable sheathing, double-wall sheets, hoses, parts of skis, snowboards, snow chains, rollers, bellows, profiles, sieves and sieve elements, ski boots and parts for ski boots, toys, housings for drills, electric planers, grinding machines, saws, Gluing devices, cordless screwdrivers. Seals, rollers, shells for casual shoes, housings for binoculars, video cameras, facade cladding, garden furniture, surfboards, lawn mower housings, letter boxes, sanitary articles, refrigerated furniture, furniture1;

Glazing, skylights, co-extruded protective layers on e.g. ABS, PVC, PC. Light guide;

Bags, shrink films, films for agriculture, construction films, films for carrier bags, automatic and laminating films, diaper films, bottles and tubes for cosmetics, pharmaceuticals and chemicals. Pipe coatings, rail washers, sealing rings, protective caps, sleeves, clips, slip closures; e) Other areas of application:

Credit cards, credit cards, rolls of adhesive, furniture foils, water filter housings, traffic signs, disposable syringes, tablet tubes, fibers, spunbonded nonwovens, foams, insulation elements, transparent covers, ballpoint pen housings.

Examples:

The following components were used:

Component A2) (S / DPE copolymer with 15% by weight DPE)

A styrene / 1,1-diphenylethene copolymer with 15% by weight 1,1-diphenylethene and a weight average molecular weight M _w of 245,000 g / mol was produced according to the examples in WO 95/34586:

A 10-1 metal kettle with a double jacket for cooling and heating and stirrer was inertized for several hours with a refluxing solution of DPE / sec-butyllithium in cyclohexane.

After the cleaning solution had been drained, 3760 ml of cyclohexane and 586 ml (600 g; 3.33 mol) of 1,1-diphenylethene were introduced and titrated with sec-butyllithium until the color turned red. Now 72.4 ml of a 0.27 M sec-butyllithium solution in cyclohexane were added and the reactor contents were thermostatted to 70.degree. Then 3748 ml (3400 g; 32.7 mol) of styrene were added in 200 ml steps every 10 min. After a reaction time of 180 min, titration was carried out with ethanol until colorless, the polymer was precipitated by dropping the polymer solution in ethanol and the white powder which had been filtered off and washed several times with ethanol was dried in vacuo (1 mbar) at 200 ° C. for 2 h.

Yield: 3948 g (98.7%); Styrene content (FTIR): 85.1% (85% theor.); DPE content (FTIR): 14.9% (15% theor.); Tg (DSC): 121.5 ° C

(Width of the glass step: 9 ° C); Molar masses (GPC, polystyrene calibration, g / mol): M _n 177 000, M _w 245 000.

Components AI), A3), A4) and A5) were produced analogously to components A2):

Component AI) (S / DPE copolymer with 12% by weight DPE)

Component A3) (S / DPE copolymer with 18% by weight DPE)

Component A4) (S / DPE copolymer with 30% by weight DPE) Component A5) (S / DPE copolymer with 45% by weight DPE) Component Bl):

Standard polystyrene with a viscosity number VZ of 96 ml / g (0.5% in toluene, 23 ° C), a molecular weight M _w of 250,000 g / mol and a non-uniformity M _w / M _n of 3.5.

Component B2):

Translucent, impact-resistant polystyrene with a viscosity number VZ of 76 ml / g (0.5% in toluene, 23 ° C) and a melt volume rate MVR (200 ° C / 5 kg) of 4.3 ml / 10 min. Capsule particle morphology with 0.4 μm diameter), polybutadiene content 10%.

Component B3):

Poly (2,6-dimethyl-1,4-phenylene ether) with a reduced viscosity η _re of 0.65 (1% in chloroform, 25 ° C)

Production of molding compounds:

Components A), B) and C) were melted in the proportions by weight given in Table 1 in a twin-screw extruder (ZSK 30 from Werner & Pfleiderer) at a temperature of 250 ° C., homogenized and extruded as a strand into a water bath. The dried granules were then sprayed into standard test specimens.

Measurement methods:

The glass transition temperature (Tg) was determined by means of differential scanning calorimetry (DSC) in accordance with DIN 53 765.

The melt volume rate MVR (200 ° C / 5 kg) was determined according to ISO 1133 at 200 ° C / 10 kg.

The notched impact strength ak (Charpy) was determined from the impact test according to DIN 53453.

The transparency was assessed visually and rated as follows:

+ transparent 0 translucent opaque Table 1: Composition and properties of the molding compounds

The comparative experiments show that the molding compositions made of S / DPE copolymers with 18% by weight DPE and crystal-clear or impact-resistant polystyrene (VI, V2) or 45% by weight DPE and polyphenylene ether lose their transparency or translucent and become opaque. At the same time, two separate glass levels occur in the DSC (Differential Scanning Calorimetry).

Claims

claims

1. Thermoplastic molding compositions containing

A) 5 to 95% by weight of a copolymer of styrene and 1,1-diphenylethene with a diphenylethene content in the range of 1 to 15% by weight,

C) 0 to 90% by weight of further additives

the sum of A), B) and C) being 100% by weight.

2. Thermoplastic molding compositions according to claim 1, containing

A) 25 to 90% by weight of a copolymer of styrene and 1,1-diphenylethene with a diphenylethene content in the range of 1 to 15% by weight,

B) 10 to 75% by weight of crystal-clear or impact-resistant polystyrene or polyphenylene ether and

C) 0 to 65 wt .-% additives

the sum of A), B) and C) being 100% by weight.

3. Use of the thermoplastic molding compositions according to claims 1 or 2 for the production of films, fibers and moldings.

4. Use of the thermoplastic molding compositions according to claim 3 for the production of transparent films and moldings in

Food, automotive, electrical, electronics, construction, construction and leisure areas.

5. Films, fibers and moldings obtainable from the thermoplastic molding compositions according to claims 1 or 2.