DD203063A1 - COMBINATIONS OF THERMOPLASTS AND PARTICULATE REMAINING MATERIALS - Google Patents

Abstract

It should be developed thermoplastic combinations that have a high heat resistance, Maszhaltigkeit, hardness, stiffness and good dielectric properties. These requirements are met by combinations of 20 to 99% ethylene-norbornene copolymers and 1 to 70% particulate Verstaerkerstoffen, optionally with the addition of elastomers and thermoplastics. Suitable particulate reinforcing materials are inorganic particulate reinforcing materials such as chalk, silicates, metal oxides or organic particulate reinforcing materials such as wood flour or thermoset microspheres. The combinations of ethylene-norborne copolymers and particulate reinforcing substances can be used in electrical engineering as well as in mechanical engineering and vehicle construction and in container construction.

Description

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- Λ -

VEB Leuna-Werke Leuna, November 20, 1981

"Walter Ulbricht" -

LP 81 104

Title of the invention

Combinations of thermoplastics and particulate compounders

Field of application of the invention

The invention relates to thermoplastics filled with particulate reinforcing materials, which are used under high continuous loads and at high temperatures. The combinations are used in applications requiring high heat resistance, compressive strength, resistance to hydrolysis and good dielectric properties.

Characteristic of the known technical solutions

Particulate Yerstärkerstoffen filled thermoplastics are used in applications in which semi-finished and plastic moldings are exposed to high static Bauer loads.

-t. OtL 1331 * 975654

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The selection of the special thermoplastic-reinforcing material combinations is carried out according to the specific requirements of the specific application case. The heat resistance of the thermoplastics filled with particulate reinforcing materials is largely determined by the heat resistance of the plastic matrix. Of particular importance for good material properties is the particle size of the particulate reinforcing material and its homogeneous distribution in the polymer matrix and the addition of adhesion promoters for improving the interfacial adhesion between reinforcing material and plastic matrix (K. Thinius, Plaste und Kautschuk 17 (1970) 9, 653-59; S. Sinbinder, Mech. Kunststoffe (1969) 5, 1038-45, R. Hauser, La.Tel.Technol 15 (1969) 12, 33, Japan Plastics Age 18 (1980) 173, 38-44, DD-PS 111 086, DE-OS 2425 259).

Polyamide-6 and polyamide-6,6 which is filled with particulate reinforcing materials such as aluminosilicates, chalk or glass microspheres, has over unfilled polyamide-o or polyamide-6, б improved strength, toughness and lower tendency to warp, also with prolonged use at higher (Chem. Rundschau (Solothurn) 33 (1980) 1/2, 1-12; Chem. Industrie (Dusseldorf 103 (1980) 3, A 110) .Coamides of polyamide and finely divided iron oxide or barium nitrite have magnetic properties (Modern Plastics (Lausanne) 10 (1980) 3, 44) and are used in micromotors.

Ir. PVG-hard, the addition of particulate fillers -L-і the calcium carbonate causes a significant improvement in the notched impact strength when the particle size is about 1μπ (H. Schlumpf, Kunststoffe 70 (1980) 6, 331-336).

The addition of particulate fillers, such as talc and mica, in combination with polypropylene results in an improvement in hardness, stiffness, creep rupture strength and heat resistance; Pcmstcffa has a reduced shrinkage and low coefficient of thermal expansion.

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Low-density PE combinations with 50 % kaolin and 10% ethylene-vinyl acetate copolymer have a 3 times higher flexural stress than unmodified low-density PE, tensile strength and impact resistance are retained despite the high level of particulate enhancer.

Although pearlescent reinforcing materials are superior to particulate reinforcing materials in terms of increasing heat distortion resistance and bending strength, the high cost of fibrous reinforcing agents over particulate reinforcing materials tends to limit the use of these combinations. On the other hand, combinations with particulate reinforcing materials are lower in price than unmodified plastics.

Purely specific applications in mechanical and automotive engineering, in the Peinwerktechnik, electrical engineering and electronics, where good dielectric properties, high heat resistance, dimensional stability and rigidity are required, the aforementioned combinations are unsuitable. With combinations of polyamides and spherical reinforcing materials, the water absorption of the polyamide matrix leads to a decrease of the dielectric properties, the stiffness and changes in the dxmenus. The HacJ part of PE and pVC booster combinations lies in the low continuous service temperature. Polyethylene and polypropylene / repellent combinations have too low a stiffness for the aforementioned ' ¹ ' applications.

Object of the invention

The aim of the invention are Thermoplasxkombinationen with particulate reinforcing materials, which have good performance properties.

Explanation of the essence of the invention

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The invention has for its object to develop thermoplastic combinations that have a high heat resistance, dimensional stability, hardness, rigidity and good dielectric properties.

This object is achieved by combinations of thermoplastics and particulate reinforcing materials, optionally with the addition of stabilizers, adhesion promoters, crosslinking agents, glass fibers, lubricants and pigments, where according to the invention the combinations 1 to 70 % particulate reinforcing materials, 20 to 99 % ethylene-sorbornene copolymer and optionally 1 to 60 # of a further thermoplastic and / or 1 to 35% elast ·

Advantageously, the combinations contain as particulate reinforcing materials inorganic reinforcing materials such as chalk, chalked limestone, ground marble, kaolins, mica, talc, clays, silicates, silica, fumed silica, microglass, micro hollow glass, ground glass fibers, rock flour, asbestos powder, carbon black, metal powder, metal oxides and particulate organic reinforcing materials' as Duroplastmikrokugeln, Thermoplastregenerate, wood flour, b ^T ußschalenmehl inter alia

The interfacial adhesion between the particulate repellent and the ethylene-norbornene copolymer kaoa.-xiurch adhesion promoters such as silanes and their derivatives, fatty acid salts, ороху compounds, titanates, modified fatty acids, esters, durca monomers such as acrylic acid, methacrylic acid and its derivatives, polymers and copolymers acrylic acid, methacrylic acid and their derivatives are carried out, furthermore, the interfacial adhesion amplifier / ethylene norbornene copolymer mintela pretreatment of the filler by vibratory milling, Bestraolung, Ultra3challbehandlung and others improved.

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Furthermore, the material properties of combinations of ethylene-norbornene copolymers and particulate reinforcing materials can be modified by the addition of further thermoplasts such as polyethylene, polypropylene, polyamides, polyesters, polycarbonates, polyethers, polyphenylene oxide, polyfluoroolefins *

The impact strength and notched impact strength of the combinations of ethylene-norbornene copolymers and particulate reinforcing materials are improved by addition of elastomers such as natural rubber, elastomeric ethylene-co-and terpolymers or graft copolymers, polybutadiene, elastomeric butadiene, co-and terpolymers or graft copolymers, chlorinated and chlorosulfonated polyethylene, polyisobutylene, polyisoprene, polychloroprene, chlorohydrin rubbers, butyl rubber, silicone rubber, polysulfide rubber, chlorofluorocarboxylic acid, nitrosocarbon rubber, carboxy-cyrositrocryl rubber, polyacrylate rubber and polyurethane rubber, or mixtures of these elastomers.

The. Production of the combinations takes place in single-screw or twin-screw extruders with good homogenizing effect at processing temperatures in general. Range from 500 to 560K. The components may be dosed simultaneously or pre-homogenize individual components, e.g. Preparation of a Batea of Particulate Repellent with the Elast, Blending of the Batch with the Ethylene-Norbornene Copolymer and Homogenization in the Extruder.

As the particulate enhancer content increases, the modulus, hardness, Vicat temperature, and solvent resistance of the combinations increase.

Of major influence on the material properties of the combination are also composition and morphology of the particulate repellent, type and concentration of the

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Haftvermitilers and the Elastzusatzes and composition and molecular weight distribution of the ethylene-norbornene copolymer.

EMBODIMENTS Example 1

70 parts of a 0.2 % 4,4'-thio-bis-O-methyl-o-tert-butylphenol) stabilized ethylene-norbornene copolymer having a Yicat temperature of 402 K, a flexural modulus of

2 2

3800 N / mm, a ball hardness of I46 H / mm, a notch

impact strength of 1.2 KJ / m and a Heρtanaufhähme of 21 % after 170 hours. Storage at 298 K are mixed with 30 parts of untreated chalk and homogenized at 520 K in the extruder.

The Vica-c temperature of the methylene-norbornene copolymer filled with chalk as a particulate Yerstärkeratoff is 411 K,

ρ ρ

bending B-module 4500 IT / mm, ball-bearing hardness 171 U / mm,

- 2

the impact strength 1.3 KJ / m and the Heρtanaufhähme

13 % after 170 hours «. Storage at 298 K · Example 2

48 parts of a 0.2 % 4,4'-thio-bi3- (3-methyl-6-tert-butylphenol) stabilized Ethjlen-iiorbomen copolymer according to Example 1 with 40 parts of unbehandalker chalk and 12 parts of a Sthenylene Yinylazetat copolymer (vinyl acetate content of 32 % and melt index β g / min at 373 K) homogenized at 520 K in the extruder.

The Yicat temperature of the combination is 407 K, the flexural modulus of elasticity 3300 N / mm ² , the ball-bearing hardness 120 ^ Т / літ ² , the score

Impact strength 2.8 KJ / m and heptane uptake 18 % after 170 hours · storage at 298 K

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Example 3

63 parts of the ethylene-norbornene copolymer used in Example 1 are mixed with 30 parts of glass microspheres 0 1 to 2 ^ m and 7 parts of ethylene-propylene terpolymer rubber and homogenized at 5 ° K in the extruder · The combination has a Vicat temperature of 404 K. , a bending modulus of 3800 N / mm, a notch impact strength of 2.2 KJ / m ² and a hardness of 150 U / mm ·

Example 4

50 parts of the ethylene-orbornene-r copolymer used in Example 1 are mixed with 15 parts of polyamide-6 and 35 parts of ground thermoset waste and homogenized in the extruder at 520 K. »The combination has a visa temperature of 416 K, a bending e Module of 4400 11 / mm, a notch

Impact strength of 1.4 KJ / m, a hardness of 158 N / mm and a heptane uptake of 9 % after 170 hours storage at 298 K.

Example 5

80 parts of the ethylene-norbornene-type copolymer used in Example 1 are homogenized with 20 parts of kaolin at 520 K in the extruder. The combination has a Yicat temperature

2 of 420 K, one bending modulus of 4300 N / mm, a notch

• 2 2

Impact strength of 1.8 mj / mm and a hardness of 138 N / mm.

Example б

20 parts of the ethylene-norbornene copolymer used in Example 1 are homogenized in an extruder with 35 parts of polyphenylene oxide, 15 parts of styrene-butadiene rubber and 30 parts of asbestos flour at 525 K. The combination has one

2 temperature of 405 K, a bending modulus of 3800 U / mm,

2 has a notched impact strength of 2.8 mJ / mm and a hardness of

130 ϊί / mm ² .

Claims (2)

235394 1 invention claim 1. Combinations of thermoplastics and particulate reinforcing agents, optionally with the addition of stabilizers, adhesion promoters, crosslinkers, glass fibers, lubricants and pigments, characterized in that the combinations 1 to 70 % particulate reinforcing agents, 20 to 99 % ethylene-urorbornene copolymer and optionally 1 contain up to 60 % of another thermoplastic and / or 1 to 35 % of blast. 2. Combinations according to item 1, characterized in that the combinations as particulate reinforcing materials inorganic particulate reinforcing materials such as calcium carbonate, mica, kaolins, clays, silicates, silica, metal powder, metal oxides, salts, carbon black and / or organic particulate Ver3täa: kerstoffe such as thermoset microspheres , Wood flour, thermoplastic regenerants included.