Thermoplastic composition

 

(57) Abstract:

The invention relates to thermoplastic polymer compositions based on polyamides, which can find application in mechanical engineering, in particular in the automotive industry, for the manufacture of structural parts of the interior and exterior of the car. Describes a thermoplastic composition comprising a linear aliphatic polyamide, polymer-olefin, dispersed inorganic filler and modifier, characterized in that the dispersed inorganic filler composition contains a combination of thin split mica with a characteristic ratio of not less than 30, the surface of which is covered with oxide of polyvalent metal, and powder filler with a particle size of not less than 90 μm, and the modifier is chemically active connection with at least two homogeneous functional groups from among epoxy, maleimide or isocyanate, the following ratio of components in the composition, wt.%: polymer-olefin 1,0-30,0; width mica with a characteristic ratio of not less than 30 2,0-20,0; powder filler with a particle size less than 90 μm to 0.5 to 20.0; modifier 0,2-4,0; linear al who I am. 4 C.p. f-crystals, 2 tab.

The invention relates to thermoplastic polymer compositions based on polyamides, which can find application in mechanical engineering, in particular in the automotive industry, for the manufacture of structural parts of the interior and exterior of the car.

Polymeric materials used for these purposes must possess good processability during molding, in particular, large parts, elasticity, impact resistance, heat resistance, no distortion of parts during manufacturing and operation, and must also meet the aesthetic requirements of modern design.

The most suitable polymers for these purposes are aliphatic polyamides, which have good processing properties, high elasticity and strength, but have a number of disadvantages: low impact strength with notch, high absorption, insufficient heat resistance and dimensional stability of the products.

The task of increasing the impact strength and lower water absorption of the polyamide compositions are solved to a considerable extent by incorporating polymer-olefins or copolymers of ethylene and propylene or topolinnyj copolymers, obtained by grafting to the ethylene-propylene copolymer alkylacrylate (2) or ethylenepropylene the copolymer of styrene and Acrylonitrile, (3) etc.

Patent company ICI (4), declared in our country, protects thermoplastic polymer compositions with high impact strength, is more efficient due to better compatibility of the polyamide with the ethylene copolymer containing from 40 to 95 wt.% ethylene units, from 2 to 50 wt.% hydroxy - or epoxysilane essential links ,-unsaturated C3-C6acids and, if necessary, up to 55% can copolymerisate with ethylene vinyl monomer (styrene, methacrylate, methacrylamide and others). The content of the polyamide in the composition of 50 to 90 wt.%. As polyamides can be used as a linear aliphatic and aromatic polyamides.

Introduction polyolefin polyamide composition, improving shock resistance and water resistance, leads to a decrease of other indicators - modulus of elasticity and heat resistance. To improve these properties of thermoplastic compositions can be reinforced with inorganic fillers.

In the description of the patent (4) noted that the composition may contain mineral fillers, one the awning does not use filler, i.e. actually the firm patent concerns unfilled compositions.

Most similar in essential characteristics to offer us the solution of a thermoplastic polyamide composition adopted for the prototype (5), which includes:

65-95 weight.h. linear polyamide or copolyamid, or mixtures thereof;

35-5 weight.h. copolymer of ethylene hydrocarbon and an unsaturated carboxylic acid (acrylic, methacrylic - ethylacrylate) and the maleic takenaway), in which part of the carbonyl groups neutralized by a metal ion (sodium, potassium, magnesium, calcium, barium or zinc).

0.1 to 5.0 weight.h. at least one modifier containing monoepoxide or carbonate group (glycidyloxy simple or complex esters, alicyclic epoxides or epoxyalkanes, ethylene carbonate resulting, propylene carbonate or butylaniline).

To improve the mechanical properties of the composition in its composition can be introduced reinforcing inorganic fillers in the amount of 20 to 150 wt.% (to the mixture of polymers) selected from the group comprising svetlanamodel (fiber, beads), silicates of calcium, aluminum or magnesium, phosphate, magnesium, titanium sulfate and calcium sulfite, calcium carbonate, chlorides alumetal can be used both in non-activated form, and after activation of their surface by treatment with organosilanes, organoborate or thermal treatment.

Optionally, the composition can be introduced to different target additives, such as plasticizers, heat stabilizers, light stabilizers, dyes, etc..

The composition of the prototype, as noted in the description of the patent, provides for the improvement of various physical properties, particularly impact resistance, compared with the previous technical level of similar developments. As physico-mechanical characteristics for the filled composition (example 8) in the description provides data only on toughness and strength at break.

The purpose of the composition of the prototype - production of interior parts and exterior parts of the car.

The technical task of the invention to provide thermoplastic compositions based on aliphatic polyamides with an excellent combination of modulus, impact strength and heat resistance with good dimensional stability and aesthetic qualities in the product.

The problem is solved in that a thermoplastic composition comprising a linear aliphatic p is dispersnogo filler contains a combination of thin split mica with a characteristic ratio of not less than 30 the surface is covered with oxide of polyvalent metal, and powder filler with a particle size less than 90 μm, and the modifier is chemically active connection with at least two homogeneous functional groups from among epoxy, isocyanate or maleimide in the following ratio of the components of the composition, wt.% :

The polymer of the olefin - 1,0 - 30,0

Thin split mica with a characteristic ratio of not less than 30 - 2,0 - 20,0

Powder filler with a particle size less than 90 μm is 0.5 to 20.0

Modifier - 0,2 - 4,0

Linear aliphatic polyamide - Rest

As the polyamide composition may contain a polymer obtained by decimoprimera lactam (polycaprolactam - PA-6, paleodynamic - PA-12) or the polycondensation of aliphatic diamine with a dicarboxylic acid (polyhexamethylenediamine - PAS-66, polyhexamethylenediamine - PAS-610), and copolymers of polyamides or mixtures thereof.

As polymers of olefin composition may contain Homo - and copolymers of ethylene and propylene, ethylene-propylene-diene ternary copolymer (rubber), graft copolymers of polyethylene and/or polypropylene with an unsaturated carboxylic new), etc. preferably, polyethylene, grafted copolymers based on polypropylene or ethylene-propylene copolymer with acrylic acid or maleic anhydride.

Thin split mica with an average characteristic ratio (the ratio of the average linear dimension of a particle or its nominal diameter to thickness) of at least 30 can be a Muscovite or phlogopite. The surface of the mica to give it the necessary physico-chemical properties covered by the oxide of one or more polyvalent metal, preferably aluminum, titanium, iron or mixtures thereof, in the amount of 18 to 40%, preferably 21 to 28% by weight of the modified mica.

As a powder filler with a particle size less than 90 μm, the composition may contain dispersed inorganic fillers with natural or finished surface, mainly, chalk, calcite, talc, titanium dioxide.

Examples of the modifier are bismaleimide mainly of N,N'-timelimit on the basis of m-phenylenediamine or p,p'-diaminodiphenylmethane; epoxy Dianova resins with different degrees of condensation; as isocyanate compounds are used, mainly, di - or triisocyanate, natov with terminal isocyanate groups. These modifying additives contribute to the combination of organic and inorganic components of the composition and provide, thus increasing the whole complex of mechanical properties of the material.

The composition may also contain known additives target - thermal and light stabilizers, dyes, flame retardants, lubricants, etc., in an amount up to 10 wt. % by weight of the composition.

The polymer composition is prepared by mixing all components with subsequent extrusion and granulation.

Example 1. In the mixer of the type "drunken barrel" is mixed for 10 minutes granulated PA-6 brand 210/310 in the number 828 g (82,8%), HDPE brand 10803 -020 - 20 g (2%), talc brand A1 - 60 g (6%), mica Temic M63 Cf. - 80 g (8%), epoxy resin grade e-41 - 10 g (1%), thermo stabilizer lrganox 1010 - 2 g (0.2%). The mixture is then loaded into the dispenser twin screw extruder MP-2000 Baker-Perkins, the temperature of extrusion is 240-250oC. the resulting melt compositions in the form of strands are cooled in a water bath and granularit. Samples for the determination of physico-mechanical characteristics obtained by the method of injection molding according to the following mode: the temperature of the melt 245-255oC, mold temperature 80oC, a pressure of 1000 kg/cm2.

rum him using universal bursting machine Instron 1195

Specific impact strength Charpy determined on the cleats HH mm GOST-80 on pendulum impact-testing machine KM-0,4 when the speed of the pendulum 2.9 m/s

Heat bending is measured according to GOST 12021 - 84 sample size HH mm under a load of 0.45 MPa.

Water absorption was measured according to GOST 4650 - 80 samples HH mm during aging in water at a temperature of 21-23oC within 24 hours.

The distortion measured on samples in the form of a disc with a diameter of 100 mm and a thickness of 2 mm as double the value of the maximum deviation of a sample from a horizontal surface, expressed in mm (not standardized laboratory method).

The force required to extract the products from the form, determine out of line in the manufacture of test specimens of size mm., the maximum force was estimated score <+1>, minimal - <-1> average <0>.

Examples 2-9. Polymeric compositions prepared according to the method described in example 1, the compositions and the results of their testing are shown in table 1.

Examples 10-18 and control (polymeric composition prepared by the method described in example 1).

Examples 10-13 illustrate compositions based on PA 6, and examples 14-16 - n is 15 - no polymer-olefin,

example 11 - no powdery filler

examples 12, 14 - no mica,

examples 13, 16 - no modifier

example 17 illustrates the significance of the sign of the "aspect ratio" for mica, and example 18 - size particles for powder filling.

Control examples confirm the compliance of this design criterion of "inventive step": only the combination of all the claimed features - multi-component composition and characteristics of individual components - achieve combination of properties exhibited by the claimed compositions.

The comparison of our proposed technical solutions to the prototype, unfortunately, is complicated by the fact that in the description of the patent specification (5) shows only one example (N 8, experiment 21) the composition and properties of the composition, a comparable degree of filling (40%) claimed us, and considers only the strength properties determined by the standards adopted in the United States. To reproduce the composition of the prototype is not possible due to the lack of identical components. For this reason for carrying out mapping were conducted th viscosity Izod with notch (ASTM-D-256) of the composition of the proposed structure, comparable with the above structure of the prototype (see table 2).

These examples show that the composition of the proposed structure, surpassing the prototype on the strength properties, provide in comparison with the control examples the best balance of modulus and toughness. This creates the preconditions for a wider range of use of these materials, in particular in products for structural purposes, used in the manufacture of vehicle parts (housings of the headlights, interior, wheel caps, etc).

Products made from the compositions of the claimed composition, have a good decorative appearance, not susceptible to noticeable warping. The inventive composition also provides an easy way of removing the molded articles from the mold, which is especially important for parts of complex configuration.

The list of technical documentation of the materials used (examples 1 to 18 of the claimed invention).

1. The polyamide PA-6 brand 210/310 (polycaprolactam) - OST 6-06-C9-93.

2. Polyamide PA 66 (polyhexamethylenediamine) - OST 6-06-C23-79.

3. High density polyethylene HDPE 10803-020-GOST 16397-77.

4. Polybond 1006 - grafted polypropylene copolymer is a new anhydride company Exxon Chem.

6. Chalk fine - TU 6-18-38-85.

7. Omycarb 15-GU-calcium carbonate company Omya GmbH.

8. Talc brand A1 - TU 21-25-217-78.

9. The titanium dioxide pigment - GOST 9808-84.

10. Mica Temic brands: M-K-63 (content of titanium dioxide 19%, iron oxide 4%); M-Cf - 40 (content of titanium dioxide 21%, aluminum oxide, 7%); f=63 (content of titanium dioxide 21%) of THE 113 - 83-6-90.

11. Epoxy resin Dianova ED-20 - GOST 10587-76.

12. Epoxy resin Dianov e-41 - TU 6-10-607-78.

13. Polyurethane rubber SKU PFL -100 - TU 38.103137-78.

14. Maleimid f (N,N'-m-phenylene-bismaleimide) - TU 6-14-1004-87.

15. lrganox 1010-thermo stabilizer company Ciba.

16. Melincourt - flame retardant, a pilot batch production of JSC "Sintez".

17. Calcium stearate is a lubricant, THE 6-14-722-76.

18. Ultramarine blue 05 - dye company Holiday Pigments Int.

Sources of information

1. German patent N 1138922, NCI 39 B 22/06, publ. 1962

2. U.S. patent N 4594386, NCI 525-66, publ. 1986

H. European application N 400964, C 08 L 77/00, publ. 1990

4. Patent USSR N 346880, C 08 L 77/00, publ. 1972

5. U.S. patent N 4086295, NCI 260-857 L, publ. 1978 (reclassif 525-183) prototype.

1. Thermoplasticity and modifier, characterized in that the dispersed inorganic filler composition contains a combination of thin split mica with a characteristic ratio of not less than 30, the surface of which is covered with oxide of polyvalent metal, and powder filler with a particle size less than 90 μm, and the modifier is chemically active connection with at least two homogeneous functional groups from among epoxy, maleimide or isocyanate in the following ratio of the components of the composition, wt.%:

The polymer of the olefin - 1,0 - 30,0

Thin split mica with a characteristic ratio of not less than 30 - 2,0 - 20,0

Powder filler with a particle size less than 90 μm is 0.5 to 20.0

Modifier - 0,2 - 4,0

Linear aliphatic polyamide - Rest

2. The composition according to p. 1, characterized in that as the width of the mica with the characteristic attitude of not less than 30 composition contains Muscovite or phlogopite with a coating of oxide of aluminum, titanium, iron or mixtures thereof.

3. The composition according to PP.1 and 2, characterized in that as a powdered mineral filler with a particle size less than 90 μm, the composition comprises compounds of the group, is as a modifier it includes connection, selected from the group consisting of epoxy Dianova resin, aromatic N, N'-bismaleimide and oligoether with terminal isocyanate groups.

5. The composition according to PP.1 to 4, characterized in that it further comprises a target additives, stabilizers, lubricants, flame retardants, dyes in amounts up to 10 wt % by weight of the composition.

 

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