Composite thermoplastic material

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer material science and can be used to manufacture structural elements of various functional destinations. Composite thermoplastic polyolefin-based material contains filler and fire-retardant additive, the former being thermally treated silicate, namely product of treatment of naturally occurring silicates by heat stroke with gradient 800-1000°C, and the latter being halogen-containing oligomer selected from group including chloroparaffin and fluorine-containing oligomer ("Foleoks"), whereas above-mentioned polyolefin is selected from group including polypropylene, low-pressure polyethylene, high-pressure polyethylene, ethylene/vinyl acetate copolymer, and thermomechanically combined mixture of polyolefins with polyolefins, polyacetals, or styrene-containing plastics.

EFFECT: improved physico-mechanical characteristics of composite polyolefin-based material and increased resistance to burning and to action of negative temperatures.

2 tbl

 

The invention relates to polymeric materials and can be used in machinery for the manufacture of products for structural purposes that is used, for example, in the construction of machinery, technological equipment and other

For the manufacture of many designs of machines, mechanisms, devices, etc. applied details of the structural materials, which provide the necessary strength, the stability of the product to the effects of vibration, shock loads. Most modern structural materials based on polymer matrices have complex requirements on physico-mechanical, thermal, adhesive, and other characteristics. In this regard, when creating composites it is necessary to select the components that have complex effect on the polymer matrix, providing a synergistic effect. These components include modifiers, particle size not exceeding 100 nm. According to the modern classification of the modifiers is called nanodispersed or nanophase and composite materials that contain them, respectively nanocomposite materials or nanocomposites.

Known composite material for tribological coatings based on a polyamide matrix containing the polyolefin modifier uglerodny filler, including nanoscale product of detonation synthesis (RF Patent 2219212). Material effective when used as a coating of friction parts, but for structural products has insufficient impact strength. Furthermore, the data material Flammability not meet the requirements for the materials, which are used in modern engineering.

Known composite materials based on polyolefins with low inflammability, which are used in machine construction and for the manufacture of household goods (self-extinguishing polypropylene composition THAT 38-3080-80).

The materials contain as flame retardants halogenated products (hexabromobenzene, decabromodiphenyl oxide) and mineral fillers (asbestos, talc). The lack of materials is low frost (-5° (C)that does not allow them to be used in mechanical engineering for the construction of important structural products.

Known polymeric composition based templating polyurethane containing as a modifier is a copolymer of formaldehyde with dioxolane (IFD) and mineral oil (A.S. USSR 897809, 1982).

The material has high wear resistance, toughness, however, does not meet the requirements for resistance to elevated temperatures, as it contains components that will destroy the s with the formation of low molecular weight products, initiating thermal-oxidative degradation of the matrix.

Famous initiated anti-friction material based on polyamide 6 containing thermoplastic additives (Polyacetals - IFD, STF, the polyolefin is HDPE, LDPE, PP) and oligomeric waxes in combination modified mineral oil (Vahelduda, Vastral, Sci. Inhibitors of the wear of metal-polymer systems. - M.: Chemistry. - 1993. - S). This material is effective for the manufacture of parts operated when exposed to corrosive environments, because able to suppress the processes of galvanic corrosion.

The disadvantage of the material is low impact strength at low temperatures, due to the significant absorption of polyamide 6.

Known composite material based on a thermoplastic matrix containing thermoplastic elastomer and functional modifier, providing homogenization of the composite during its processing method injection molding (Vahelduda, Vastral, Sci. Inhibitors of the wear of metal-polymer systems. - M.: Chemistry. - 1993. - S).

The disadvantages of this material, limiting its widespread use in engineering are: not enough high strength properties; Flammability material; high moisture absorption.

The closest in technical essence to tawlae the th solution is self-extinguishing composite material based on polypropylene for products of the electronics industry. The material contains as a matrix of polypropylene, talc and fire retardant. (Self-extinguishing compositions of polypropylene and a copolymer of propylene for products of radio industries TL6-05-266-85. Brand 21-01. - P.4.)

This composition adopted for the prototype. The disadvantages of the prototype are relatively low strength characteristics and low resistance to low temperatures.

The objective of the invention is to develop a composite thermoplastic material with the physico-mechanical characteristics varied within wide limits depending on the functional purpose of the product.

Technical result achieved in the implementation of the invention is to increase the strength characteristics of composite materials, while maintaining the required resistance to shock loads and increase resistance to negative temperatures.

The problem is solved in that thermoplastic composite material based on polyolefin containing a filler and a flame retardant, as filler contains heat-treated silicate - product of the processing of natural silicates heat stroke with a gradient of 800-1000°as a flame retardant is a halogenated oligomer selected from the group chloroparaffin, fluorine-containing oligomer "Freaks", and to the operation of the polyolefin - polypropylene, low density polyethylene, high density polyethylene, a copolymer of ethylene with vinyl acetate or thermomechanical combined mixture of polyolefins with polyolefins, polyacetylene or Staroladozhsky plastics in the following ratio, wt.%:

- heat-treated silicateof 0.01 to 10.0
- halogenated oligomer- 0,1-10,0
the polyolefin or mixture of polyolefins
with polyolefins, polyacetylene or
Staroladozhsky plastics- the rest is up to 100

The compositions of the composite materials according to the prior art and the invention are shown in table 1.

As thermoplastic polymers used polyolefins - polyethylene (HDPE), high density polyethylene (HDPE), copolymers of ethylene and vinyl acetate (CMEA) with different content of acetate groups, polypropylene (PP), and other thermoplastics: a copolymer of formaldehyde with dioxolane (IFD), acrylonitrilebutadienestyrene plastic (ABS), polystyrene (PS). For modifying matrices used halogenated oligomers: chloroparaffin production Novopolotsk JSC "Polymir" and fluorinated oligomers "Freaks" production is odstv research Institute of synthetic rubber to them. Lebedev (Saint-Petersburg). As the fluorine-containing oligomers used oligomers brands "Poleax-1" and "Freaks-14". They are products of perfluorinated carboxylic acids and are produced by THE 38.03.1.073. Molecular weight oligomers 2200 units of the Oligomer brand f-1 has the formula Rf-COOH,

Oligomer brand f-14 has the structural formula Rf-Rfwhere Rf- fluorinated radical, similar to the radical of poleaxe f-1.

The oligomers are supplied in the form of 1-2 wt.% solution halon or freon. When used as a modifier solvent evaporates and does not affect product properties.

As filler was applied and heat-treated silicate is a product obtained by heat treatment with a gradient of 800-1000°With natural minerals type layered silicates, Tripoli, kaolin, illite etc. Heat treatment was carried out by making the hinge mechanically crushed mineral to a size not more than 50 μm in the working area of a heating Cabinet at a temperature of up to 1500°and exposure within 5-30 minutes, This method provides a thermal shock, which is the destruction of the crystal lattice of the mineral particles and the formation of coarse (nanoscale) product with high activity.

Thermomechanical somese is their thermoplastic composites was carried out in the extruder with a screw plastication when modes, ensure melting and mechanical stirring of the melt.

Physico-mechanical, thermal and rheological characteristics of composite materials for the prototype and the claimed compositions are given in table 2.

Example of composite thermoplastic material of the composition (part II, table 1). Natural silicate Tripoli, representing a mixture of layered minerals and timber frame structure was subjected to grinding to size fraction is not more than 50 μm. Pellets of the polyolefin (polypropylene) were introduced in the working volume of the mixer, for example, a ball mill type MBL, and subjected to mixing together with the balls within 5-10 minutes Later in the working volume of the drum mixer was introduced a solution of chloroparaffin and stirred to obtain a homogeneous composition. A portion of powdered silicate in a given wt.% regarding put on for 5-10 minutes in a heat chamber with a temperature of 1000°C. In the particles of silicate experienced thermal shock with a gradient 975° (1000°25° (C)that caused their activation due to the removal of adsorbed moisture and processes of dehydration and dehydroxylation. Activated silicate particles after extraction from the working volume of the heating Cabinet after no more than 5 minutes were placed in a drum mixer and mixed until a homogeneous composition. When quality is the result of the mixing of each granule of polyolefin (polypropylene) obvolakivala particles of silicate and halogenated oligomer.

When used as a polymer matrix of polypropylene, modified copolymer IFD (XI, table 1), technology consisted in the following. The mixture of granules of the base polyolefin (polypropylene) and copolymer IFD processed chlorine oligomer (chloroparaffins) and half of the particles heat-treated silicate. The resulting mixture was melted in an extruder with a screw plasticities and got granules of a mixture of thermoplastic - modified polyolefin. The presence in the composition of the particles heat-treated silicate provides higher compatibility of thermoplastic components. Next, the resulting granules were mixed with the remaining part thermoactivation silicate.

In the presence of co-rotating twin screw mixers use simple technology of obtaining of material (part XII, table 1). Pre-mixture of pellets of the polyolefin (HDPE) and polystyrene (PS) are mixed in a drum mixer. Then add the estimated amount of the halogen-containing oligomer (chloroparaffin in the form of a solution) and stirred to obtain a homogeneous composition. In the structure add powdered termoaktivirovannye silicate (kaolin) and stirred in the presence of steel balls to obtain a homogeneous product. The resulting material process technology, the traditional high-pressure polyethylene.

How should the duty to regulate from the data of tables 1 and 2, the claimed compositions (I-XIV) are superior to the prototype in terms of strength, frost resistance, while maintaining the required rheological and thermophysical characteristics. The effect is achieved by using as a matrix or pure polyolefin (compounds I-VIII, X), thermomechanical mixture of polyolefin compounds (IX-X) or thermo-mechanical blends of polyolefins with other thermoplastic resins (compositions XI-XIV) with the introduction of termoobrabotannyj silicates (kaolin, Muscovite, illite, quartz, Tripoli, talc) and various halogenated oligomers (chloroparaffin and poleaxe). A feature of the receipt of thermomechanical combined matrix is the implementation of comprehensive thermal and mechanical effects on the melt components in the presence of particles of natural minerals. The decrease in the contents of the components are below the stated limits (part XVI) or exceeding (part XV) or reduces the cumulative effect or does not provide any additional effect.

Thus, the claimed compositions in the claimed value exceeds the prototype in overall characteristics.

The invention consists in the following. When introduced into the polymer matrix of inert mineral filler is an increase of some structural properties (such as hardness, compressive strength), but completion of the enhanced defect of material, deteriorating the fluidity of the melt, reduced impact strength. The heat treatment of stroke ensures the formation of the natural minerals of low-dimensional particles (nanoparticles), with activity due to the acquisition of uncompensated charge. Active nanoparticles leads to the formation in the amount of nanocomposites nanocomposite three-dimensional network of physical nodes crosslinking, which increases the strength of the matrix and its resistance to thermal oxidation processes (including burning). The modifier necessary at the same time contributes to the homogenization of the mixture is thermodynamically incompatible polymers, due to the formation of intermolecular bonds adsorption type and alignment of molecular mobility. This causes increase in strength composite matrix and its resistance to mechanical stress. The presence of the grid physical links in the volume of the composite increases its resistance to thermo-oxidative degradation, including resistance to burning. At the same time reduces the plasticizing effect of oligomeric modifier, leading to a decrease in strength of the composite.

Use as oligomers halogenated components in combination with the active modifier significantly increases the resistance of the composite to burn.

Developed material used for production is possible parts of road vehicles, automotive engineering and construction accessories.

-
Table 1
The compositions of thermoplastic composite materials
ComponentThe content in the composition in %
Prototype [6]The inventive compositionsXVXVI
IIIIIIIVVVIVIIVIIIIXXXIXIIXIIIXIV
Polyolefin:
- polypropylene (PP)7699.89 per94,58094,594,594,594,594,5to 89.5-to 89.5---7099,945
- HDPE----------to 89.5-to 89.5to 89.584,5--
- HDPE----------5------
- CMEA---------5----5--
Thermoplastic modifier:
- IFD------- ----5-----
- SS------------5----
- ABS-------------55--
Filler*
kaolin----0,5----0,50,50,50,50,50,5--
- Muscovite-----0,5-----------
- illite------0,5----------
the natural quartz-------0,5---------
- Tripoli--------0,5--------
- talc200,010,510----------150,005
Fire retardant:
- chloroparaffin-0,1510554,54,5-555555150,05
- Freaks-1------0,5----------
- Freaks-14-------0,55--------
(hexabromobenzene) 3----------------
Thermo stabilizer1----------------
* Mineral fillers (kaolin, Muscovite, illite, quartz, natural, Tripoli) were introduced in the composition of the claimed compositions after processing by thermal shock at 900°C for 10 min.

Composite thermoplastic material based on polyolefin containing the filler and the flame retardant, characterized in that the filler it contains heat-treated silicate - product of the processing of natural silicates heat stroke with a gradient of 800-1000°as a flame retardant is a halogenated oligomer selected from the group: chloroparaffin, fluorine-containing oligomer "Freaks", and the polyolefin is polypropylene, low density polyethylene, high density polyethylene, a copolymer of ethylene with Winnie the acetate or thermomechanical combined mixture of polyolefins with polyolefins, polyacetylene or Staroladozhsky plastics in the following ratio, wt.%:

Heat-treated silicateof 0.01 to 10.0
Halogenated oligomer0,1-10,0
The polyolefin or mixture of polyolefins
with polyolefins, polyacetylene or
Staroladozhsky plasticsThe rest is up to 100



 

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