SK156399A3 - A polymeric composite material with improved flame resistance - Google Patents

Abstract

Magnesium hydroxide with surface modified by surface-active agent consists of crystal agglomerates with particles diameters less than 4.0 um, 50 % of particles of diameter less that 1.4 um and specific surface determined by a BET method is less than 25 m2/g. Magnesium hydroxide is powdered crystalline product, with the size of crystals defined by X-ray powder diffraction method in direction <004> more than 150 A and less than 500 A, aspect ratio in range from 2 to 5, deformation in <004> direction maximally 402 x 10exp(-3) and deformation in <110> direction maximally 3.0 x 10exp(-3). Disclosed is also preparation method of surface-modified magnesium hydroxide and polymeric composite material with increased fire resistance, which contains 25 to 75 wt. parts, preferably 35 to 60 wt. parts of thermoplastic substance and 75 to 25 wt. preferably 65 to 40 wt. magnesium hydroxide surface of which is modified by surface-active agent and/ or which is evenly mixed with surface-active agent.

Description

Polymer composite material with increased fire resistance

Technical field

FIELD OF THE INVENTION The present invention relates to a polymer composite material with increased flame resistance used in the cabling, electrical and automotive industries, comprising a surface-treated powdered magnesium hydroxide and a polymeric material. Furthermore, the invention relates to a surface-treated powdered magnesium hydroxide, which causes an increased flame resistance of the polymer composite material, and to a process for the preparation of such magnesium hydroxide.

BACKGROUND OF THE INVENTION

Numerous applications in the cabling, electrical and automotive industries require polymeric materials that are thermoplastically processable and yet have increased fire resistance. Most of the previously known polymer materials with increased flame resistance consisted either only of a polymer that had already incorporated halogen atoms in the polymer matrix, or consisted of a non-halogenated polymer and a flame retardant based on an organohalogen compound. In addition to increased fire resistance, such polymeric materials had several disadvantages: they were not self-extinguishing and released large amounts of smoke, toxic and corrosive fumes into the environment during thermal-oxidative decomposition.

The above mentioned technological and ecological deficiencies are eliminated by the use of powdered magnesium hydroxide as halogen-free flame retardant for polymeric substances. Thermal decomposition of magnesium hydroxide releases chemically bound water, thereby promoting the internal self-extinguishing process, and no thermal and corrosive fumes that are of magnesium hydroxide origin are released in the thermal oxidative decomposition of the composite material.

A disadvantage of using magnesium hydroxide as a flame retardant in plastics is that the effective reduction of the flammability of the polymer composite material is only achieved after the incorporation of a large amount of magnesium hydroxide into the plastic. Typically, this amount is between 40 to 65% of magnesium hydroxide in the polymer composite material. Evenly incorporating such a large one

The amount of magnesium hydroxide in the polymeric substance is very demanding, since the polymer has a mostly non-polar linear matrix composed of long chains, while the magnesium hydroxide molecule is polar and its powdered particle can, depending on the method of preparation, either hexagonal or spherical. In addition, upon incorporation of such a large amount of magnesium hydroxide into a polymeric material, some of the properties of this material will deteriorate, in particular its impact strength, strength, ductility, and elongation. The degree of deterioration of these properties also depends on how the magnesium hydroxide has been treated prior to incorporation into the polymeric substance, in order to maximize its acceptability by the polymeric matrix and thus the uniformity of its dispersion in the matrix. It has been shown that the water cleaved from the magnesium hydroxide molecule is self-extinguishing only in the immediate vicinity and therefore only with perfect dispersibility of the surface-treated magnesium hydroxide can the desired degree of flame retardancy V-0 be achieved. From this point of view, the disadvantage is the natural property of crystalline magnesium hydroxide - its tendency to aggregate. There is usually no affinity between the polymeric substance and magnesium hydroxide. Here, it has been shown that the phase interface between the polymer matrix and the magnesium hydroxide particles, the so-called &quot; interphase (J. Manson, L. Sperling: Polymer Blends and Composites. Heyden, London 1976). The interphase has a finite thickness and properties that fluently change over the respective properties of the polymer and magnesium hydroxide [P. Theocaris: Adv. in Polymer Sci. 66, 149 (1985)]. Correctly selected surface treatment of the magnesium hydroxide particles leads to the formation of an interphase which achieves maximum adhesion of the magnesium hydroxide particles to the polymer and thus a voltage transfer from the polymer to the filler. The interphase must ensure dissipation of the energy and prevent voltage concentration [P. Mardsen, L. Ziemiansky: Br. Polym. J., 11, 199 (1977)].

The presently most widely used method of positively influencing the incorporation of magnesium hydroxide into the polymeric material and the resulting properties of the composite is the surface treatment of the magnesium hydroxide powder particles prior to incorporation. The correctly selected surface treatment of the magnesium hydroxide powder particles must meet the entire complex of the above requirements, which results in the fact that a given amount of magnesium hydroxide is used with conventional compounding equipment (Wemer & Pfleiderer twin screw extruder, Buss KO-kneader)

- 3 Berstorff ZE 40 EA) kneading and granulating equipment is incorporated into the polymer fabric without problems and such material has the desired appearance and satisfactory non-flammable, processing and performance properties. A properly selected surfactant must therefore reduce the energy barrier to the incorporation of magnesium hydroxide into the plastic, remove the electrical charge from the magnesium hydroxide surface and make it more acceptable both for incorporation into the plastic and for even distribution of magnesium hydroxide particles in the plastic. thus, adhering to each other between the organic polymer and the inorganic filler, to ensure a homogeneous distribution of the magnesium hydroxide particles in the composite, to act as a binding agent and binder between the magnesium hydroxide particles and the polymer matrix, and as a means of improving the compatibility of the composite material.

Japanese Patent 60243155, but also U.S. Pat. Nos. 4,098,762, 5,144,365 and German Patent Nos. DT 26,224,065 A1 and DE 26 59,933 B1 use a surfactant based on the alkali salts of higher fatty acids, or the corresponding alkyl sulfates or sulfonates or alkylarylsulfonates, or the alkali salts of the sulfosuccinic ester, the number of carbon atoms in the aliphatic acid chain being 8 to 30. Specifically, the surfactants used were: sodium stearate, sodium or potassium oleate, sodium or potassium palmitate, sodium or potassium laurate, potassium behenate, sodium laurylbenzenesulfonate , sodium octadecenate, sodium lauryl sulfonate and disodium 2-sulfoethyl-α-sulfostearate.

In the Czechoslovak patent 241 640 it is recommended to use some of the hydrophobic substances, such as a mixture of higher fatty acids or silane or titanate, as an addition to the magnesium hydroxide before its incorporation into the plastic. Specifically, a mixture of higher fatty acids, aminopropyltriethoxysilane, ethylenediaminopropylprimethoxysilane and triisostearoylisopropyltitanate were used.

The use of alkoxysilanes for the surface treatment of magnesium hydroxide is also disclosed in PCT WO 90/13516, but in particular no alkoxysilanes are named.

In U.S. Pat. No. 4,769,179, the magnesium hydroxide coating is carried out using titanates containing a phosphorus atom. In particular, they are organophosphitotitanates and organophosphate titanates. Preferred are: tetraisopropyl di (dioctylphosphito) titanate, tetraisopropyl di (laurylphosphito) titanate, tetra (2,2-4 dialyoxymethyl-1-butoxy) di (di-tridecyl) phosphitotitanate, isopropyl tris (dioctylpyrophosphate) titanate and bis (dioctylpyrophosphato) titanate ) oxyacetate titanate.

Other complicated phosphorus-based compounds are recommended by the European patent 0 356 139 A1 for the surface treatment of magnesium hydroxide. These are the dialkoholamino salts of the alcohol-phosphate esters or the alcohol-phosphate esters or their metal salts. In particular, the diethanolamine salt of dioleyl alcohol phosphate ester, the sodium salt of lauryl alcohol phosphate ester, the diethanolamine salt of stearyl alcohol phosphate ester, the sodium salt of erucylalcohol phosphate ester and the diethanolamine salt of aralkylalcohol phosphate ester were used. In a comparable example, the coating was made with sodium oleate.

According to U.S. Pat. No. 4,698,379 and European Patent No. 0 189 098 A2, it is preferable to use saturated or unsaturated fatty acids, metal fatty acid esters, fatty acid esters, fatty acid ethers, surfactants, silanes or titanates for surface treatment of magnesium hydroxide spherical particles, titanates being preferred. Specifically, stearic acid, sodium stearate, glycerin monostearyl ester, glycidylsilane and tetrastearyl titanate were used.

All of these methods of surface treatment of powdered magnesium hydroxide have one common feature and that the surfactant is only one substance. In view of the complex requirements of incorporating magnesium hydroxide into a polymeric material and consequently the mechanical, electrical and processing properties of the resulting composite, it is highly unlikely that only one surfactant can provide such a complex function. For this reason, it is preferable to use a combination of two or more surfactants for the surface treatment of magnesium hydroxide.

The use of not only stearic acid, oleic acid, lauric acid, palmitic acid, sodium or potassium stearate, potassium behenate, sodium montanate, sodium or potassium oleate, sodium palmitate is known from the patent literature (PCT WO 95/19935, PCT WO 96/16902). or potassium, sodium or potassium laurate, sodium dilaurylbenzenesulfonate, potassium octadecylsulfonate, sodium lauryl sulfonate, disodium 2-sulfoethyl-α-sulfostearate, ammonium salts of fatty acids, but also mixtures thereof.

According to U.S. Pat. No. 4,396,730, an improved effect is obtained when magnesium hydroxide is treated with an alkali (e.g. sodium oleate) surface.

- 5 is mixed with another agent which is one of a pair of magnesium oleate or aluminum oleate. The higher effect of such a combination was compared to a magnesium hydroxide whose surface was untreated but was mixed with magnesium stearate.

In the Czechoslovak patent 261 162, it is recommended to incorporate untreated magnesium hydroxide into polyolefins together with partial esters of C 12 -C 22 carbon atoms with polyhydric alcohols having 3 to 10 carbon atoms or a mixture thereof with said fatty acids or salts thereof.

According to German patent DE 39 27 861 A1, an improvement is achieved when a mixture of a (Ca, Mg, Zn) fatty acid salt (CpCjg), preferably palmitic acid or stearic acid with fatty acid amides, preferably stearanamide, is mixed with the inorganic filler , oleaamide, behananamide.

A disadvantage of all these processes is the fact that the above-mentioned surfactant mixtures consist of chemically similar compounds which have a similar effect and do not complement each other. They are mostly higher fatty acids, or salts or derivatives thereof, which act to a greater extent as lubricants, lubricants and, to a lesser extent, as binding agents.

On the other hand, European patent 0 426 196 A1 recommends silane or titanate or aluminate or zirconate or zirconium aluminate or combinations thereof. Again, these are agents of a similar nature and effect, which primarily act as binders, and therefore even their mixture cannot provide the entire complexity of the requirements imposed on the surface treatment of magnesium hydroxide as mentioned above.

Some improvement can be expected from U.S. Pat. No. 4,913,965. However, it relates only to a crystallographically well-defined magnesium hydroxide having a crystal size in the <101> direction greater than 800 A and a deformation in the <101> direction not greater than 3.0. 10, wherein the plastic is an ethylene-vinyl acetate copolymer containing 25 to 60 parts by weight of vinyl acetate per 100 parts by weight of the copolymer. For such a system, it is recommended to treat the surface of the magnesium hydroxide with one or more carboxylic acids (C8-C24) or their metal salts. The amount of such agents is 0.1 to 5 parts by weight per 100 parts by weight of magnesium hydroxide. One of the additives used in the incorporation of surface-treated magnesium hydroxide is organosilane, which performs the function of a binding agent in a very

- 6 low concentrations (0.017 to 0.277 parts by weight per 100 parts by weight of magnesium hydroxide). However, only two parameters are used to assess the effects, namely the oxygen limit number and the melt index, which is insufficient in terms of processing properties in the cable industry. The results of mechanical properties such as strength, ductility, hardness and elasticity are missing.

The disadvantages of the prior art solutions are, in particular, the fact that they have not been able to provide the whole complex of requirements for the surface treatment of magnesium hydroxide in terms of its incorporation into the polymeric material and consequently the required non-combustible and processing properties of the thus formed composite. This is evidenced by the fact that in bulk. in most cases, a one-component coating is recommended and, when a blending agent is used, it almost exclusively consists of chemically and functionally similar components that cannot produce a significantly higher effect. This is further evidenced by the fact that the individual effect of the above-mentioned patent documents does not sufficiently demonstrate the higher effect of the proposed surface treatment methods. When evaluating the whole process, it is necessary to mention the achieved performance of the compounding device (consumption of magnesium hydroxide per unit of time), the appearance of the composite molding, the parameter characterizing the flammability and the required processing properties of the composite material. The unwillingness of the molten polymer material to receive the required amount of magnesium hydroxide into its volume is manifested by the "float" of the powdered filler on the melt surface, but also by the low power of the compounding device. These parameters characterize deficiencies in terms of adhesion and bonding of organic and inorganic material. In unfavorable cases, the appearance of the composite molding may exhibit a non-homogeneous structure, the so-called &quot; 'Marbling', indicating the inhomogeneous distribution of magnesium hydroxide in the plastic. This is related to insufficient depolarization of the magnesium hydroxide surface (insufficient dissipation of electric charge from its surface) and poor functionality of the interphase.

In addition to the surface treatment of magnesium hydroxide particles, crystalline magnesium hydroxide particles also have a significant influence on its incorporation into the polymeric substance and on its processing and non-combustible properties. The interaction of the particles with the polymer matrix depends on a number of factors, the most important of which are the surface porosity of the particles, mostly indirectly characterized by Sbet, particle size, particle size distribution and the willingness of the magnesium hydroxide crystals to agglomerate [G. R. Cotten:

- 7 Rubber Chem. Technol., 58, 744 (1985)]. The crystals (primary particles) of magnesium hydroxide have a natural tendency to agglomerate at birth, forming secondary particles, the size of which is usually up to tens of microns. These secondary particles then form a powdered crystalline product which is incorporated into the polymeric material. When the aggregation of the primary particles is large, magnesium hydroxide is difficult to incorporate and its uniform distribution in the composite material becomes very difficult. To date, the known solution to this problem consists either in grinding large aggregate magnesium hydroxide particles (for example, according to Czechoslovakian patent 241 640 aggregates larger than 50 µm) or in controlling the precipitation and crystallization process to form large-sized crystals (primary particles). the affinity for aggregation is already minimal (for example, according to US patents 4,098,762.4,913,965 and German patents DE 26 59 933 B1, DT 26 24 065 A1, the crystal size in the <101> direction must be greater than 800 A).

The disadvantage of these procedures is that they are energy and financially demanding. Grinding itself requires the inclusion of a costly apparatus in the technological line, and its operation is energy intensive. The industrial preparation of large single crystals is energy intensive because of the use of dilute solutions, long crystallization times and consequently handling large quantities of mother liquors.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a polymer composite material having improved flame resistance and having desired processing characteristics, the retarding component of which is magnesium hydroxide.

It is a further object of the present invention to provide a magnesium hydroxide surface which is treated with a surfactant to ensure that the required amount of magnesium hydroxide is incorporated into the thermoplastic, is evenly distributed throughout the thermoplastic, compatible with the substance, and increased flame resistance and processing and performance requirements. characteristics.

Another object of the present invention is a process for preparing magnesium hydroxide, the surface of which is treated with a surfactant.

-8.

Other essential features of the invention will be apparent from the following description.

The flame resistant polymer composite material of the present invention comprises 25 to 75 parts by weight, preferably 35 to 60 parts by weight of polymeric material (per 100 parts by weight of polymer composite material) and 75 to 25 parts by weight, preferably 65 to 40 parts by weight. magnesium hydroxide (per 100 parts by weight of polymer composite material), the surface of which is treated with a surfactant and / or which is uniformly mixed with the surfactant. The polymer composite material may include other additives which are commonly used for this purpose, as desired and depending on the polymer material selected.

For the purposes of the present invention, magnesium hydroxide must meet the general conditions imposed on an inorganic powder filler. Preferably, its specific BET surface area is less than 25 m ² / g and at least 50% of the particles have a diameter of less than 1.4 µm, with no particle having a diameter of more than 4 µm. The small particles thus characterized are the product of minimal aggregation of crystals (primary particles). We have found that when the magnesium hydroxide is a powdered crystalline product whose crystals have a plate hexagonal shape, its willingness to aggregate can be minimized by preparing such magnesium hydroxide crystals having defined shape and geometric characteristics and energy ratios on their surface. Specifically, when the crystal size determined by powder diffraction X-ray in the <004> direction is 0 by greater than 150 A but less than 500 A, the aspect ratio is in the range of 2 to 5, the deformation in the <004> direction is maximum 4.2.10 ' ³ and the deformation in the <110> direction is at most 3.0.10' ³ , at which time aggregation of such crystals is minimal and secondary particles are obtained having a suitable size and specific surface area as described above. The aspect ratio is defined as the ratio of the crystal size in the <110> direction and the crystal size in the <004> direction. It is an important shape parameter because it gives the ratio between the width of the hexagonal crystal plate and its thickness. The deformation values characterize the energy conditions on the walls of such a crystal. For more details, see HP Klug, LE Alexander: X-RAY DIFFRACTION PROCEDURES, Second Edition, John Wiley & Sons, New York 1974. Equations for calculating crystal sizes and deformations are also found in the Philips PC-APD X-ray machine manual. SOFTWARE OPERATION MANUAL

- 9 Fourth Edition, April 1992. The process of preparing such crystals with limited aggregation capability is not as energy intensive as the process of preparing large crystals that no longer aggregate and are prepared, for example, according to US patents 4,098,762, 4,913,965 and German patents. DE 26 59 933 B1, DT 26 24 065 A1.

An important finding of the present invention is that the incorporation of magnesium hydroxide into the polymeric material is improved and such polymer composite material has increased flame resistance and good processing and utility properties when a mixture of two or more substances in a combination that it will ensure that the entire complex of coating agent requirements mentioned above is met. Such a surfactant may be a mixture of titanate and metal salts of fatty acids and / or fatty acid amides, a mixture of titanate and higher fatty acids, a mixture of silane and higher fatty acids. Using any of these mixtures in certain amounts and concentration ratios gives better results than using only one of the components of these mixtures.

Another important discovery of the present invention is that when an aromatic organic compound with at least three conjugated double bonds is added to the surfactant formed by the above compositions, the appearance and properties of the polymer composite material are further improved, which is likely to be associated with more efficient electron discharge. magnesium hydroxide. This effect is already significant at low concentrations of the aromatic organic compound. Such an improvement has also been observed in cases where the aromatic compound with at least three conjugated bonds is added to titanate alone, to silane alone, to metal fatty acid salts and / or fatty acid amides alone, and to higher fatty acids alone, when these substances were used alone.

The recommended amounts of the surfactant mixture when using a mixture of titanate and metal salts of higher fatty acids and / or fatty acid amides or a mixture of higher fatty acids and titanate are 0.5 to 4.0 parts by weight of such a mixture, preferably 1.5 up to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide.

-10-.

The amount of titanate in such a surfactant is 0.05 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight, per 100 parts by weight of magnesium hydroxide.

The amount of metal salts of fatty acids and / or fatty acid amides as well as the amount of higher fatty acids in such a surfactant is 0.05 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight per 100 parts by weight of magnesium hydroxide. .

The recommended amounts of the surfactant mixture when using a mixture of titanate, metal salts of fatty acids and / or fatty acid amides and an aromatic organic compound with at least three conjugated bonds or a mixture of higher fatty acids, titanate and an aromatic organic compound with at least three conjugated double bonds are 0.5 to 4.0 parts by weight, preferably 1.5 to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide.

The amount of titanate in such a surfactant is 0 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight per 100 parts by weight of magnesium hydroxide.

The amount of metal salts of fatty acids and / or fatty acid amides as well as the amount of higher fatty acids in such a surfactant is 0 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight per 100 parts by weight of magnesium hydroxide.

The amount of the aromatic organic compound with at least three conjugated double bonds in such a surfactant is 0.002 to 0.1 parts by weight, preferably 0.005 to 0.05 parts by weight, per 100 parts by weight of magnesium hydroxide.

The recommended amounts of the surfactant mixture when using a mixture of higher fatty acids and silane are 0.5 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide.

The amount of silane in such a surfactant is 0.3 to 3.0 parts by weight, preferably 0.5 to 2.0 parts by weight per 100 parts by weight of magnesium hydroxide.

The amount of higher fatty acids in such a surfactant is 0.05 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight, per 100 parts by weight of magnesium hydroxide.

-11-.

The recommended amounts of the surfactant mixture when using a mixture of higher fatty acids, silane and an aromatic organic compound with at least three conjugated double bonds are 0.5 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide.

The amount of silane in such a surfactant is 0 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight, per 100 parts by weight of magnesium hydroxide.

The amount of higher fatty acids in such a surfactant is 0 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight, per 100 parts by weight of magnesium hydroxide.

The amount of the aromatic organic compound with at least three conjugated double bonds in such a surfactant is 0.002 to 0.1 parts by weight, preferably 0.005 to 0.05 parts by weight, per 100 parts by weight of magnesium hydroxide.

For the purposes of the present invention, preferably monoalkoxytitanate, chelated titanate, quatized titanate, coordination type titanate, cycloheteroatom type titanate or neoalkoxytitanate may be used as the titanate. Examples of monoalkoxytitanate include titanium IV 2-propanoate, tris isooctadecanan-O; titanium IV bis 2-methyl-2-propenane-O, isooctadecanane-O-2-propanoate; titanium IV 2-propanoate, tris (dodecyl) benzenesulfonan-O; titanium IV 2-propanolate, tris (dioctyl) phosphate-O; titanium IV (4-amino) benzene sulfonate-O, bis (dodecyl) benzene sulfonate-0,2-propanoate; titanium IV, tris (2-methyl) 2-propenane-O, methoxydiglycolylate; titanium IV 2-propanolate, tris (dioctyl) pyrophosphate-O; titanium IV, tris (2-propenane-O), methoxydiglycolylate; titanium IV 2-propanolate, tris (3,6 diaza) hexanolate. Examples of chelated titanate include titanium IV bis [4- (2-phenyl) 2-propyl-2] phenolate, oxoethylenediolate; titanium IV bis (dioctyl) pyrophosphate-O, oxoethylenediolate, (adduct), (dioctyl) (hydrogen) phosphite-O; titanium IV oxoethylenediolate, tris (2-methyl) -2-propenane-O; titanium IV bis (butyl, methyl) pyrophosphate-O, oxoethylenediolate, (adduct), bis (dioctyl) hydrogen phosphite; titanium IV bis (dioctyl) phosphate-O, ethylenediolate; titanium IV bis (dioctyl) pyrophosphate-O, ethylenediolate, (adduct), bis (dioctyl) hydrogenphosphite. Examples of quatized titanate include titanium IV bis (dioctyl) pyrophosphate-O, oxoethylenediolate, (adduct), 2 moles of 2-N, N-dimethylamino-2-methylpropanol; Titanium IV bis (butyl, methyl) pyrophosphate-O, (adduct), 2 moles of 2-N, N-dimethylamino-2-methylpropanol; titanium IV ethylenediolate, bis (dioctyl) pyrophosphate-O, bis (triethyl) amine salt; titanium IV

-12-.

bis (dioctyl) pyrophosphate-O, bis (dialkyl) amino alkyl-2-methyl propenane ethylenediolate; titanium IV bis (dioctyl) pyrophosphate-O, ethylenediolate, (adduct), 2 moles acrylate-0 active amine; titanium IV bis (dioctyl) pyrophosphate-O, ethylenediolate, (adduct), 2 moles 2-methylpropenoamido-N active amine; titanium IV bis (butyl, methyl) pyrophosphate, ethylenediolate, bis (dialkyl) amino alkyl acrylate salt; titanium IV (bis-2-propenolatomethyl) -1-butanolate, bis (dioctyl) pyrophosphate O, (adduct), 3 moles of Ν, Ν-dimethylaminoalkyl propenoamide, titanium IV 2,2 (bis 2-propenolatomethyl) butanolate, tris (dialkyl) pyrophosphate- O, (adduct), n moles of N, N-dimethylaminopropylmethacrylamide, wherein alkyl is octyl or isooctyl and n = 1-3. Examples of coordination type titanate include titanium IV tetrakis 2-propanoate, (adduct), 2 moles (dioctyl) hydrogen phosphate; titanium IV tetrakis octanoate, (adduct), 2 moles (ditridecyl) hydrogen phosphite; titanium IV tetrakis (bis 2-propenolate methyl) -1-butanolate, (adduct), 2 moles (di-tridecyl) hydrogen phosphite. Examples of cycloheteroatom-type titanate include titanium IV bis octanoate, cyclo (dioctyl) pyrophosphate-O, O; titanium IV bis cyclo (dioctyl) pyrophosphate-O, O. Examples of neoalkoxytitanates include titanium IV 2,2 (bis 2-propenolate methyl) butanolate, tris (dioctyl) phosphate-O; titanium IV 2,2 (bis 2-propenolate methyl) butanolate, trisneodecanane-O; titanium IV 2,2 (bis 2-propenolate methyl) butanolate, tris (dioctyl) pyrophosphate-O; titanium IV 2,2 (bis 2-propenolate methyl) butanolate, tris (dodecyl) benzenesulfonan-O; titanium IV 2,2 (bis 2-propenolatomethyl) butanolate, tris (2-ethylenediamino) ethyl acetate; titanium IV 2,2 (bis 2-propenolate methyl) butanolate, tris (3-amino) phenylate; titanium IV 2,2 (bis 2-propenolate methyl) butanolate, tris (6-hydroxy) hexanane-O. Preference is given to the use of quatized titanates, in particular titanium IV 2,2 (bis 2-propenolatomethyl) butanolate, tris (dialkyl) pyrophosphate-O, (adduct), n moles of N, N-dimethylaminopropyl methacrylamide, wherein alkyl is octyl or isooctyl and n = 1-3. A mixture of appropriately selected titanates may also be used instead of one titanate. The choice of a suitable titanate is not limited to the above titanate list.

For the purposes of this invention, metal salts of fatty acids and / or fatty acid amides having an alkali metal or alkaline earth metal cation and a C 8 to C 24 carbon chain can be used. Examples of such salts or amides are sodium or potassium oleate, sodium or potassium palmitate, zinc or magnesium stearate, palmitic acid amide, stearic acid amide, oleic acid amide or mixtures thereof. Preferably a technical blend of metal salts of fatty acids and fatty acid amides can be used.

For the purposes of this invention, higher fatty acids having a carbon chain of 8 to 24 carbon atoms can be used. Examples of such higher fatty acids are oleic acid, palmitic acid, stearic acid, preferably a technical blend of higher fatty acids, especially palmitic acid and stearic acid, may be used.

Various organofunctional silanes can be used as silane for the purposes of the present invention. Examples of such silanes include octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-metoxyetoxysilán), gamma-methacryloxypropyltrimethoxysilane, beta- (3,4epoxycyklohexyl) ethyl trimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamamerkaptopropyltrimetoxysilan, gamma-aminopropyltrimethoxysilane, gamaaminopropyltrietoxysilan, N-beta - (Aminoethyl) gamma-aminopropyltrimethoxysilane, gammaureidopropyltriethoxysilane or another aminofunctional, triaminofunctional or isocyanatofunctional silane or polysulfidosilane or vinyl-modified polydimethylsiloxane or organosilane ester, preferably a gammaaminopropyltriethoxane.

Examples of the aromatic organic compound with at least three conjugated double bonds are 4-dimethylaminoazobenzene, 1,4-diaminoanthraquinone or preferably 2,2 '- (1,2-ethanediyldi-4,1-phenylene) bisbenzoxazole.

Examples of polymeric materials that can be used to prepare the polymer composite material of the present invention include polyolefins, polyamides, PVC, ethylene-propylene copolymers (EPM), ethylene-propylene-diene terpolymers (EPDM), ethylene-vinyl acetate copolymers (EVA). and block copolymers thereof, polystyrenes, styrene-based elastomers (e.g., SBS, SIS, SEBS), ether-ester-block copolymers (EEBC), thermoplastic PUR-elastomers (TPU), polyether-polyamide-block copolymers (PEBA), thermoplastic silicone rubbers (TPQ), styrene-acrylonitrile copolymers (SAN), ethylene-ethyl acrylate copolymers (EEA), isobutylene-isoprene copolymers (IIR), rubbers ABS, AAS, AS, MBS, chlorinated polyolefins (chlorinated PE, chlorinated PE, chlorinated PE) - propylene copolymers, polyvinyl acetates, polyacetals, polyimides, polycarbonates, polysulfones, polyphenylene oxides, polybutylene terephthalates, methacrylic polymers and their mixtures in suitable combinations.

The polymer composite material may include other additives, such as antioxidants, UV stabilizers,

- 14 antistatic agents, pigments, dyes, plasticizers, fillers, viscosity adjusting agents, metal deactivators, crosslinking agents, reinforcing fiber fillers and others.

Examples are: a) for antioxidants: mono-cumyldiphenylamine, 4,4'-dicumidiphenylamine and their technical mixture, phenyl-α-naphthylamine, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri- tert-butylphenol, thiobis (β-naphthol), styrene phenol, distearyl thiodipropionate, dilauryl thiodipropionate, [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate] methane, 2,2-thio [diethyl- bis-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate], N, N'-diphenyl-p-phenylenediamine, N, N'-di-3-naphthyl-phenylenediamine, N-isopropyl-N ' -phenyl-p-phenylenediamine, trinonylphenyl phosphite, 4,4'isopropylidene-bisphenol, phenol, 1,1-bis- (4-oxyphenyl) cyclohexane, dialkylene trialkyl phenols, 2-mercaptomethylbenzimidazole; b) for UV stabilizers: carboxyphenyl salicylate, ptert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, benzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate; (c) for antistatic agents: sulphonated oleic acid, pentaerythritol monostearate, phosphate esters, lauryltrimethylammonium chloride, aliphatic amines, alkylphenols; (d) for coloring matters: rhodamine, methyl violet, Prussian blue, yellow cadmium, red cadmium, titanium dioxide, t

red iron oxide, barium sulfate, zinc sulfate, ultramarine, eosin, cobalt violet, benzidine yellow, carmine 6B, carbon black; e) for plasticizers: dimethyl phthalate, diethyl phthalate, noctyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl adipate, di-n-decyladipate, tributyl phosphate, tri-2-ethylhexyl phosphate, dioctyl sebacate, oil bearing oil, epoxide; (f) for fillers: calcium carbonate, asbestos, glass fibers, aluminum powder, copper powder, iron powder, alumina, talc, gypsum, graphite, carbon black, barium sulphate, dolomite, silica gel, titanium oxide, iron oxide, silicon carbide; (g) for crosslinking agents: dicumyl peroxide, tert-butylcumyl peroxide, α, α'-bis (tert-butylperoxy-m-isopropylbenzene), tetramethylthiuram disulfide, tetraethylthiuram disulfide, 2-mercaptobenzothiazole, dibenzothiazyl disulfide; (h) for reinforcing fibrous fillers: asbestos, glass fibers, potassium titanate, fibrous magnesium hydroxide, fibrous magnesium oxide, carbon fibers; wherein the examples do not limit the scope of the additives used.

The amounts of these additives are selected individually and are, for example, from about 0.01 to 5% by weight for antioxidants, from about 0.01 to 1.0% by weight for UV stabilizers, from about 0.1 to 2.0% by weight for antistatic agents, from about 0.1 to 5% by weight of colorants, from about 10 to 60%

- 15% by weight for plasticizers, from about 5 to 60% by weight for fillers, about 1.0 to 10% by weight for crosslinking agents, about 5 to 50% by weight for fiber reinforcing fillers, all percentages based on the weight of the polymeric substance .

It is important that all of the ingredients of the surfactant of the present invention be contacted with the magnesium hydroxide simultaneously, since only this will ensure their proportional representation on the surface of the magnesium hydroxide. In this case, it is said that the surface of the magnesium hydroxide particles has been treated with a complete surfactant. It is also possible to contact only a portion of the surfactant components with magnesium hydroxide, and the surface-treated magnesium hydroxide together with the missing portion is incorporated into the complete surfactant combination of the present invention, incorporated into the polymeric substance. In this case, it is said that the surface of the magnesium hydroxide particles has been treated with an incomplete surfactant. This latter case is less advantageous because the portion of the surfactant that is added to the already treated magnesium hydroxide prior to incorporation into the plastic acts less efficiently than if applied directly to the magnesium hydroxide surface due to the surface already occupied incomplete surfactant.

The surface-treated magnesium hydroxide can be prepared according to the invention in such a way that the complete surfactant or an incomplete part thereof in the form of a solution or emulsion is added to the aqueous magnesium hydroxide suspension, mixed and the water is separated. In the case of dissolving higher fatty acids, their metal salts or amides in water, it is possible to increase their solubility by adding a small amount of ammonia. The surface treatment is usually carried out at a normal temperature of 20 to 30 ° C. The process can be carried out in a continuous mixer or batch process in an agitator apparatus. In the case of a batch process, the contact and mixing time is not longer than 45 minutes, usually only 30 minutes. After filtration, the filter cake is dried at a temperature of 110 to 130 ° C to constant weight.

In another method for preparing a surface-treated magnesium hydroxide, the mixture of the magnesium hydroxide and the complete surfactant or an incomplete portion thereof is stirred in an agitator at an elevated temperature at which the surfactant is uniformly applied to the surface of the magnesium hydroxide particles and then cooled. Usually, high speed fluid mixers, e.g.

-16-.

whose heat required to increase the flowability of the surfactants and their application to the surface of the magnesium hydroxide particles results from the conversion of the kinetic energy of the particles during their collisions.

In another method for preparing a surface-treated magnesium hydroxide, all or part of the surfactant is added to the aqueous magnesium hydroxide slurry, then the slurry is hydrothermally treated at 110 ° C to 200 ° C, 0.2 to 1.6 MPa, cooled and water is separated by filtration and drying.

The following examples illustrate the invention in more detail, but the scope of the invention is not limited to the examples below.

Example 1

2258 kg of magnesium hydroxide in the form of a filter cake with a dry matter content of 35,2% by weight, in which the magnesium hydroxide has a crystal size determined by powder diffraction (X-ray machine PW 1820 with detector type PW 1710, f. PHILIPS) in <004> A 'aspect ratio of 2.2: 1, deformation in <004> direction 1.92. 10, deformation in <110> direction 2.85. 10 ', d 50 = 1.01 pm determined by a laser diffractometer for particle size measurement and particle size distribution (SK Laser Micron Sizer PRO-7000, SEISHIN) and Sbet = 8.6 m ² / g evaluated from adsorption isotherms based on nitrogen adsorption (ACUSORB 2100 E, f. MICROMERITICS), was shaken in 9120 kg of demineralized water at 30 ° C in a stirrer vessel. Separately, 2500 kg of an aqueous solution containing 7.95 kg of titanium IV 2.2 (bis 2-propenolatomethyl) butanolate, tris (diisoctyl) pyrophosphate-0 in the addition compound with N. N-dimethylaminopropyl methacrylamide and 11.92 kg of a mixture of metal fatty acid salts are prepared. of fatty acid amides (Struktol Polydis TR 016). The magnesium hydroxide slurry and reagent solution are continuously metered into a flow mixer and after filtration, dried at 110-130 ° C to obtain surface-treated magnesium hydroxide.

A polymer composite material consisting of 65 parts by weight of surface-treated magnesium hydroxide and 35 parts by weight of polypropylene (a homopolymer characterized by a melt flow rate of 5 g / 10 min, 230 g) is prepared in a kneader-granulation extruder (Wemer & Pfleiderer ZSK 30).

-17-.

° C, 2.16 kg). Test specimens are prepared by injection molding at 230 ° C. The material properties are given in Table 1.

Example 2

The procedure was as in Example 1, except that instead of 11.92 kg of a mixture of metal salts of fatty acids and fatty acid amides, 10.33 kg of a technical mixture of higher fatty acids, mainly containing palmitic acid and stearic acid, were used. presence of a small amount of ammonia. The material properties are given in Table 1.

Example 3

The procedure of Example 1 was followed except that the aqueous surfactant solution additionally contained 0.08 kg of 2,2 ' - (1,2-ethylenedildi-4, 1-phenylene) bisbenzoxazole. The material properties are given in Table 1.

Example 4

The procedure of Example 2 is followed except that the aqueous surfactant solution additionally contains 0.08 kg of 2,2 ' - (1,2-ethylenedildi-4, 1-phenylene) bisbenzoxazole. The material properties are given in Table 1.

Example 5

2273 kg of magnesium hydroxide in the form of a filter cake with a dry matter content of 35.1% by weight, in which the magnesium hydroxide has a crystal size as determined by powder diffraction X-ray <354 A *, 3.2: 1 aspect ratio, deformation at <004 > direction 2.92. 10 ' ³ , deformation in <110> direction 2.25. 10 ' ³ , d 50 = 1.03 µm and Sbet ⁼ 9.4 m ² / g, is suspended in a stirrer vessel in 9120 kg of demineralized water at a temperature of

-18-.

C. Separately, 2500 kg of an aqueous solution containing 23.9 kg of titanium IV 2,2 (bis 2-propenolatomethyl) butanolate, tris (diisooctyl) pyrophosphate-0 in an NN-dimethylaminopropylmethacrylamide addition compound and 0.160 kg of 2,2 '- ( l, 2-eténdiyldi-4, lfenylén) bisbenzoxazole. The magnesium hydroxide slurry and the reagent solution are continuously metered into the flow mixer and, after filtration, dried at 110-130 ° C to obtain surface-treated magnesium hydroxide.

The polymer composite material was prepared according to the same procedure as in Example 1. The material properties are shown in Table 1.

Example 6

The procedure is as in Example 5 except that 23.85 kg of a mixture of metal salts of fatty acids and fatty acid amides (Struktol Polydis TR 016) is used instead of titanate. The material properties are given in Table 1.

Comparative Example 1

The procedure is as in Example 5, except that no 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole is added to the aqueous solution so that the aqueous solution contains only titanate. The material properties are given in Table 1.

Comparative Example 2

The procedure is as in Example 6, except that no 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole is added to the aqueous solution so that the aqueous solution contains only a mixture of metal salts of fatty acids and fatty amides acids. The material properties are given in Table 1.

Example 7 kg of an aqueous suspension of magnesium hydroxide having a dry matter content of 7.5% by weight, in which the magnesium hydroxide has a crystal size determined by the X-ray powder diffraction method in the < aspect ratio 4.65: 1, deformation in <004> direction

- 19 3.96. ΙΟ ' ³ , deformation in <110> direction 1.92. ΙΟ ' ³ , dso = 0,98 μιη and Sbet = 9,6 m ² / g, are mixed at room temperature with 4 kg of aqueous ammonia solution containing 0,0225 kg of technical mixture of higher fatty acids, mainly palmitic acid and acid stearic acid and 0.5 kg of an aqueous solution of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole containing 2,25. 10 * ⁴ kg of active substance. The mixture was stirred for 30 minutes and after filtration dried at 110 ° C to constant weight.

A Brabender mixer prepared a composite material according to the following recipe: 100 wt. parts by weight of Levapren 400 (EVA copolymer, 40% VAC, Bayer A.G.), 150 parts by weight, parts treated with magnesium hydroxide, 20 parts by weight; parts of carbon black FEF, 6 parts, parts dioctyl sebacate (plasticizer), 8 parts, parts Perkadox BC 40K (peroxide), 1.5 parts by weight parts of Dusantox 86 (antioxidant) and 2 wt. TAIC parts. The results are shown in Table 2.

Comparative Example 3

The procedure was as in Example 7, except that the addition of an aqueous solution of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole was not used. The material properties are given in Table 2.

EXAMPLE 8 kg of an aqueous suspension of magnesium hydroxide having a dry weight of 7.5%, in which magnesium hydroxide has the same properties as described in Example 7, is mixed at room temperature with 0.68 kg of an aqueous solution containing 0.034 kg of gamma-aminopropyltriethoxysilane and 0 5 kg of an aqueous solution containing 4.5. 10 ^-4 kg of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole. The mixture was stirred for 30 minutes and after filtration dried in an oven at 110 ° C to constant weight.

In a Brabender kneading machine a polymer composite material is prepared at a temperature of 160 ° C according to the following recipe: 9.66 mass, parts of Escorene LL

20 1004 YB (LLDPE), 29.00 wt. % of parts of Escorene Ultra UL 00226 (EVA copolymer with 26% VAC content), 61.10 wt. parts of surface-treated magnesium hydroxide, 0.04 wt. parts of Triganox (peroxide) and 0.20 wt. parts of Irganox 1010 (antioxidant). The material properties are given in Table 2.

Comparative Example 4

The procedure was as in Example 8, except that the addition of an aqueous solution of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole was not used. The material properties are given in Table 2.

Example 9 kg of an aqueous magnesium hydroxide slurry having a dry matter content of 7.5%, in which magnesium hydroxide has the same properties as described in Example 7, is mixed at room temperature with 4 kg of an aqueous ammonia solution containing 0.0225 kg of a technical mixture of higher fatty acids. and 0.68 kg of an aqueous solution containing 0.034 kg of vinyl tris (2-methoxyethoxysilane). The mixture was stirred for 30 minutes and after filtration dried in an oven at 110 ° C to constant weight.

The preparation of the polymer composite material is as described in Example 8. The material properties are shown in Table 2.

Example 10

The procedure is as in Example 9 except that an additional 0.5 kg of an aqueous solution containing 1.05 is added to the aqueous magnesium hydroxide suspension. 10 * ⁴ kg of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole. The material properties are given in Table 2.

Example 11

- 21 To 8000 kg of a magnesium hydroxide suspension in an aqueous medium containing 320 kg of magnesium hydroxide is added 800 kg of a solution containing 4.8 kg of titanium IV bis (butylmethyl) pyrophosphate-0 in an addition compound with 2-N, N-dimethylamino 2-methylpropanol, 4.8 kg of zinc stearate, and 1.6.10 kg of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole. The mixture is subjected to a hydrothermal treatment at 140 ° C and a pressure of 0.7 MPa for 15 minutes. After cooling to 60 ° C and filtration, the product is washed with water and dried at 110-130 ° C. The polymer composite material was prepared by the same procedure as in Example 1. The material properties are shown in Table 1.

EXAMPLE 12 kg of dry powdered magnesium hydroxide with the same properties as in Example 1 are placed in a high-speed fluidic mixer and together with 149.2 g of titanium IV 2,2 (bis-2-propenolate methyl) butanolate, tris (dioctyl) pyrophosphate-0 ground inert carrier, 750 g of a mixture of metal salts of fatty acids and fatty acid amides (Struktol Polydis TR 016) and 30 g of 2,2 '- (1,2-ethylenedildi-4, 1-phenylene) bisbenzoxazole are stirred at 130 ° C. After cooling, the product obtained is used to prepare the polymer composite material in the same manner as in Example 1. The properties of the material are shown in Table 1.

Example 13

The procedure was as in Example 3 except that 19.1 kg of titanium IV 2-propanoate, tris (dioctyl) phosphate-0 was used as the titanate, instead of 11.92 kg of the structure, only 2.4 kg of the structure was used and aromatic compound with conjugated double bonds was used 20 g of 1,4-diaminoanthraquinone. The polymer composite material was prepared in the same manner as Example 1. Material properties are shown in Table 1.

Example 14

The procedure is the same as in Example 3 except that an aqueous solution of only the titanate addition compound and the bisbenzoxazole derivative is added to the aqueous magnesium hydroxide suspension. After drying, the product obtained is uniformly mixed with 10.3 kg of a mixture of powdered metal salts of fatty acids and fatty acid amides (Struktol Polydis TR 016). The polymer composite material was prepared in the same manner as in Example 1. The material properties are shown in Table 1.

Example 15

The procedure is the same as in Example 3 except that 2500 kg of aqueous solution contains 2.35 kg of titanium IV bis (dioctyl) pyrophosphate-O, oxoethylenediolate in the addition compound with 2-N, N-dimethylamino-2-methylpropanol, 2. 35 kg of stearic acid and 0.08 kg of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole. The polymer composite material was prepared as in Example 1. The material properties are shown in Table 1.

Example 16

The procedure of Example 9 was followed except that 4.5 g of a technical mixture of higher fatty acids and 6.75 g of gamma-aminopropyltriethoxysilane were used. The polymer composite material was prepared by the same procedure as in Example 8. The material properties are shown in Table 2.

Example 17

The procedure was as in Example 16, except that an additional 0.5 kg of an aqueous solution of 2,2 '- (1,2-ethylenedildi-4,1-phenyl) bisbenzoxazole containing 2.25 was used. 10 ^-4 kg of active substance. The material properties are given in Table 2.

Example 18

The procedure was as in Example 7 except that only 67.5 g of higher fatty acids were used.

- 23 Polymeric composite material is prepared according to the recipe: 100 wt. parts by weight of Buna AP 437 (EPDM terpolymer), 200 wt. parts by weight of surface-treated magnesium hydroxide, 1 wt. % of gamma-aminopropyltriethoxysilane, 40 wt. parts of bearing oil (plasticizer), 40 wt. parts of carbon black FEF, 10 wt. parts by weight Perkadox BC 40K (peroxide), 1.5 wt. parts of Dusantox 86 (antioxidant) and 1.8 wt. TAIC parts. The material properties are given in Table 2.

Example 19

The procedure was as in Example 18, except that an additional 0.5 kg of an aqueous solution of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole containing 2.25 was used. 10 * ⁴ kg of active substance. The polymer composite material was prepared as in Example 18. The material properties are shown in Table 2.

Example 20

The procedure was as in Example 18 except that only 9.0 g of higher fatty acids were used.

The polymer composite material was prepared according to the same recipe as in Example 18 except that 6 wt. parts of gamma-aminopropyltriethoxysilane. The material properties are given in Table 2.

Example 21

The procedure was as in Example 20, except that an additional 0.5 kg of an aqueous solution of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole containing 2.25 was used. ⁴ kg of active substance. The polymer composite material was prepared by the same procedure as in Example 20. The material properties are shown in Table 2.

Example 22

The same procedure as in Example 3 is followed except that the magnesium hydroxide has a crystal size in < 004 >

-24-.

deformation in <004> direction 1.96. 10 ' ³ , deformation in <110> direction 3.12. 10 ^-3 , d 50 = 1.35 µm and Sbet = 20.6 m ² / g. The material properties are given in Table 1.

Example 23

The surface-treated magnesium hydroxide was prepared in the same manner as in Example 7 except that 4 kg of an aqueous ammonia solution containing 67.5 g of a mixture of higher fatty acids, 0.68 kg of an aqueous solution containing 11.25 g were used. gamma-aminopropyltriethoxysilane and 0.5 kg of an aqueous solution of 2,2 '- (1,2-ethylenedildi-4,1-phenylene) bisbenzoxazole containing 2.25. 10 ^-4 kg of active substance. The polymer composite material was prepared according to the same recipe as in Example 18, except that gamma-aminopropyltriethoxysilane was no longer added. The material properties are given in Table 2.

Table 2 thermoplastic content h. ductility elongation,% hardness elasticity

substance magnesium. % MPa 1) 2) Sh A 5) % 6) Example 7 EVA • 52,2_ · · original values 7.46 485 83 24 V-0 after aging 3) 7:41 435 85 24 V-0 Por. Example 3 EVA 52.2 original values_ 7.06 439 80 20 V-0 after aging 3) 6.37 385 81 20 V-1 Example 8 PE + EVA 61.1 original values 8.09 425 86 20 V-0 after aging 3) 7.98 405 86 20 V-0 Por. Example 4 PE + EVA 61.1 WITH original values ¹ 7.54 401. 81 18 V-0 after aging 3); and 6.82 350 82 18 V-1 Example 9 PE + EVA ! 61.1 1 1 1 and 1 original values 1 8.05 454 ' 87i > 22 V-0 after aging 3) ! 7.89 420 86 22 V-0 Example 10 PE + EVÁ 61.1 original values 8.34 465 92 23 V-0 after aging 3) 8.08 450 90 . 23 V-0 Example 16 PE + EVA 61.1 original values 7.86 416 84 21 V-0 after aging 3) 7.55 400 84 21 V-0 Example 17 PE + EVA 61.1 original values T 7.95 422 86 21 V-0 after aging 3) 7, 88 412 85 21 V-0 Example 18 EPDM 50.9 original values 6.87 560 76 32 V-0 after aging 4) 6.7 520 76 32 V-0 Example 19 EPDM 50.9 original values 6.65 637 76 34 V-0 after aging 4) and 6.6 611th 76 34 V-0 Example 20 EPDM 1 1 50.9 1 I I original values 7.05 527 · 76 30 V-0 after aging 4) 6.98 517 76 _30 V-0 Example 21 EPDM 50.9 original values 7.21 545 77 33 V-0 after aging 4) 7.14. • 545 77 33 in-b 1

1) The tensile strength y of tear according to STN 62 143 & Podfe STN 34 7470 requires a minimum strength of 6.5 MPa for EVA cable cojolymers, a tolerance of +/- 30% is allowed after aging; for cable EPP rubbers the required minimum strength is 5 MPa, after aging a minimum of 4.2 MPa with a tolerance of +/- 25%.

2) Ductility according to STN 621436. According to STN 34 7470, a minimum ductility of 200% is required for cable copolymers ÉVÄ, a tolerance of +/- 30% is allowed after aging; for duvet ÉPĎM__ rubbers, a minimum elongation of 200% is required, a tolerance of +/- 25% is allowed after aging.

3) Geer aging, 10d / min _; ____________

4) Geer age, 7 days / 10 ° C; _____

5) Hardness according to SCN 621431 __ ~~

6) UL 94 (3)

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Claims (34)

PATENT CLAIMS CLAIMS 1. Polymer composite having increased fire resistance, characterized in that it comprises 25 to 75 parts by weight, preferably 35 to 60 parts by weight of thermoplastic material (per 100 parts by weight of polymer composite material) and 75 to 25 parts by weight. preferably 65 to 40 parts by weight of magnesium hydroxide (per 100 parts by weight of polymer composite material), the surface of which is treated with a surfactant and / or which is uniformly mixed with the surfactant. The polymer composite having increased fire resistance according to claim 1, characterized in that the magnesium hydroxide consists of agglomerates of crystals having diameters of all particles smaller than 4.0 µm, 50% of the particles having diameters smaller than 1.4 µm and the specific surface area determined by the BET method is less than 25 m ² / g. The fire-resistant polymer composite material according to claims 1 and 2, characterized in that the magnesium hydroxide is a powder crystalline product having a crystal size as determined by the X-ray powder diffraction method in the direction <004> greater than 150 A * and less than 500 A * an aspect ratio ranging from 2 to 5, a deformation in <004> up to a maximum of 4.2.10 ^-3 and a deformation in <110> up to a maximum of 3.0.10 ^-3 . ¹ 1 The flame-resistant polymer composite material according to claims 1 to 3, characterized in that the surfactant is a mixture of titanate and metal salts of fatty acids and / or fatty acid amides or a mixture of higher fatty acids and titanate, wherein the amount of surfactant is 0. . 5 to 4.0 parts by weight, preferably 1.5 to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide. - 26 5. The flame-resistant composite material of claims 1 to 3, wherein the surfactant is a mixture of titanate, metal fatty acid salts and / or fatty acid amides and an aromatic organic compound with at least three conjugated double bonds or a mixture. higher fatty acids, titanate and an aromatic organic compound with at least three conjugated double bonds, wherein the amount of surfactant is 0.5 to 4.0 parts by weight, preferably 1.5 to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide. 6. The flame-resistant composite material of claim 4, wherein the amount of titanate in the surfactant is 0.05 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight per 100 parts by weight. magnesium hydroxide. Polymeric composite material with increased fire resistance according to claim 5, characterized by. in that the amount of titanate in the surfactant is 0 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight, per 100 parts by weight of magnesium hydroxide. The flame-retardant composite material according to claim 4, characterized in that the amount of metal salts of fatty acids and / or fatty acid amides in the surfactant is 0.05 to 3.5 parts by weight, preferably 1.0 to 3.5 parts by weight. 2.5 parts by weight per 100 parts by weight of magnesium hydroxide. 9. The flame-resistant composite material of claim 5, wherein the amount of metal salts of fatty acids and / or fatty acid amides in the surfactant is from 0 to 3.5 parts by weight, preferably from 1.0 to 2 parts. 5 parts by weight per 100 parts by weight of magnesium hydroxide. The flame-resistant polymer composite material according to claims 1 to 3, characterized in that the surfactant is a mixture of higher fatty acids and silane, wherein the amount of surfactant may be 0.5 to 4.0 parts by weight, preferably 1, by weight. 0 to 3.0 parts by weight per 100 parts by weight of magnesium hydroxide. 11. The flame-resistant polymer composite material of claims 1-3, wherein the surfactant is a mixture of higher fatty acids, silane and an aromatic organic compound with at least three conjugated double bonds, wherein the amount of surfactant is 0.5 to 4. 1.0 parts by weight, preferably 1.0 to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide. Polymer composite material with increased fire resistance according to claim 10, characterized in that the amount of silane in the surfactant is 0.3 to 3.0 parts by weight, preferably 0.5 to 2.0 parts by weight, per 100 parts by weight of magnesium hydroxide. Polymer composite material with increased fire resistance according to claim% 11, characterized in that the amount of silane in the surfactant is 0 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight, per 100 parts by weight of magnesium hydroxide. 14. The fire-resistant polymer composite material according to claim 4, wherein the amount of higher fatty acids in the surfactant is 0.05 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight per 100. parts by weight of magnesium hydroxide. 15. The flame-resistant polymer composite material according to claim 5all, wherein the amount of higher fatty acids in the surfactant is 0 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight per 100 parts by weight. magnesium hydroxide. 16. The flame-resistant polymer composite material according to claim 5all, wherein the amount of the aromatic organic compound with at least three conjugated double bonds is 0.002 to 0.1 parts by weight, preferably 0.005 to 0.05 parts by weight per 100 parts by weight. parts of magnesium hydroxide. I Magnesium hydroxide, the surface of which is treated with a surfactant, characterized in that the surfactant is a mixture of titanate and metal salts of fatty acids and / or fatty acid amides, or a mixture of higher fatty acids and titanate, the amount of surfactant being 0.5 up to 4.0 parts by weight, preferably 1.5 to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide. 18. Magnesium hydroxide, the surface of which is treated with a surfactant, characterized in that the surfactant is a mixture of titanate, metal salts of fatty acids and / or fatty acid amides and an aromatic organic compound with at least three conjugated double bonds or a mixture of higher fatty acids; titanate and an aromatic organic compound with at least three conjugated double bonds, wherein the amount of surfactant is 0.5 to 4.0 parts by weight, preferably 1.5 to 3.0 parts by weight, per 100 parts by weight of magnesium hydroxide. Magnesium hydroxide, the surface of which is treated with a surfactant, according to claim 17, characterized in that the amount of titanate in the surfactant is 0.05 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight per 100 parts by weight of magnesium hydroxide. Magnesium hydroxide, the surface of which is treated with a surfactant, according to claim 18, characterized in that the amount of titanate in the surfactant is 0 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight, per 100 parts by weight. magnesium hydroxide. - 29 Magnesium hydroxide, the surface of which is treated with a surfactant according to claim 17, characterized in that the amount of metal salts of fatty acids and / or fatty acid amides in the surfactant is 0.05 to 3.5 parts by weight, preferably 1.0 parts by weight up to 2.5 parts by weight per 100 parts by weight of magnesium hydroxide. Magnesium hydroxide, the surface of which is treated with a surfactant according to claim 18, characterized in that the amount of metal salts of fatty acids and / or fatty acid amides in the surfactant is 0 to 3.5 parts by weight, preferably 1.0 to 2 parts by weight. 5 parts by weight per 100 parts by weight of magnesium hydroxide. Magnesium hydroxide, the surface of which is treated with a surfactant, characterized in that the surfactant is a mixture of higher fatty acids and silane, wherein the amount of surfactant may be 0.5 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight per 100 parts by weight of magnesium hydroxide. 24. A magnesium hydroxide surface-treated with a surfactant, characterized in that the surfactant is a mixture of higher fatty acids, silane and an aromatic organic compound with at least three conjugated double bonds, wherein the amount of surfactant is 0.5 to 4.0 parts by weight, preferably 1.0 to 3.0 parts by weight per 100 parts by weight of magnesium hydroxide. Magnesium hydroxide, the surface of which is treated with a surfactant according to claim 23, characterized in that the amount of silane in the surfactant is 0.3 to 3.0 parts by weight, preferably 0.5 to 2.0 parts by weight, per 100% by weight parts of magnesium hydroxide. Magnesium hydroxide, the surface of which is treated with a surfactant according to claim 24, characterized in that the amount of silane in the surfactant is 0 to 3.0 parts by weight, preferably 0.4 to 1.5 parts by weight, per 100 parts by weight of hydroxide magnesium. Magnesium hydroxide, the surface of which is treated with a surfactant, according to claims 17 and 23, characterized in that the amount of higher fatty acids in the surfactant is 0.05 to 3.5 parts by weight, preferably 1 part by weight. 0 to 2.5 parts by weight per 100 parts by weight of magnesium hydroxide. Magnesium hydroxide, the surface of which is treated with a surfactant, according to claims 18 and 24, characterized in that the amount of higher fatty acids in the surfactant is 0 to 3.5 parts by weight, preferably 1.0 to 2.5 parts by weight per 100 parts by weight of magnesium hydroxide. Magnesium hydroxide, the surface of which is treated with a surfactant, according to claims 18 and 24, characterized in that the amount of aromatic organic compound with at least three conjugated double bonds is 0.002 to 0.1 parts by weight, preferably 0.005 to 0, 05 parts by weight per 100 parts by weight of magnesium hydroxide. Magnesium hydroxide according to claims 17 to 29, characterized in that the magnesium hydroxide consists of crystal agglomerates having 50% particles with diameters less than 1.4 µm, 100% particles with diameters less than 4.0 µm and * BET specific surface area less than 25 m / g. Magnesium hydroxide according to claim 30, characterized in that the magnesium hydroxide is a powder crystalline product having a crystal size as determined by powder diffraction X-ray diffraction in the direction <004> of greater than 150 Å and less than 500 Å, an aspect ratio in the range from 2 to 5, a deformation in <004> in the direction of maximum 4.2.10 ' ³ and a deformation in <110> in the direction of maximum 3.0.10' ³ . Process for the preparation of the surface-treated magnesium hydroxide according to claims 17 to 31, characterized in that the surfactant or part thereof is added as a solution or emulsion to the aqueous magnesium hydroxide slurry, mixed and the water is separated to form the surface-treated magnesium hydroxide. . A process for the preparation of a surface-treated magnesium hydroxide according to claims 17 to 31, characterized in that the mixture of the magnesium hydroxide and the surfactant or part thereof is stirred in an agitator at an elevated temperature at which the surfactant is uniformly applied to the surface. then the product is cooled. A process for the preparation of a surface-treated magnesium hydroxide according to claims 17 to 31, characterized in that the surfactant or part thereof is added to the aqueous magnesium hydroxide suspension, the suspension is then hydrothermally treated at a temperature of 110 to 200 ° C, a pressure of 0.2 to 1.6 MPa, cooled and water was separated to give the surface-treated magnesium hydroxide.