Polyolefin composition, inhibiting inflammation, low smoke generation and toxicity

 

(57) Abstract:

The invention relates to the development of materials for coating electrical wires and cables and materials for paper Wallpaper, manufacture and use are safe. Polyolefin composition, inhibiting inflammation with low smoke emission and toxicity, contains 100 weight parts of the polyolefin resin, 80-150 parts by weight of inhibitor ignition and 2-10 weight parts of stannate zinc as excipients inhibitor of ignition. In inhibiting the ignition of the polyolefin composition as an inhibitor of ignition preferably uses a sophisticated HYDR oxide of the metal. 3 C.p. f-crystals, 6 PL.

The invention relates to a polyolefin compound having a low smoke generation and toxicity, and specifically to the vast blameworthy material with low smoke emission and toxicity, for use as a material for coating electrical wires and cables or as a matter - component paper Wallpaper.

Description of the prior art

As polyolefine resins are mostly flexible, have excellent insulating svobodov and component material paper for Wallpaper, in particular it was used in large quantities as a material for coating electrical wires. But because of serious fires in the past when used as the material covering the electrical wiring requirements for the suppression of ignition are rising, and have been developed and are currently used in nuclear cable material and various other types of suppressing ignition of materials for cables. Such cables, however, produce large amounts of smoke in case of fire, and this makes it difficult evacuation and extinguishing the fire, when the fire occurs in an enclosed space such as an underground shopping Mall, subway or plane, possibly causing a secondary accident. There is therefore a need to develop a material with low smoke emission, which results in significantly less smoke in case of fire. Furthermore, in addition to the suppression of the ignition there is a requirement to reduce the emission of toxic gas, such as carbon monoxide (co) carbon during combustion.

Mainly high-molecular substances are lit so that the gas in thermal decomposition reacts with oxygen, and if the heat of combustion at this time enough, this also causes the formation of drugee three factors: 1) the presence of a combustible material, 2) oxygen, and (3) maintaining the temperature (thermal energy). The absence of at least one of these three factors leads to the cessation of burning.

Among the polyolefin resins, polyethylene, polypropylene and their copolymers, such as ethylenevinylacetate copolymer (hereafter called EVA resin) and ethylenically copolymer (hereafter called EEA resins) are widely used as molding materials, film materials, and others. And as a material for coating electrical wires they have good electrical and mechanical properties, good processing and is widely used as insulation and coating materials. However, the polymers presented in such a polyethylene and its copolymers with properties easy flammable due to their chemical structure. And to make such resins, suppressing inflammation, you need to add a large number of overwhelming ignition of the substance and support for him, substances and the like, for example at least 180 parts by weight of the overwhelming ignition of the substance per 100 parts by weight of this resin. In addition, compounds that inhibit Wopla out many shortcomings in the practical application.

On the other hand, the PVC resin is also widely used as a material for coating electrical wires and cables and material component Wallpaper paper. This polyvinylchloride resin contains chlorine and is itself overwhelming inflammation. Therefore, it is widely used as a material for coating electrical wires and material for Wallpaper. In particular, this polyvinylchloride resin has the inhibitor of ignition, reinforced by adding a combination of substances for stopping the reaction with radicals (additive on the basis of halogen and so on), substances for discontinuation of oxygen (for example, substances that suppress inflammation, based on bromine, represented by substances that inhibit the ignition on the basis of halogen, nitrogen and phosphorus) and substance to absorb heat to reduce the temperature (aluminum hydroxide, magnesium hydroxide, zinc borate, and so on). In particular, a commonly used inhibitor of ignition - inhibitor ignition on the basis of halogen was widely used in combination with antimony trioxide. But the inhibitor of ignition, with this combination, partially decomposed in the process of its production and highlights the halogen gas that corrodes the equipment DL the th in producing large amounts of smoke, including HCl gas, and toxic gas in case of fire.

It was therefore urgently needed to develop materials for coating electrical wires and cables and materials for paper Wallpaper, manufacture and use are safe.

To resolve the above shortcomings, it was necessary to develop an inhibiting ignition of the material having excellent mechanical properties, which contains mainly the above-mentioned halogen-free resin-based polyolefin and does not produce HCl gas.

The invention was made in view of the above problems and has as its purpose the obtaining of inhibiting inflammation polyolefin compounds suitable as the material for coating electrical wires and material for Wallpaper that has improved mechanical properties and properties as an inhibitor of inflammation, through decreasing adding material that inhibits inflammation, specifically hydroxide, to the extent possible, halogen free material based on the polyolefin resin.

The vast majority blameworthy polyolefin composition having low smoke generation and toxicity of this invention is, that the above-mentioned composition contains from 2 to 10 weight parts of stannate zinc as the vast blameworthy excipients.

In the above polyolefin composition, the inhibitor blameworthy may be hydroxides of metals of different types, such as aluminum hydroxide, magnesium hydroxide, and a mixture of complex metal hydroxide; complex metal hydroxide is particularly preferred because it becomes a function of the vast flame of a substance by the absorption of heat when water is produced by the decomposition of complex metal hydroxide during the combustion and the effect of catalysis accelerate carbonization of the metal in the complex hydroxide of the metal. This complex hydroxide of the metal complex hydroxide of a metal having a chemical composition expressed by the formula Mg1-xM+x2(OH)2in which M+2is at least one selected from the group of ions divalent metals Mn+2, Fe+2, Co+2, Ni+2, Cu+2and Zn+2and x is a numerical value satisfying 0.001 x 0,9.

As the polyolefin resins are polyethylene, polypropylene and their copolymers, and among such copolymers person"ptx2">

Stannate zinc as mentioned above the vast ignition auxiliary substances is expressed by the formula ZnSnO3and thermally decomposed at high temperature, which is reflected by the following formula reaction:

ZnSnO3Zn2SnO4+ SnO2(580 - 800oC).

It was found that when the above-mentioned stannate zinc is added to the PVC resin, the quantity and speed of reaction of the smoke and produced by resin CO is significantly reduced in comparison with commonly used tin trioxide. With this mechanism, the zinc contained in the chemical composition, serves as a catalyst for the reaction of dehydrohalogenation resin to accelerate the formation of carburized layer and suppress the production of smoke, and an endothermic reaction due to evaporation the amount of water that is released during thermal decomposition, reduces the combustion temperature. In addition, it is clear that platypodinae effect of the gas phase due to partial evaporation of zinc (Zn) and tin (Sn) at 550oC or more effective for reducing CO, and significant effects can be obtained by using synergies between the condensed layer by formation of a carbonized layer is fully attributed to halogen-free resin, namely, the resin is not based halogen, and these effects are not expected.

The inventors conducted dedicated to this research and found that the above effects can be obtained by using dehalogenases resin, when stannate zinc combined with platypetalum substance on the basis of the metal hydroxide.

This stannate zinc is used in combination with inorganic inhibitor of ignition, such as metal hydroxides. Specifically, when the metal hydroxides represented by aluminum hydroxide and magnesium hydroxide or mixture of hydroxides of metals and complex metal hydroxide are used in combination, the oxygen index can be improved without lowering physical properties, and rate of combustion in the test of fire resistance can be reduced. In addition, adding a small amount of stannate zinc can significantly reduce the above-mentioned additive metal hydroxide, making it possible to achieve the required properties platypodinae a small amount of a metal hydroxide. Thus, the composition can be improved in physical properties, namely mechanical and electrical properties.

When burning the metal hydroxide IU in the range from 80 to 150 weight parts per 100 weight parts of resin. When it is less than 80 weight parts, one cannot expect a very good platypodinae effect, and when it exceeds 150 parts by weight of the workability of the composition and mechanical properties of the product is far worse. More preferably, the metal hydroxide is added in the range from 100 to 140 weight parts.

The number of stannate zinc under overwhelming fire polyolefin compositions according to this invention is in the range from 2 to 10 weight parts per 100 weight parts of resin. When it is less than 2 weight parts, it is impossible to obtain a sufficient suppressing ignition effect, and when it exceeds 10 weight parts, it is impossible to obtain a dynamic thermal stability required in the production of compositions and processing in floor wiring, and basic physical properties after processing becomes worse. Preferably the number of stannate zinc is in the range from 2 to 5 weight parts.

When stannate zinc together with metal hydroxide is used as inhibitors of ignition in relation to resin-based polyolefin, properties suppression ignition combustion of the composition based on the polyolefin can be the value of the improved ability of the composition to the processing and mechanical and electrical properties after processing.

Examples 1-4.

To 100 weight parts of EEA with the rate of melting 1,2 and content of the acrylate equal to 15 mol %, was added to 0.2 weight parts of an antioxidant and a complex metal hydroxide as the vast ignition of the substance expressed by a chemical formula of Mg1-xM+x2(OH)2in which M+2is at least one selected from the group divalent metal ions Mn+2, Fe+2, Co+2, Ni+2, Cu+2and Zn+2and x is a numerical value satisfying the condition 0.001 x 0,9; stannate zinc as excipients overwhelming ignition means and coal as a coloring agent to provide stability to the environment in amounts shown in table 1, to obtain the tested compositions.

The comparison examples 1 to 4.

As examples of the comparison were obtained in the same manner as in examples 1 to 4, the samples of compositions containing the same number of components, which are shown in table 1, except that no added stannate zinc as excipients overwhelming ignition means.

These compositions were mixed in smashits.com.

On laminar samples was determined by oxygen index according to the method of JIS K7201, ultimate tensile strength, elongation and volume resistivity.

With the use of these compositions as a material for coating produced 600V Poperechnaya cables with polyethylene insulation and tested for combustion in a vertical trays according to the method of JIS C3521. They were two sizes, one 3.5 mm2and the other 14 mm2. For each size were tested by two cables.

Table 2 shows the results of the tests.

Table 2 shows that, when added stannate zinc as excipients overwhelming ignition means to the complex hydroxide of the metal as an inhibitor of ignition of this invention, resistance to ignition is improved. In particular, when using a complex metal hydroxide, passing tests in a vertical chute requires its amount equal to 150 weight parts per 100 weight parts of the polyolefin resin. However, this invention can provide the same level of properties suppression of ignition by adding 3 weight parts of stannate zinc, even when the complex hydroxide of a metal from the resin during combustion due to the effect of multiplying the catalytic action of a complex metal hydroxide and stannate zinc. And also greatly improves the mechanical strength. In addition, the specific volume resistance is maintained at a high level of 1015.

When comparing sample 2 and sample comparison 2 when tested in the vertical chute, it is obvious that adding stannate zinc as an aid reduces the burning rate.

Examples 5 to 8.

In examples 5 through 8 for receiving the tested compositions were used EEA resin, 130 parts by weight of magnesium hydroxide having as a main component of Mg(OH)2used instead of a complex metal hydroxide expressed by the chemical formula Mg1-xM+x2(OH)2used in examples 1 to 4, 130 parts by weight of a complex metal hydroxide expressed by the chemical formula Mg1-xM+x2(OH)2used as an inhibitor of inflammation, and stuns zinc used in varying amounts as shown in table 3. The tests were made in the same manner as in examples 1 to 4.

The comparison examples 5 to 6.

In the comparison examples 5 and 6 compositions prepared using 130 parts by weight of the complex hydroxide is and ignition and stannate zinc in varying amounts, as shown in table 3, outside the limits specified in this invention, were tested. But, when used 15 weight parts of stannate zinc, it was very difficult to obtain a coating of electrical wires. Test methods were the same as in examples 5 to 8.

Table 4 shows the results of the tests. In particular, when as an inhibitor of ignition used the Mg(OH)2found that the properties of the suppression of ignition slightly improved, but it wasn't noticeable effect unlike the case of the use of complex metal hydroxide expressed by the chemical formula Mg1-xM+x2(OH)2. And the specific volume resistance was at a low level, equal to 5.3 x 1013.

When stannate zinc is added in the quantity is less than the limit specified in the invention, the properties of the suppression of ignition improve unsatisfactory, and when it is added in excess of the specified limit, the properties of the suppression of ignition also won't improve. In addition, the mechanical properties for practical use is also very bad.

Examples 9 through 11.

As the test sample used low-density polyethylene (hereafter nativement, containing 0.2 weight parts of an antioxidant, was added to complex metal hydroxides expressed in a chemical formula Mg1-xM+x2(OH)2and Mg(OH)2as inhibitors of ignition in amounts shown in table 5, and were added 3 weight parts of stannate zinc as excipients inhibitor of ignition. They were mixed in the mixer was plastifitsirovanie using dvuhpaltsevoe mill and molded by pressing at the plate. Thus gained the lamellar samples for testing. The samples were measured ultimate tensile strength and elongation. In addition, they determined the characteristics of combustion UL-94VE.

The comparison examples 7 and 8.

For sample comparison procedure of examples 9 to 11 were as follows, except that added 150 parts by weight of complex metal hydroxides, expressed by the chemical formula Mg1-xM+x2(OH)2and Mg(OH)2as inhibitors of ignition, and stannate zinc as excipients inhibitor of ignition was not added.

Table 6 shows the results of examples 9 to 11 and comparison examples 7 and 8.

It was found the ignition was less than in the comparison samples 7 and 8, as well as when used EEA resin.

On the other hand, the specimen 7 and 8, which were not added stannate zinc as excipients inhibitor of ignition, it was found that the mechanical properties were significantly reduced, even when added 150 parts by weight of complex metal hydroxides, expressed by the formula Mg1-xM+x2(OH)2and Mg(OH)2as an inhibitor of ignition in order to pass the test on combustion.

As described above, in order to have passed the test of fire resistance according to UL-94VE, to 100 weight parts of the polyolefin resin need to add 150 parts by weight of Mg(OH)2or a complex metal hydroxide.

But according to this invention added 3 weight parts of stannate zinc, to make possible the reduction of the inhibitor of ignition, which you want to add essential. Accordingly, the mechanical strength is significantly improved.

In particular, when as an inhibitor of ignition using a complex metal hydroxide and stannate zinc is used as excipients for inhibitor ignition, Ude is, than in the case when using Mg(OH)2and stannate zinc. And it was found that the use of complex metal hydroxide and stannate zinc gave a sufficient effect in relation to the properties of suppression of ignition and other properties.

Adding a metal hydroxide as an inhibitor of ignition and stannate zinc as an auxiliary suppressing ignition of the substance to a polyolefin resin containing no halogen, delay time of ignition and can contribute to the achievement of low smoke generation and toxicity. At the same time significantly reduces the amount of metal hydroxide, and you can avoid significant deterioration of mechanical properties associated with the addition of a large amount of hydroxide.

1. Polyolefin composition, inhibiting inflammation, low smoke generation and toxicity, including polyolefin, an inhibitor of ignition and auxiliary substance is an inhibitor of inflammation, characterized in that as an inhibitor of ignition it contains a complex metal hydroxide of the General formula Mg1-xMx(OH)2where M is at least one divalent metal selected from the group consisting of Mn, Fe, Co, Ni, is eating the ratio of the components, wt.h.:

The polyolefin - 100

Inhibitor of ignition - 80 - 150

Excipient inhibitor of ignition - 2 - 10

2. The composition according to p. 1, characterized in that the polyolefin contains at least one polymer selected from the group consisting of polyethylene, polypropylene, copolymer of ethylene and acrylate, and copolymer of ethylene with vinyl acetate.

3. The composition according to p. 2, characterized in that it further comprises less than 3 wt.h. coal to 100 wt.h. song.

4. The composition according to PP.1 to 3, characterized in that it has an oxygen index equal to 26 or more.

 

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