CS268272B1 - Linear polyethylene based Smis - Google Patents

Abstract

The invention relates to a linear polyethylene-based emulsion containing 8 to 12 parts by weight of carbon black per 100 parts by weight of linear polyethylene and stabilized with 0.05 to 0.3 parts by weight of an organic phosphate-based stabilizer and 0.1 to 0.75 parts by weight of a coating agent stabilizer.

Description

The invention ββ relates to a mixture based on linear polyethylene in an antistatic treatment.

The antistatic treatment of polyethylene ae is achieved most initially by the addition of carbon black and a large specific surface area. This material is used mainly for the production of transport containers for flammables and explosives, which must be avoided by the possibility of the formation of eggs caused by the discharge of electrical electricity. For the same reason, entlethetic treatment is required in the case of pipes and articles intended to be installed in potentially explosive atmospheres. The discharge of static electricity can also damage sensitive electronic components. According to ČSN No. 332 030, in order to suppress charging with athletic electricity, it is necessary to reduce the surface electrical resistance of the material to a value of less than 10 Λ. These low values of electrical resistance cannot be achieved by the advent of conventional antiatatics. Soot is a known means of annihilating the electrical resistance of plastics. It is known that the most effective type of eosion in terms of annihilating the electrical resistance of the sheet 2 - 1 is eezo with a specific surface area of BET 500 to 1,200 m .g. Due to the euro wool used and the method of production, these eaza eločonlny contain vanadium, nickel, iron, iron and other elements. The obeah of atopic elements in eszich is the cause of their chemical activity, which affects the thermooxidation behavior and editation of polyethylene.

The presence of special stabilizers capable of suppressing the thermal oxidation of the polymer is necessary to achieve good processable properties of the polyethylene surrounding the eaza. The well-known yes, e.g. the use of p-phenylenedlamine derivatives or dl phenylenemide. In some cases, however, their function as ethellers fails.

These disadvantages are solved on the basis of linear polyethylene and surface el. with a resistance of less than 1⁄2 and an internal resistance of less than 100 Λ.cm, consisting of 100 wt. 2 N «1Χ. 0.6 and at 190 ° C / 212 N mln. 4 g / 10 mln. and 8 to 12 parts by weight and a specific BET surface area of min. 800 m 2 / g, the pH of the aqueous extract has a content of 6 to 8.5 and an ash content of max. 1 to 0.75 parts by weight. The design of the use of these stabilizers was based on the fact that it was found that the function of the emulsifier was similar to the pH of the aqueous extract. Compounds based on organic foams have not proved to be suitable for the establishment of linear polyethylene with aesia, the aqueous extract of which has been reacted with hydrogen. The increase in the pH value of the aqueous leachate of carbon black occurs when the technological conditions of the production of carbon black change. The increase in pH is usually accompanied by a reduction in the sulfur circulation in the seasons. This ekidenoet, in addition to the idea of using for etebillzsci polyethylene ee sesemi stebillzátor, which contains in its molecule er.

□ Either tris (nonylphonyl) foefit, or diolkylpontaerythrityldlfoaflt, or trle (2,4-di-tert-butyl) phenylfoefIt, or a mixture of orally substituted triphenylphosphites o is used as the organic foefl. up to 18 carbon atoms, or alkyldleulfide, wherein the alkyl is a saturated linear hydrocarbon group containing 12 to 18 carbon atoms. In addition to these additives, it may contain additives to improve the dispersion of eos and granules, perfume waxes and oils, monten waxes with non-glycine-based waxes. To increase the toughness and low stiffness, an ethylene-propylene-rubber or ethylene-propylene rubber may be added.

Said stabilizers used for the enthma treatment of linear polyethylene-based amales have a synarginal effect in the presence of asia. It is an aase produced by partial oxidation of petroleum and tar raw materials in the presence of an oxygen-supported mixture. These carbon blacks have a specific surface area of at least 800 m 2, an ash circulation of at most 1% and a pH of the aqueous extract in the range of 6 to 8.5.

CS 268 272 Bi

Fig. 1 shows the dependence of the induction period of tormooxidac linear polyethylene containing 10% carbon black and the pH of an aqueous extract 8 and a specific surface area of about 850 a, g on the circulation of trio (nonylphenyl) phosphite (TNPP) and diethearylthiodoproplonate (DSTDP). This irrigation is shown by curve 1. Curve 2 shows the dependence of the induction period not based on arylaubstituted triphonyl phosphates (A 0 6) and according to tearyl thiodopropionate (DSTDP). Curve 3 shows the reversal of the induction period of tormooxidation in the circulation of trle (nonylphenyl) foefith in combination with diethearyl dieulfide. The curves show that the organic foils based on organic fools show a combination of thlodlopropionic acid esters or diol alkyldieulfides.

The invention is explained by the following specific examples.

Example 1

-3,100 parts by weight of copolymers of ethylene with 1-butone with a density of 0.953 g.cm and a flow index of MFI 190 ° C / 21.2 N - 0.18 g / 10 min, produced by gas phase polymerization, were arenic and 12 parts by weight of aazi and a specific surface area of 800 n .g, pH - 7.8 and both and hem airy 0.25% ash 0.8%. The mixture was stabilized by the addition of trie (nonylphenyl) fofit (TNPP) combined with diatearylthiodoproplonate (DSTOP). The ice and induction periods were thermooxideco at 190 ° C to a DSTDP concentration at a constant TNPP concentration of 0.25 parts by weight per 100 parts by weight of PE. This screw is shown in Fig. 2, curve 1. Curve 2 represents the standard screw for the case that ground TNPP is used using substituted phenylphosphes (AO 6). The specific internal resistance of these materials was BOTl.cm.

Example 2

100 parts by weight of ethylene copolymers with a bulk density of 0.953 g.cm ^-3 and a flow index of MFI 190 ° C / 21.2 N - 10 g / 10 min, produced by gas phase polymerization, were mixed and 10 parts by weight surface area 960 · .g, pH »7.6, sulfur content 0.20 and ash content 0.0%. The mixture further contained 0.5 parts by weight of glycerol monostearate. The mixture was stabilized by combining 0.2 parts by weight of a mixture of aryl substituted triphenylphosphites (AO 6) with 0.2 parts by weight of dllauryl thlodiproplonate. Elolok was mixed in a fluffy skull, homogenized in melt and grenulcco was performed on a two-wire Wernor-Pfloidorer granulator at temperatures of 180 to 220 ° C. Audas with a volume of 40 1 were produced from the granulator. The material properties measured on the pressed plates are given in Table II. ·

Example 3 n

BO parts by weight of copolymers of ethylene with 1-butonone with a density of 0.953 g.cm. with a flow index MFI of 190 ° C / 21.2 N <0.26 g / 10 min, produced by polymerocl in the gas phase, were mixed with 20 parts by weight of concentrate no. based EPCM coach (Dutrol TP 50 F). Furthermore, the emes circulated 10 parts by weight of asia with a specific surface area of 900 m. g ”, pH 7.6 with an ether content of 0.2% and an ash content of 0.8%. The decoder and lubricant mixture contained 1 part by weight of paraffin and had a melting point of 100-110 ° C. A mixture of 0.3 parts by weight of tribosrylthlodloproplone and 0.2 parts by weight of trsyl (2,4-difluorobutyl) phenylfoft was used for stabilization. Melt homogenization and granulation were performed on a Werner-Pfleidarar granulator at temperatures of about 200 ° C. The granulator was used for blowing tebular films intended for the production of bags for packaging electronic components. Vlaetnoetl material measured in lleovo children is given in tobulco II.

Example 4

100 parts by weight of ethylene e> butene copolymers with a weight of 0.957 g.cm ^-3 with a flow index MFI of 190 ° C / 21.2 N 0.6 g / 10 min, produced by gas phase polymerization, were emitted by β β mass parts of ees of with a specific surface area of 1 000 m, g, pH - 6.5, a circulation of 0.5% and an ash circulation of 0.6%. In addition, the emee contained 0.2% nontane wax (wax E). The mixture was stabilized by the addition of 0.2 parts by weight of trle (nonylphenyl) fofit (TNPP) combined with 0.2 parts by weight of diethearyl thlodipropionate (DSTDP). The granulate was prepared according to the procedure described in Example 2. The granulate was treated with exhaust CS 268 272 81 3 nln per 1 l bottle. When measuring the induction period of thermooxidation at 1 ° C, a value of 17 hours was measured, which proves that said combination of stabilizers is effective 1 when using kyaele reacting eazl and high sulfur content. The slight internal resistance of the material was 85-Λ.

Cm.

Example 5

100 parts by weight of high molecular weight polyethylene with a density of 0.956 g.cm ³ and a flow index MFI of 190 ° C / 21.2 N 4 g / 10 min were mixed with 10 parts by weight of carbon black and a specific surface area of 900 m 2 g, pH <7.6. , with a sulfur circulation of 0.2% and an ash circulation of 0.8%. Furthermore, the amis contained 3 parts by weight of paraffin oil. The mixture was stabilized with 0.2 parts by weight of dearearyl pentaerythritol diphosphite combined and 0.2 parts by weight of diethyl arylproplonate (OSTDP). The preparation of the granulate was carried out according to the procedure described in Example 2 at a temperature of * 200 to 250 ° C. The granulate was blown into 1 L bottles. The induction period of thermal oxidation of the material was 8 hours, specific internal resistance approx. 8O4.c «. The material ea exhibited a high value of tsh impact strength at -20 ° C, which reached 2,480 k3.m.

Table 1

Influence of pH of aqueous extract eazl on induction period of thermal oxidation of linear PE e 10% by weight and tni ml eazl.

Measurement temperature 180 ° C, induction period in hours The pH of the aqueous extract is lower

Concentration

TNPP (%) <72 7

0.2 16 '3

0.4 253

Table 2

Vlaetnoeti slektroetatlcky conductive polyethylene B - material for the production of euds and canisters F - material for the production of foil

Mez kluzu MPa 22 1Θ Pevnoat in tension MPa 22 13 Relative elongation at the yield point % 10 Ta žnoa t % 25 640 E-module in bending MPa 900 700 Shaped standard for hot Vlčat A ° c ^s 125 120 Notched toughness at -20 ° C k3.m ^-2 6 50 Impact tensile strength in tension at -20 ° C kO. » ^-2 240 340 Melt flow index at 190 ° C / 21.2 N g / 10 min 5 12 Surface resistance JX <lo ⁴ 4 10 ⁴ Specific internal resistance -Λ. cm 70 40

Claims (3)

OBJECT OF THE INVENTION 1. A reduction based on linear polyethylene with a surface electrical ^{resistance of more than 10 4} Λ of internal resistance of more than 100 IU. consisting of 100 parts by weight of linear polyethylene with a density of 0.94 at 0.96 g.ca ^- ^, MFI flow index at 190 ° C / 21.2 N max. 0.6, at 190 ° C / 21.2 N · 1st 4 g / 10 win and 8 to 12 haotnostal parts eazí o aěrnýa po2 -1 vrchem BET sin. 800 a .g, pH of aqueous extract 6 to 8.5 and ash content aax. 1% by weight, characterized in that the organic fofit etebillizer is incorporated in an amount! 0.05 to 0.3 parts by weight and stabilizers containing sulfur in an amount of 0.1 to 0.75 parts by weight, wherein either tris (2,4-tert-butyl) phenylphosphate or ante-substituted aryl triphenylphosphines are used as the organic phosphate, and the sulfur compound used is either dlalkyl ether of thlodipropionic acid, where alkyl is an unsaturated hydrocarbon chain containing 8 to 18 carbon stones, or dlalkyldisulfide, where alkyl is an unsaturated linear hydrocarbon chain containing 12 to 18 carbon atoms. 2. A composition according to claim 1, characterized in that it contains calcium or zinc stearates, paraffin waxes and oils, aontane waxes β waxes based on glycerol monoethersate, in an amount of 0.2 to 3% by weight, 3, The composition according to claim 1 and / or 2, characterized in that it contains ethylene-propylenedlene rubber or ethylene-propylene rubber in an amount of 10 to 30% by weight.