CS209334B1 - Electrostatically conductive tubes based on vinyl chloride polymers - Google Patents

Abstract

The purpose of the invention is to improve the electrostatic properties of pipes intended for use in conditions excluding the formation of static electricity by adding carbon black and dispersing agents. The essence of the invention is the composition of a mixture for the production of electrostatically conductive pipes, which includes vinyl chloride polymers, conductive carbon black and dispersing agents. Dispersing agents increase the "effective surface area" of carbon black in the mixture, thereby reducing their dosage. The invention can be used in the mining and chemical industries, in the transport of flammable media, in air conditioning and ventilation.

Description

The present invention relates to tubes prepared from blends based on polymers of vinyl chloride, which are electrostatically conductive, δο allowing them to be specifically used in conditions which exclude static electricity. Vinylchloride based polymers have been used in everyday practice for over 40 years. They have moved in engineering, construction, semi-agriculture and special cases. However, their use could be much wider if their electro-insulating properties causing the generation of static electricity are removed. As a result, there is a risk of explosion and fire. This unfavorable phenomenon can be eliminated by using tubes with a surface electric resistivity R p of less than 10 ft, which can be achieved by adding special conductors to the base mixture. The patents mentioned below characterize the possibilities of achieving better electrical conductivity.

British Patent 1.114.133 recommends the addition of 25% carbon black to improve electrical conductivity. According to U.S. Pat. No. 3,753,765, the addition of carbon black reduces the surface resistivity. In Japanese Patent 47,440 / 78, 15 - 35% of the volume of iron powder is mixed into PVC.

In addition, other additives may be added, as disclosed in NSR 1.469.877, where 4-5% by weight polyethylene glycol is added to the carbon black.

Similar data are available in other literary sources.

However, carbon black is the most widely used to achieve good electrical conductivity. However, it is disadvantageous that a considerable amount (from 10-30% w / w) of the carbon black must be added, which impairs the mechanical properties of the plastics. This fact is very unfavorable for pipes and therefore it is necessary to optimize the carbon black content so that the mechanical properties are satisfactory. This can be achieved in the case of electro-static tubes of polymers of the vinyl chloride according to the invention, which consist of a mixture of 60 to 94% by weight. mixtures of polymers of vinyl chloride with stabilizers, lubricants and lubricants, 5 to 30 wt. % of conductive carbon black, 1.0 to 10.0% by weight, preferably 3% by weight, of at least one dispersing surfactant and / or mixtures thereof of R-CON - ("^ΗΗΟΟ) nH wherein R is unsaturated saturated alkyl in the range of C? to C>> or unsaturated alkyl having an odd number of C ^ ^ to G21 *s by one or more -CbamiC- bonds in the molecule, z = 1 to 5, n »1 to 5 R-C 0 - (- C 2 H 2 O 2) f H, wherein R is an odd alkyl of odd numbered carbons in the C 1 to C 8g range or unsaturated alkyl having an odd number of C 1 to C 8 carbons and one or two -C = C- bonds in the molecule, z = 1 to 6, n = 1 to 45 R-O-f-CjHg ^ O) χΗ, wherein R is a saturated alkyl of C ^-Cg v in the molecule or an unsaturated alkyl of even-numbered carbons of up to one bond - C »C- in the molecule, z = 1 to 5 »n * 1 to 55

Ar-O - (- C 2 H 2 O) aH where Ar is octylpheayl, nonylphenyl, dodecylphenyl, z = 1 to 5, n = 1 to 60

[R-CHg-O- (CH 2 CH 3 O) n-x "I> 04 · kd-'e R is an even-numbered saturated alkyl of C 1 to C 20 in the molecule or octylpheayl, nonylphenyl, dodecylphenyl, n = 1 to 50, z = 1 to 5, x = 10 to 10 and R - / - fOH 2) n CH-O- (x-CH 2 -OH), wherein R is saturated alkyl having carbon numbers of ^- to 2323 and one bond of -CaC- in a molecule, n = 1 to 6, x = 1 to 200 RO-SO 2 Me, wherein R is an even-numbered saturated alkyl of Οθ to C22 or an unsaturated alkyl having an even number of carbon atoms of Cnou to P 20 and a 3-bond C »C - in a molecule, or C 1 - 3 (CPg) / n 6 6 to 40 /, Me is Na +, K +, 1 / 2Ca 2 + E-SO 2 Me, where R is a saturated alkyl of even C 8 to C 22 or unsaturated alkyl with even carbon with the number of carbons C 1 - g to C 2q and one bond with C = C - in the molecule, or C 1-3 - (θ 2 - 2) Λ, (a = 7 to 4 1), Me is Na +, K +, 1/2 Ca 2+, 1/2 Mg2 + R-COOMe, where R is a saturated alkyl with an even number of carbons σθ to C22 or unsaturated alkyl with an even number of carbons C ^ gg, θθθ and one bond -CxC- in the molecule, orCE3- ( 0-2) and, (n-5-39), Me is Na +, K +, WH4 +, 1/2 Ca 2+

By the addition of nonionic surfactants, a more even dispersion of carbon black in the polymeric mixture is achieved, providing a new, enhanced effect and improvement of the electrical conductivity, as illustrated by the following examples: Example 1.

A powder mix of PVC agglomerate containing 100 wt. of a suspension PVC having a K-value of 68 suitable for the production of pressure tubes, 2.5 wt. a mixed stabilizer containing tribasic lead sulfate, dibasic neutral lead stearate, calcium stearate and lubricant, 2 wt. d. fillers provide calcium carbonate and a small amount of pigment to achieve the desired color mixing in the hot mixer to 120 ° C followed by cooling at 40 ° C in the cooling stage. Pipes of 110 x 5.3 mm are produced from the mixture thus prepared by extrusion on a twin-screw extruder, while the technological parameters are at least so that the melt temperature at the inlet to the extrusion head is at least 205 ° C and the extrusion head zone temperatures are. in the range of 180 - 200 ° C.

The electrical surface resistance R of the tubes is above I0 ^^ jTL.

Jt Example 2

Of the mixture as set forth in Example 1 but additionally with 10 wt.%, 20 wt.% And 30 wt. acetylene carbon black under the same conditions as in the example. 1 prepare pipes of the same size. The electrical surface resistance of the pipes is as follows:

With a carbon black content of 10 wt. is 4.10 <RTIgt; 0- </RTI>, at a carbon black content of 20 wt. is 1. Example 3

From the mixture as described in Example 2, with the addition of oethylene carbon black and with the addition of 1 wt.%, 3 wt. and 5 wt. a nonionic thiazide of the type -) mH, where k «2., n« 5, R is a radical with θ ^ 2-14 ® * ZM of the same condition-1 prepare tubes of the same size. Electrical surface resistance of surfactant 5 wt. is 2.10, at the content of • 1 1 wt. the thiazide is 1. 10 µl, at the content of 3 wt. the surfactant is 9.5. 10 ^ -Q. . ΚζΟΟ- (O-CkH2k nok as in Example R tubes with a carbon black content of 10 wt.% And 20 wt.

As in Example 1, mixtures of PVC are prepared but are added with the addition of 5 wt.%, 10 wt. and 15 wt. conductive retort carbon black. The procedure of Example 1 of the tube 110 x 5.3 mm was prepared from the mixture, having the following electrical surface resistances Rp: at a carbon black content of 5 wt. - 5. 10 µT, at 10 wt.%. - 5. 10? Q.a at a carbon black content of 15 wt. - 1.5 <102-Ω-. Example 5

As in Example 4, mixtures of PVC containing conductive retort carbon black are prepared in addition to the addition of 3 wt. d. and 7 wt. mixtures of surfactants in a 1: 1: 1 ratio of the following composition: R-C 0- (O-C 6 H 21 f) -mH, where k 2, n = 6 and R is a radical and C 2-12 R-O- (k 2 k) ^ 2k ”® ^ n ^, 'where R is a radical with C] _g_ig * = * 6

Ar-O-fckH 2k-O) and H where Ar is nonylphenyl, k 2, n-5 From the prepared PVC mixture, the tubes according to Example 1 are prepared having surface electric resistances Rp: at a carbon black content of 5 wt. and surfactant content 7 wt. is 9. 10%, with a carbon black content of 10 wt. d. and surfactants of 3 wt. d. is 1.4. 10 J-L and with a carbon black content of 15 wt. and surfactants 5 wt. is 9.6. 10 JI. Example 6

As in Example 2, a PVC mixture containing 10 wt.%, 20 wt. and 30 wt.% acetylene carbon black, in addition to the addition of 2 wt.%, 4 wt. and 6 wt. a 1: 1 mixture of surfactants; , R-CO- (O-C k H 2 k) n H where R is a radical with C 16-18, k = 2, and R 6 is C-COOX where R is C 3-9 (CP 2) -as n-11-13 and X is Me 1+, 1 / 2Me 2+ (Na +, 1/2 Ca 2+) 4 Tubes are prepared from the PVC mixture thus prepared as described in Example 1, the electrical properties of which are as follows: at a carbon black content of 10 wt. d. and surfactant mixtures of 4 wt. is the specific surface resistance Rp = 1.2. loVl. , with a carbon black content of 20 wt. d., and surfactant mixtures 6 wt. is Rp »8.5. 10 J-L and with a carbon black content of 30 wt. d. and surfactant blends of 2 wt. is Rp ® 9.1 · 10¾} ..

Example 7

From a mixture like. with the addition of acetylene carbon black and with the addition of 1 wt. d., 3 wt. and 5 wt. the anionic thiazide R-O-SO4Na, where R is alkyl and pipes of the same size are prepared under conditions such as those of Example 1. FIG. The electrical surface resistivity of Rp tubes at a carbon black content of 10 wt. and surfactant 5 wt. is 2.5 * 10¾}. and 1 wt. and at a carbon black content of 30 wt. and 3 wt. teazidu is 9.8, 1ο \ t

ExampleS

From the mixture as described in Example 2 with the addition of acetylene carbon black and with the addition of 2 wt.%, 4 wt. and 7 wt. perfluoro surfactant R COOMe where R is C 1-6 and Me is K +, pipes of the same size are prepared under the same conditions as in Example 1. Electrical surface resistance of Rp pipes at a carbon black content of 10 wt. and surfactant 4 wt. is 2.3. 10: 3 at a carbon black content of 20 wt. and surfactant 2 wt. is 2.0. ΙΟΊΓλ- and carbon black content 30 wt.%, Surfactant 7 wt. is 8. 10 ^ -TL, Example 9

As in Example 4, mixtures of PVC containing conductive retort carbon black are prepared in addition to the addition of 2 wt.%, 4 wt. and 8 wt. a 1: 1: 1 mixture of surfactants: R-CO- (θ-C 6 H 8) - H where k = 2, n = 6, R 2 is R-SO 2 Me where R is G 12-14

Me is NH + 4 R-COOMe wherein R is CF-j (CF8) 2 -alkyl

Me is 1/2 Ca 2+ Pipes having a Rp: 5 wt. carbon black and 8 wt. surfactants 8.10 ^ -0.

Qt. 10 mass.d. carbon black and 4 wt. surfactants 1.4. 10 ___ 15 Mass. carbon black and 2 wt. surfactants 8.5. 1θ Ώ- Example 1Ó

As in Example 4, mixtures of PVC containing conductive retort carbon black are prepared

Claims (1)

moreover, with the addition of 3 wt.%, 7 wt.% and 10 wt.%, 1: 1 surfactants are precipitated: Ar-O-Ar is dodecylphenyl, k = 2, n = 7 RO-SO2Me R is alkyl 0 The tubes were obtained from the prepared mixture according to the procedure of Example 1 and having the surface resistances Rp: 5 by weight. aadzí and 10 wt. tensides 8. 104 wt. d. carbon black and 7 wt. tensides 1.5. 10 «Li 15 mass. aadzí and 3 mass.d. surfactants 8.5. 10ΪΩ. Example 1 As in Example 2, a PVC blend of 10 wt.%, 20 wt. and 30 weight percent acetylenes, in addition to 3, 5, and 9 weight percent. surfactant mixtures 1: 1: 1 composed of R-00N- (C 2 H 2 O 2) mH, R is alkyl C 12-14, z = 2, n = 5 Ar-O 2 C 2 H 2 O, O) -H, Ar is nonylphenyl, z = 2, n = 7 R Tubes whose electrical properties are as follows according to Rp: 10% by weight are prepared from the PVC mixture thus prepared. carbon black and 9 wt. tenside 1.5. 10 ^ 20 wt. carbon black and 5 wt. surfactant 9 · ιο2-Ω. 30 mass. carbon black and 3 wt. tenside 8.5 10 ^ X2. SUBSTANCE EFFECTED Electrostatically conductive polymers based on vinyl chloride polymers, characterized in that they consist of a mixture of 60-94% by weight. mixtures of polymers of vinyl chloride, with stabilizers, lubricants and fillers of 5 to 30 wt. % of conductive carbon black, 1.0 to 10.0 wt.%, preferably 3.0 wt. at least one dispersing surfactant and / or mixtures thereof: R-CON - (- C 0 O) r H where R is saturated alkyl having an odd number of carbons in the range of C 2 to C 8g or unsaturated alkyl having an odd number carbon atoms C 1 to C 2 and one or two bonds C 1 - C- in the molecule, z = 1 to 5, a = 1 to 5 R-CO - (- C 2 H 2ζθ) ΛΗ, where R is a saturated alkyl with an odd number of carbons in C range? up to C2g or unsaturated alkyl having an odd number of carbons C ^ ^ to Cy a and one or two of bami = = 0- in the molecule, Z = 1 to 6, n = 1 to 45 R-0 - (- C2H2z ° ^ nR 'hde'R Is a saturated alkyl with a number of carbons σ ^ θ to C2 ^ in a molecule or an unsaturated alkyl with a number of carbons in the range of C14 to C22 and one bond of -C = C- in the molecule, z = 1 to 5, n = 1 up to 55 Ar-O - (- C 2 H 2 O) flH, where Ar is octylphenyl, nonylphenyl, dodecylphenyl, z = 1 to 5, a = 1 to 60 έ / R-CH 3 -O- (HH 2 CH 2 O) Μ- / χ " Θ'θ4 »where E 3e is a saturated alkyl with even carbon atoms of C1Q to C20 in the molecule or octylphenyl, nonylphenyl, dodecylphenyl, n = 1 to -50, z to 1 to 50, z to 1, 5, x = 10 to 100 / R - - (θΗ2) ηΟΗ-Ο- / χ-ΟΗ2-ΟΗ, where R is saturated alkyl with carbon numbers of C- q and up to one bond - CaC- in the molecule, n = 1 to 6, x = 1 to 200 RO- SO2Me, wherein R is saturated alkyl having a carbon number of C8 to C22 or an unsaturated alkyl having an even number of carbon atoms of C1 to C20 * by a single -G-G- moiety in the molecule, or esy (en> 2) a-, (ns6 to 4θ), Me is Na +, K +, 1/2 Ca 2+ R-SO 4 Me, where R is saturated carbon-containing alkyl of Οθ to C22 or C unsaturated alkyl ^ g to 02θ and one bond -C = C- in the molecule, ores (* '7 M 4 4l), Me is Na +, K +, 1/2 Ca2 +, 1/2 Mg2 + R-COOMe, where R is a saturated alkyl with even the number of carbons Cg to C22 or the unsaturated alkyl having an even number of carbons C gg to C20 and one bond -C = «C- in the molecule, or Cyi (- σσ2) .Λ, (n-5 to 39), Me is Na +, K +, NH 4 +, 1/2 Ca 2+.