CS210364B1 - Polyolefinic mixture with improved electrical conductivity - Google Patents

Abstract

The invention relates to plastic substances and honeycomb products with improved properties. It solves the improvement of the electrical conductivity of polyolefins due to additives - carbon black and binding agents. The essence of the invention is a polyolefin mixture with improved electrical conductivity, which contains conductive carbon black in the amount of 3 to 35% by mass. and binding agents in the amount of 0.1 to 5.0% by mass. As binding agents, substances prepared by the reaction of fatty acids, alcohols, amines, aradides, as well as alkylphenols with alkylene oxides, or of different alkylene oxides with each other. Reaction products of fatty acids with amino alcohols can also be applied. The object of the invention can be applied in the production of plastic products that must not be electrically charged, such as profiles, pipes, foils, moldings, moldings and others, used in engineering, electrotechnical, chemical, food processing and mining industries.

Description

210364

The present invention relates to polyolefinic compositions having improved electrical conductivity by binding agents.

Polyolefins and their copolymers have found more practical application from all thermoplastics. Thanks to their excellent electro-insulating properties, they have switched to electrical engineering. However, this property causes static electricity to accumulate on their surface, discharging which can cause explosions and considerable damage to the environment of gases, vapors, dusts, combustibles, and so on.

This unfavorable phenomenon can be eliminated by improving the electrical conductivity of the thermo-polyolefinic mixture by adding to the natural polymer either antistatic or conductive additives such as spitter types, inorganic salts, metal powders and the like.

As antistatic additives, cationic, anionic and nonionic surfactants are used, especially ethylene oxide, propylene oxide or alkylolamine adducts (U.S. Patents 3,720,652, 3,296,019, Jap.). 28 607/68, 2 092/69, USSR 328 117). Also used are phosphoric, sulfuric, tin, imidazoline, siliceous and boronic compounds. 126 338, USSR 334 227, NSR 2 053 489,

Me p. 2 972/70, 24 044/67, Cancer. 290 003 and Franc. 2,025,541]. The most common are nitrogen compounds derived from fatty amines and amides (US 3,369,435, V. Brit.). 1 1 25 248, · Franc. 2 054 369, NSR 1 669 480, USSR 360 350 /. By using surfactants having a concentration of 0.1 to 5% by weight, an electrical surface resistance of at least 10θ Ohm is achieved, with an internal el. resistance is slight, although it is sufficient to remove power, but is not sufficient for particularly hazardous environments with potential for explosion and fire.

Therefore, other conductive additives are used in a relatively high amount, e.g., with a particle size below 1 µm and up to 25% by weight. /Briton. pat. 1,114,133, US 3,733,765].

When U.S. Pat. No. 2,779,684 uses carbon black sizes below 54 .mu.m, surface resistances of 8.2 .mu.m Ohm can be achieved with polypropylene films.

Mixing low molecular weight polyethylene with 29 wt. the soot and lamination of high molecular weight polyethylene with this blend, according to South African Patent 75 00 033, the conductivity and static electricity generation are improved.

Carbon black is also combined with other additives and carriers. Thus, according to the German patent 1 469 877, carbon black is combined with 1-methylene glycol, thus improving electric power in the final result. By adding aluminum powder, an improvement in electrical conductivity is achieved, as described in the French patent: 2,645,244. Other additives may also be added. In Japanese Patent 78 47 440, it is recommended to apply 15-35% by volume of iron powder.

However, the most widespread use is the use of various types of carbon black, which provide good conductivity parameters for the blends, respectively. products.

However, we need to add a significant amount (5-50% by weight) of carbon black, according to their type, resulting in a deterioration of other useful properties such as strength, ductility and impact resistance.

Therefore, it is desirable to reduce their amount in the polymer to an optimum limit, while at the same time providing better electrical and other useful properties, in particular mechanical properties.

This can be achieved with a polyolefinic composition with improved electrical conductivity of the present invention, which comprises 40 to 96.9% by weight of the composition. polyolefins, 3 to 35 wt. carbon black 0.1 to 5.0% by weight; surfactants such as binding agents of the following composition: 210364 2 R-CO / O-ch 2 -CH / -oh «1

R-CO-NH / O-CH2-CH / n-OH

R-O / CH, -CH-O / nH

R 1 is R-CO-N 1 / O-CH 2 -CH / nOH 2

R-NH / O-CH 2 -CH 2 OH

I R1 R-N - {/ O-CH2-jH / n-Hj2R1 r / ch-ch2o / xch-ch2-oh

CH, -CH-OH, R-COO-CH-CHO-N ^ r, I \ t

D X

Ar-0 / .CH2-CH-O / nH / r-coo-ch-ch2 / 2-n-ch2-ch-oh R, R,

(R-COO-CH-CH 2), - N 2 R 1 where R is alkyl of C atoms 8 to 3-0, x = 1 to 5; n = 1 to. 30; = H, methyl,

Ar is nonylphenyl or dodecylphenyl.

The scavenging agents of the present invention provide in the polyo -efin mixture such that they mediate "conductive bridges" between the soot particles separated by the non-conductive polymer. Here, the synergistic effect is shown in that the electrical resistance of the mixture falls below the values achieved by the pure ingredients.

Such modified polyolefin compositions can be used in new applications requiring polymers with increased electrical conductivity. Example 1

Polyolefinic compositions prepared by calendering and plating, comprising a high density polyethylene having a melt index of IT = 2 g / 10 min, high density polyethyleneIT = 5 g / 10 min and polypropylene IT = 0.7 g / 10 min. Addition of 0.1 to 5% by weight antistatic type: 0.1% - A-1 ro (C12-ch2-o) -6h, where R is c8-30 alkyl 1.5 7. - A-2 Ar-o {cH2 -CH2O} gH, wherein Ar 'is nonylphenyl or dodecylphenyl 5% -A-R-NH (O-C112CH2) 7H wherein R11 is C8-30 alkyl.

Said modified polyolefins have the following properties: 3 1 0364

Electrical Internal Resistance / Ohm. m / P olyme Additive A - 1 A - 2 A - 3 rPE 4.5. 1015 3.2. 10 1 5 7.8. 1 0 1 3 1PE 3.5. 1 θ '5 3.8. 1 o'5 4.9. 1 0 1 4 PP 5.8. 10 ’5 4.2. 1015 9.9. 1013

Electrical Surface Resistance / Ohm / Polymer Additive A - 1 A - 2 A - 3 rPE 1.7. 1 o '1 2.2. 1 0 1 0 9.6. 1 o9 1PE 7.3. 10 ’2 5.6. 101 1 7.4. 109 PP 8.2. 1 0 1 2 7.8. 1 0 1 2 5.3. Example 2

Polyolefinic blend prepared by calendering and plating molding, containing a bulk density polyethylene IT = 2 g / 10.min in an amount of 70-90% by weight. and 10-30 wt. acetylene carbon black has the following electrical parameters:

Carbon black content / 7c mass / Electrical internal resistance / Ohm. m / Electrical surface resistance / Ohm / 0 over 1 0 1 5 over 10 ^ 10 7, 4. 1 0 1 4 9.5. 1θ ”20 7.0. 1 0 1 4 9.1. 10’1 30 2.4. 1014 2.1. EXAMPLE 3 Polyolefin blends as in Example 1 with 1 wt. a synergistic additive of the following formula R-CON (-O-C 8 H 11) wherein R-alkyl has the following electrical parameters: 0b carbon black loading (% w / w) Electrical internal resistance / Ohm. m / Electrical Surface Resistance / Ohm / 10 5.5. 1012 5.5. 109 20 4.55. 10’1 1,? . 109 30 5.2. 106 1, 1. 1θ3 210364 4 L: l ·. * +

Fci, uiefinic mixture, prepared by calendering and plating in the form of platelets, containing 5 5 wt. high density polyethylene IT = 5 g / 10 min and 5-15 wt. Conductive lip training takes the following electrical parameters:

Content with ad z /% mass / electrical internal resistance Electrical surface resistance / Ohm / / Ohm. m / 5 8. 104 1. 1004 10 7. 102 4. 102 15 2. 102 4. 10 ’Example 5

Polyolefinic mixture, as in Example 3 with the addition of 0.8% by weight of synergistic mixture (1: 1) of the type: R-COO-OC, where R is C 1-6 alkyl and RN 4 O-C 2 H 4 Y 4 H, wherein R is C 12-14 alkyl has the following electrical parameters:

Ob s range with ad i /% mass / electrical / ohm internal resistance. m / Electrical surface resistance / Ohm / 5 2. 104 4. 103 10 4. 102 7. 10 ’15 2. 102 4. 10 ’

Example6

The lyophilized mixture, prepared by calendering and plating, contains a polypropylene IT of 0.7 g / 10 min in an amount of 70-90% by weight. and acetylene carbon black in an amount of 10-30% by weight, has the following electrical parameters:

Ob s ah s ad z i /% mass / electrical / ohm internal resistance. m / Electrical Surface Resistance / Ohm / 10 6.5. 1 0 1 5 8.2. 1 0 1 4 20 7.2. 1014 3, 5. 1014 30 6.7. 1 0 1 3 7.2. 10'2 Example 7

Polyolefinic mixture, as in Example 5, containing 2.5 wt. mixture (1: 1: 1) of a synergistic additive composition: RO (C2H4) -3H, where R is C1-14-alkyl r-con {o-c2-H4} · 2 " Ο · (θ2Η ^ -Ο ^ βΗ, where Ar is nonylphenyl, has the following electrical parameters: 5 210364

Content with ad from i / 7c mass / electrical / ohm internal resistance. m / Electrical Surface Resistance / Ohm / 10 6.8. 10 ’2 7.7. 1010 20 4.2. 1 0 1 0 3.8. 108 30 1.9. 108 9, oh. Example 8

Polyolefinic ames, as in Example 5, with a content of 1.5 wt. synergistic additives of compound 507, ch2-ch2-ooc-r

R-COO-CH2-CH2-N '/ X

XXxCH 2 -CH 2 -OH

and 50 Z, R-COO-CH 2 -CH 2 -N (CH 2 -CH 2 OH) 2 wherein R is C 1-2-14 alkyl, has the following electrical parameters:

Rates Content /% Mass / Electrical / Ohm Internal Resistance. m / Electrical Surface Resistance / Ohm / 10 7.5. 10 1 1 θ »8. 109 20 5.2. 1 o9 7.3. 107 30 3.5. 1 o7 2.4. ΙΟ4 Example 9

Polyolefinic Compounds, as in Example 1, with the addition of 2% synergistic additive of formula, ch-chohoh

R-COO-CH2-CH-N2;

CHO with the following electrical parameters:

Carbon black content 17c mass / electrical / ohm internal resistance. m / Electrical Surface Resistance / Ohm / 10 3.2. 1012 5.3. 109 20 4.2. 1 0 1 1 9.7. 108 30 3.8 .106 1.6. 103

Claims (2)

Polyolefinic composition with improved electrical conductivity, characterized in that it consists of 40 to 96.9 wt. % of polyolefins, 3 to 35 wt. % carbon black and 0.1 to 5.0% by weight of surfactants as binders of the following composition: R-CO (O-CH ₂ -C ₁₁ ) _n -OH R-CO '1 Ro (cH ₂ -CH-o) - _n H R-NH (O-CH2-H _{) n} OH ^R1 RN- _{4-o-CH2 -jH> _n H} ₂ {R-CH ₂ OH} a - _x CH 2 CH ₂ OH ^R 1 CH, -CH-0H / ’ R-COO-CH-CH ₂ -N ^Z R, I \ R, CH, -CH-OH Ar-O {CH ₂ -Clio-O) - _n H | R-COO-CH ₂ CH _{2 S-n-CH2} -CH-OH R-C0-NH-CH {0} _n CH ₂ 0H ^ _R-COO-CH-CH2 S ₃ N wherein R is alkyl with the number of carbon atoms from 8 to 30, x = 1 to 5; η = 1 to 30; R ₁ = hydrogen, methyl, Ar is non-phenylphenyl or dodecylphenyl.