SU1240761A1 - Electric conducting material and method of producing same - Google Patents

Abstract

1. An electrically conductive material containing graphite particles with a polyolefin coating, characterized in that, in order to reduce the volume resistivity and increase mechanical strength, it contains flake-shaped graphite particles with a polyolefin coating of 0.2-2.0 µm thick, made of polypropylene mol. May 0.75-1.5-10 of the following composition, wt.%: Isotactic polypropylene93-97 Atactic polypropylene1, 5-4 Stereoblock polypropylene 1.5-3 2. Method for producing an electrically conductive material by polymerization of an olefin on the graphite surface in the gas phase , in the mass or in the medium of a hydrocarbon solvent in the presence of a catalyst consisting of four-porous titanium and diethyl aluminum chloride, which is also distinguished by the fact that, in order to reduce the specific volume resistance, increase the mechanical strength of the product and increase the manufacturer of the process, propylene is used as an olefin, and the polymerization process is carried out on the surface of flaky graphite, previously treated with dithy-paluminium chloride, and then with titanium tetrachloride with a content of tetrachloride titanium of 1.2510 -1.2510 mol per 1 m of graphite surface. Q SS (L to (a of O)

Description

one

The invention is from; 1st order to polymer chemistry, namely to electrically conductive materials, and can be used in the manufacture of resistors, strain gauge strain sensors, waveguides, screens, electrodes and heaters.

The purpose of the invention is to reduce the specific volume resistance, increase the mechanical strength of an electrically conductive material and increase the productivity of the production process t .ro.

The method is carried out as follows.

. The graphite is dried in a vacuum luiri with a flow of inert gas for 1-3 hours at 100–200 C. Then the ru-vphi organoaluminum compound is fed into the reactor (in a vacuum or inert gas flow) (it is dissolved in a hydrocarbon solvent) for 15–20 minutes at 20-70 ° C, after which they are fed to the compound of the transition metal. The atomic ratio Ti / A is from 1:10 to 1:22. The organoaluminum compound can be added either all at once (before TiCl deposition), or B in two steps. The polymerization of propylene is carried out in the gas phase, in a solvent, or in the bulk of the monomer. The maximum yield of 6.6-7.0 kg per 1 g of Ti is observed nppi conducting polymerization in the mass of the monomer.

I

The composition of the material is controlled by the amount of catalyst deposited on the surface of graphite, the polymerization time, the monomer concentration and the polymerization temperature. When discharged from the reactor, the material is a free-flowing powder, containing graphite particles coated with polypropylene.

The resulting material is unloaded from the reactor, washed with alcohol, and dried.

To study the electrophysical and physicomechanical properties, the plates are pressed, keeping for 5 minutes at a pressure of 150 atm and a temperature of 190 ° C, then cooled under pressure of 20 minutes to room temperature.

The table shows the characteristics of the materials obtained: specific volume resistance (pv), tensile strength (br) and compression (d), Dieit impact strength, which

0761. . 2

the stat (Q), as well as the composition of the material and the molecular weight of the polymer. Data on the value of the temperature coefficient (LF

AR 1 R T

is an important characteristic for electrically conductive materials used in the fabrication of resistors, waveguides and shields;

10 of example 1. In example 11 (control), the polymerization of propylene is carried out in the presence of hydrogen, which, because of its ability to participate in the reactions of limiting the growth of polymeric

15 chain leads to a decrease in molecular weight of polypropylene (PP) below the limit specified in the claims, which is accompanied by a decrease in strength characteristics.

20 EUZ-M brand graphite (GOST 10274-79) is used - low-ash, low angle coal, flake.

Example 1. 3 g of flake graphite are placed in a glass ampou 5 at 5 at vacuum vacuum at 200 ° C for 1 hour, then in a stream of inert gas or in a mixture of (C2Hj) AfC1 in the amount of 0.011 g fed in p-stirring, kept at 20 ° C for 20 minutes, after

which is served in a quantity of T1SB in an amount of 0.018 g, which is 6,

X

to 10 mol / m graphite. After that, in a stream of inert gas, graphite with a catalyst is transferred into a metal reactor with a mixer, to which monomer is fed, and then cocatalyst (in the amount of 0.201 g. Atomic ratio. Polymerization is carried out in a liquid monomer medium at 70 ° C and pressure 40 atm.

After 120 minutes, the polymerization is stopped. Total output PP 30 g. The value of the temperature coefficient

stand -

uR

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R M

in the range

4, 2-300 K is O, 2. The composition, p, the mechanical characteristics of the air, are in the table. The specific volume resistance l does not depend on the sample length, and the resistance R varies linearly with a thickness in the range of 0.1 to 1 mm.

Example 2. The process is carried out under the conditions of example 1 using 8 g of graphite, on which 0.0304 g (CjH) AlCl and 0.048 g ISH are deposited (the Ti content on the graphite surface is 6.3-10 mol / m).

3

Polymerization of propylene is carried out for 40 minutes at a pressure of 40 atm and a temperature of 70 ° C. The content of cocatalysis-; torus 0.3 g. The atomic ratio of T1 / A1 1:10. The composition of the product and properties are given in the table. The polymer yield 4.7 kg per 1 g of Ti,

Example 3. The process is carried out under the conditions of example 1 at 60 ° C using 9 g of graphite, 0.024 g (C2Hj) AlCl and 0.04 g of TiCl4 (4.7 x 10 ° mol / m). The atomic ratio of Ti / Al is 1:10.

The polymerization was carried out for 70 minutes at 70 ° C and 40 atm. Output Ш1 per 1 g of transition metal 4.28 kg. The composition and material properties are listed in the table.

 Example 4. 16g of graphite is placed in a glass ampoule, evacuated at 1 h, then in an inert gas stream is fed into a metal reactor vacuumed with an inert gas, evacuated, then the required amount of monomer is fed. -

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The temperature is raised to 70 ° C, 0.3113 g (C2Hy) gA1C1 is fed, held for 15 minutes, TiClij is fed in a quantity of -0.0228 g, which is 1.34 x Yu mol / m. The ratio of Ti / Al l222 Polymerization are 60 minutes at a pressure of 42 atm. Output SSH per 1 g of titanium 7 kg.

The composition and material properties are listed in the table.

Example 5. A 5g pre-pumped graphite is placed in a glass ampoule and evacuated. Then, 0.04 g are fed (stirred at 20 ° C for 15 minutes and 0.059 g of TiCl is introduced, which amounts to 1.25 x м mol / m. Hold at room temperature for 20 minutes and in a stream of inert gas, graphite with a catalyst is introduced into a metal reactor with a stirrer, to which 150 cm of purified n-heptane is then introduced, and 0.4 () A1C1 the temperature is raised to propylene to a pressure of 4 atm. The polymerization is carried out with stirring for 120 minutes. The Ti / Al ratio is 1: 1t. and dried. The yield of PP is 17.7 g (1.1 kg per .1 g of Ti). The composition and properties of the product are given in the table.

Example 6.5 g of pre-calcined graphite is placed in

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metal rotating reactor with blades inside (like drum rotating s.). The reactor is pumped out and fed into it. The vapors 5 (- (0.022 g) are displaced for 15 minutes and the TiCl4 (g) is fed into it, which is 6.3 U / ml. The temperature is raised to 70 ° C. In 10 0.03 g () A: 1C1 are fed to the reactor and propylene pressure is 7 atm. Ti / Al ratio is 1:16. Polymerization is stopped after 20 minutes. Total PP yield is 8.2 g (1.0 kg / g Ti), The composition and properties of the material are given in the table.

Approximately 7. 15 g of graphite are placed in a glass ampoule, evacuated at 200 1,5 1.5 h, then in a stream of inert gas are fed into a metal reactor blown with 20 inert gas, then evacuated at t 70 c, then 150 cm of purified n is fed. heptane, propylene pressure is 5 atm, 0.2 g () A1C1 is fed, held for 25–20 minutes, and 0.01878 g of TiCl4 is fed, which is 1.25 U mol / m. The ratio of Ti: Al 1:18.

The polymerization is carried out at 70 C 60. min. The yield of PP is 2.7 kg per tg of titanium - 30 tane.

Example 8c The process is conducted under the conditions of example 1 using 2.5 g of graphite. O, 0095 g (+0.02 g cocatalyst) (, p) 2 A1C1 and 0.0215 g 35 TiCl (6.3-U mol / m), the polymerization is carried out at 70 s and a propylene pressure of 41 atm . The ratio of Ti / Al 1:21, After 130 minutes, the polynerizing is stopped. The composition and properties of the material are given in the table. The polymer yield of 6.1 kg / g Ti,

Example 9. The process is conducted under the conditions of example 5 for 15 minutes. Output PP 2.15 g. The composition and properties of the material are shown in the table.

Example 10.10g of preliminarily calcined graphite is placed in a glass ampoule and evacuated. Then, 0.04 g are fed (and the solution is kept for 20 min at and 0.03 g of TiCl4 (3-10 mol / m) are introduced. The filler, with the catalyst thus deposited, is fed in a stream of inert gas to the metalogical reactor,

55 and 150 cm of n-heptane and 0.04 g of (C2Hf) 2AlCl (Ti / Al ratio 1J 21) were introduced, the temperature was lower, propylene was introduced to a pressure of 4 atm and polymerization was carried out at a displacement of 5 minutes. Output PP2a5g. The composition and material properties are listed in the table.

Example 11 (control). The process is conducted under the conditions of Example 1 using 2 g of graphite, 0.024 g () and 0.04 g of TiCl4, iTO is 4, 7 10 mol / m, Co-catalyst (). added in an amount of 0.28 g. Ti / Al ratio 1:11. Polymerization of propylene is carried out in the presence of 0.05 atm of hydrogen under a pressure of 42 atm. Of propylene at a temperature of 70 ° C for 28 minutes. The composition and material properties are given

in the table,

Example 12 (control). In grams of graphite, they are placed in a glass ampoule and vacuum at 200 ° C, then in a stream of inert gas or in vacuum, T1C1f is fed in the amount of 0.06 g under stirring, which is 7.9-10 mol / m, then into the same the flask serves 0,038-g () A1C. The graphite thus treated is transferred in a stream of inert gas to a metal reactor, to which monomer and cocatalyst (.) A1C1 are fed in an amount of 0.31 g. Polymerization is carried out in a liquid monomer medium at 70 ° C and a pressure of 40 atm. After 120 mi, the polymerization is stopped. The polymer yield per gram of transition metal is 2.8 kg. The composition and properties of the material are given in the table.

Example 13 (control). 10 g of graphite is placed in a glass ampoule, evacuated at 200 s for 1 h, then transferred in a stream of inert gas to a metal reactor and the required amount of monomer is fed.

The temperature is raised to, g (C2H5) A1C1 is fed, held for 20 minutes, TiCl is fed in an amount of 0.0098 g, which is 1.0 and 10 ° mol / m of graphite.

Polymerization is carried out at 70 ° C, pressure of 42 atm 60 min. PP yield of 8.5 g. PP output of 1 g of titanium is

2.9 kg. The composition of the product and properties are given in the table.

Example 14 (control). 4 g of graphite is placed in a glass ampoule and evacuated at 200 s, then B is injected with an inert gas stream or under vacuum (0.038 g) of AlCl () is stirred, kept for 20 min and 0.06 g of TiCl2 is fed into the same flask, which is 15.8–10 mol / m, after which, in a stream of inert gas or monomer, is transferred to a metal reactor, to which monomer and cocatalyst (C2Hy) 2A1C1- are fed in an amount of 0.31 g. Polymerization is carried out in a liquid monomer medium at and pressure 40 atm After 40 min, the polymerization is stopped. Polymer yield 1 kg per. Gram of titanium, Total 1.5th PP output 15 g. The composition and properties of the material are presented in the table.

Example 15 (control). The process is conducted under the conditions of Example 1 using 9 g of artificial graphite (spherical) with a surface of 5, 0.024 g (C2H) 2A1C1 and 0.04 g of TiCl (4.6 kU mol / m). Atomic ratio. Ji / AlflMO.

The polymerization was carried out for 70 minutes at 70 ° C and a pressure of 40 atm. Out of polypropylene per gram of transition metal 4.3 g. The composition and properties of the material are shown in the table. Example 16 (control). 15 g of graphite are placed in a glass ampoule, evacuated at 200 ° C for 1.5 h, then, in a stream of inert gas, are fed to a metal reactor blown with an inert gas, evacuated at 70 ° C, 150 cm of n-heptane is released, a propylene pressure of 5 atm is created, 0,0178 g of TiCl подают is fed, held for 20 minutes and 0.2 g (CH gAlCl (which is 1.25-10 mol / m) or 0.12% by weight of a titanium compound in relation to graphite) are supplied. The polymerization is carried out at 70 seconds and 60 minutes. PP yield per gram of transition metal is 0.24 kg. The composition and properties of the composition are given in the table.

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Editor I. Segl nick

Compiled by A, Kulakova Tehred L. Oleinik

Order 3454/20 Circulation 470

VNSHSHI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

Production and printing company, Uzhgorod, st. Project, 4

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1 Corrector I. Erdeyi

Subscription

Claims (2)

1. Electrically conductive material containing graphite particles with a polyolefin coating, characterized in that, in order to reduce the specific volume resistance and increase the mechanical strength, it contains graphite particles scaly form with polyolefin coating 0.2-2 ^ 0 μm thick, made of polypropylene mol. May 0.75-1.5 <10 ^{6 of the} following composition, wt.%: Isotactic polypropylene 93-97 Atactic polypropylene 1.5-4 Stereo _ polypropylene 1.5-3 2. A method of producing an electrically conductive material by polymerization of a ω-olefin on the surface of graphite in the gas phase, in a mass or in a medium of a hydrocarbon solvent in Φ the presence of a catalyst consisting of titanium tetrachloride and diethylaluminium chloride, characterized in that, in order to reduce the specific volume resistance, increase the mechanical strength of the product and increase the productivity of the process, propylene is used as a ού-olet fin and the polymerization process is carried out on the surface of flaky graphite, pretreated diethylaluminum chloride, titanium tetrachloride and then with titanium tetrachloride Content 1,25ΊO ^'6 -1,25'10' ⁵ mol per 1 m ² surface Graphite. 511 ,,, 1240761 ¹ 1240761 ϊ