SU286848A1 - - Google Patents

Description

METHOD FOR OBTAINING ISOBUTYL COPOLYMERS A method is known for preparing isobutylene copolymers with dienes by copolymerizing monomers in a hydrocarbon solvent in the presence of alkyl aluminum halide activated with hydrogen chloride as a catalyst 94. The proposed method, which involves the use of a qualitatively new catalyst — alkyl aluminum chloride with a molar ratio of alkyl group to chlorine in the range of 0.5–1.0, makes it possible to obtain higher molecular weight copolymers. The following hydrocarbon solvents can be used: isopentane, hexane, heptane, butane, isobutane, toluene, gasoline, etc. The catalyst is ethyl aluminum dichloride (C2I5A1C12) or a mixture of it with diethylaluminium chloride (CdHalon) with a ratio of ethyl group to chlorine and ethyl chloride / CdHylO2 with a ratio of ethyl group to chlorine and ethyl chloride / ethyl chloride (CrH2A1C12). , 5 to 1.0, also dissolved in hydrocarbon solvents, or a similar catalyst with the replacement of the ethyl group by another alkyl, in particular by the isobutyl group. Isobutylene and diolefins, mainly isoprene, are used as monomers. Any hydrocarbon may be used as the solvent of the monomers and the catalyst.

WITH DIENA, dissolvable polymer is also formed. Polymerization is carried out at temperatures ranging from -30 ° to -110 ° C. The polymer solution has a different viscosity depending on temperature, concentration and its molecular weight. Example 1 Polymerization was carried out in a glass stirred reactor equipped with a catalyst cartridge. 25 ml of isopentane and 25 ml of a mixture of isobutylene with isoprene (3% by volume of isoprene from isobutylene) were loaded into the polymerizer. Isopentane, isobutylene, and isoprene were dried with alumina before use, and evaporated in an atmosphere of nitrogen, dried and freed from oxygen. The moisture content of the products was 0.005-0,0005%. The catalyst was ethyl aluminum chloride with an e / Cl ratio of 0.5. Ethylaluminium chloride was obtained as an 80% solution in gasoline ("Galosh" brand) by reacting diethylaluminum chloride with an appropriate amount of aluminum chloride and diluted to a concentration of 0.0075 g / ml with isopentap. 1.5 ml of the diluted catalyst solution was poured into the catalyst cartridge. With stirring and temperature from - 84 °

to - 92 ° C the catalyst solution was introduced into the mixture. Stirred for 30 minutes The viscosity of the reaction mass gradually increased, the solution remained mobile and mixed easily. After 30 minutes, the reaction was terminated with alcohol. The polymer was precipitated and dried. By weight, its yield, molecular weight (io Staudinger) and unsaturation were determined.

Polymer obtained 4.2 g; polymer yield 24.3%; a pier weight. 51,000; unsaturation 2.1 mol. %; the polymer content in the solution is 12 wt. %

Example 2. The polymerization was carried out as described in Example 1, but hexane was used as the solvent.

Polymer obtained 2.84 g; polymer yield 16.2%, mol. weight. 7GOOO; saturation

1.7 mol. %; the content of polymer in solution is 8 wt. %

Example 3. Polymerization was carried out as in Example 1, but heptane was taken as the solvent, the amount of monomers in the mixture was 25 vol. %, and the content of isoprene 4 about. % of isobutylene.

The polymer was obtained 2.05 g; yield 20%; a pier weight 40,000; inconsequence 3.5 mol. %; the content of polymer in solution is 10 wt. %

Example 4. The polymerization was carried out as described in Example 1, but butane was used as the solvent.

The resulting polymer 8.03 g; yield 4.6%; a pier weight. 31,000; 1.8% molar unsaturation %; the content of polymer in solution is 23 wt. %

Example 5. Polymerization was carried out as in Example 1, but toluene and a polymerization temperature in the range of from -67 ° to 73 ° C were used as the solvent.

Polymer obtained 11.2 g; yield 64.3%; a pier weight 17,000; the unsaturation of 1.5 mol. %; the content of polymer in solution is 32 wt. %

Example 6. The polymerization was carried out as described in Example 1, but gasoline (of the “Galosha” brand) was used as the solvent.

Polymer 6.15 g; polymer yield 35%; a pier weight 36,000; nonsaturation

1.8 mol. %; the content of polymer in solution is 18 wt. %

Example 7. The polymerization was carried out as described in example 1, but the polymerization temperature was -60 ° C.

The resulting polymer is 2.5 g; polymer yield 15%; a pier weight 41,000; the saturation of 1.71 mol. %; the polymer content in the solution of 7.5 wt. %

Example 8. Polymerization was carried out as in Example I, but instead of isoprene, butadiene was taken in an amount of 3% of isobutylene and the polymerization temperature was about - 70 ° C.

The polymer was obtained 14.4 g; polymer yield 80.0%; a pier weight 48,000; unsaturation 0.5 mol. %; the content of polymer in solution is 40 wt. %

as described in example 1, but the polymerization temperature was -110 ° C.

Polymer obtained 1.7 g; yield 9.6%; a pier weight 109,000; the saturation of 1.9 mol. %; the polymer content in the solution of 4.8 weight. %

Example 10 Polymerization was carried out as described in Example 1, but hexane with a moisture content of 0.1% was used as a solvent.

A polymer was obtained of 5.24 g; yield 30.0%;

a pier weight 31,000; unsaturation of 1.9 mol. %;

the content of polymer in solution is 15 wt. %

Example 11. Polymerization was carried out in a metal (copper) reactor with

stirrer The volume of the charge is 600 ml. The content of monomers in the charge of 25 vol. %, filed catalyst solution of 5.5 ml, containing ethyl aluminum chloride 0,0182 g / ml. Polymer obtained 42 g; yield 40%;

a pier weight 36,000; 1.saturation of 1.9 mol. %; the content of polymer in solution is 10 wt. %

The Mooney polymer viscosity is 35. From this polymer, a rubber compound was prepared, the vulcanizer of which was subjected to physical and mechanical tests.

The recipe for rubber compound, weight. h .; rubber 100.0; sulfur 2.0; captax 0.65; thiuram 1.30; zinc oxide 5.0; stearin 3.0; carbon black 50.0.

The vulcanization conditions and test results were as follows: the vulcanization temperature was 143 ° C; cure time 40 min; module 300% -46 kg / cm; module 400% - 63 kg / cm2; module 500% -94 kg / slS; tear resistance 184 kg / cm; relative elongation of 740% and residual 53%.

Example 12. Polymerization was carried out on a pilot plant in a reactor with a capacity of 100 liters. Cylindrical Reactor with

a glass embedded inside and tubes for circulating the reaction mass. Mixed with a stirrer pump located at the bottom of the reactor. The polymerization was carried out at low temperature. They were cooled with ethylene boiling in the annular space. The mixture and the catalyst were continuously fed to the reactor, and the polymer solution was poured from the reactor into the tank to terminate the reaction. The solution then entered the apparatus with hot water to distill the volatile and release the polymer. The polymer was separated from the water on the sieve, then dried in a worm-squeeze press. The mixture contained 47.2% isobutylene,

0.96% isoprene, the rest isopentane. The catalyst was ethyl aluminum nitride dissolved in isopentane. The catalyst concentration is 13.5 g / l. The feed mixture 210 210 l / h, the catalyst solution 1.5-2 l / h.

Polymerization lasted for 5 hours and was terminated due to the absence of a free container for receiving the polymer solution. During the entire polymerization, the regime temperature was maintained without difficulty During the polymerization process, samples of the reaction mass at the reactor outlet were taken every hour at the reactor outlet to control the content

polymer in solution and determining the molecular weight and unsaturation of the polymer. The results of the analyzes are given in table. one.

Table 1

Example 13. The polymerization was carried out as in Example 12, but under the following conditions: the mixture of isobutylene 47.4%, isoprene 1.14%, the rest is isopentane. The concentration of the catalyst solution is 6.6 g1l. Polymerization temperature from -99 to - 102 ° C. The flow of the charge 100-130 l / h, the supply of the catalyst solution of 1.5-2.4 l / h. Polymerization lasted 8 hours and was discontinued due to the lack of raw materials. The operating temperature was maintained without difficulty, the solution was easily flowing.

The results of the analyzes are given in table. 2

table 2