A method of obtaining a catalyst component for the polymerization of butadiene-1,3

 

(57) Abstract:

Usage: as a component of the catalyst on the basis of diisobutylaluminium for the polymerization of butadiene-1,3, under the influence of cobalt containing catalyst system. The inventive source reagents-triisobutylaluminum and aluminium chloride, are taken in the ratio of 2.00:(1,06-1,23) (molar) or 1,000:(0,357-0,415)(mass) at 60-65oWith that result of their mixing product directly after filtration and dilution used in the polymerization of butadiene-1,3.

The invention relates to catalytic chemistry, in particular the production component of the catalyst on the basis of diisobutylaluminium (DIBAH) for the polymerization of butadiene-1,3, under the influence of cobalt containing catalyst system.

The proposed method can find application in the field of ORGANOMETALLIC chemistry and technology of obtaining alyuminiiorganicheskikh compounds for the synthesis of catalysts for the polymerization of dienes and olefins. Obtained with the application component of the catalyst based on DIBAH synthesized in accordance with the proposed method, CIS-1,4-polybutadiene (PB) can be used in the tyre industry for manufacturing">

Known industrial method for the synthesis of DIBAH based on the interaction of triisobutylaluminum (CHIBA) and aluminum chloride [1] According to this method in an environment purged of nitrogen is preparing a suspension of aluminium chloride in a hydrocarbon solvent (gasoline), which is the calculated amount CHIBA molar ratio trialkylamine and aluminum chloride is 2: 1,0-1,1. The temperature of the reaction mixture in the range of 60aboutWith supported by feed rate CHIBA, and the feed rate of the coolant in the jacket of the reactor. After the introduction, the number CHIBA reaction mixture is maintained under stirring for 1-2 h at 60-80aboutC, cooled and filtered. The yield of the final product is 90-95% Synthesized in accordance with the method similar to DIBAH characterized by mass (atomic) ratio CL/Al. theoretical mass ratio of CL/Al in DIBAH is 1,315 (atomic 1,00). The resulting product mass ratio CL/Al is of 1.27 and 1.35 (atomic 0,965-1,03).

When carrying out the polymerization of butadiene-1,3 under the action of cobalt containing catalyst system using DIBAH synthesized according to the method similar with the release of 85-95% PB is formed, with the shows that in the final product ratio CL/Al close to theoretically calculated. The disadvantages of the method-analogue in the case of the application of DIBAH as a component of the catalyst is cobalt containing catalyst system can include a broad range of content of CIS-1,4-units and . Some batches DIBAH obtained PB containing 90-93% CIS-1,4-units, with 100000-150000.

Closest to the proposed method of obtaining alyuminiiorganicheskikh cobalt containing component of a catalyst for technological entity and achieve results is the method of obtaining DIBAH from CHIBA and aluminum chloride contained in the source of information [2] In accordance with the method of the prototype to CHIBA add a powder of aluminum chloride at a molar ratio of 2:1 and a temperature of 70aboutC. After stirring for 1.5-2 h at 50-60aboutWith the resulting product is subjected to distillation in vacuum and get DIBAH with the release of 88-93% and a boiling point 86-88aboutWith at 0.2-0.3 mm RT.article (120-123aboutWith 2-3 mm RT.cent.), the mass ratio of CL/Al is of 1.28 and 1.35 (atomic 0,97-1,03).

When carrying out the polymerization of butadiene-1,3 under the action of cobalt containing catalyst system with ispolzuew, is 275000-320000. Analysis obtain DIBAH in accordance with the method of the prototype shows that in the final product ratio CL/Al is close to theoretically calculated and PB obtained by the use of DIBAH synthesized according to the method prototype, conform to the required microstructure and

The disadvantage of the prototype method is the use of vacuum distillation of flammable and explosive, energy-intensive process.

Comparison of methods for the synthesis of DIBAH by the method similar and the method prototype shows that, in accordance with the first of them get technically pure product with a larger output than in accordance with the method of the prototype. The polybutadiene obtained using DIBAH synthesized according to the similar, characterized by less stable properties than PB obtained by applying DIBAH synthesized by the method prototype, however, the technological scheme of the prototype method is more complicated than the method-analogue.

The purpose of the invention to develop the method for producing a component of the catalyst based on DIBAH, devoid of the above disadvantages and which allows to use it as a component of cobalt containing catalyticallyactive method of producing a component of the catalyst based on DIBAH from CHIBA in a concentrated state or in solution technical CHIBA in hydrocarbon solvent: heptane, gasoline, toluene, etc. and suspension of aluminium chloride in these solvents, taken in excess as compared with the stoichiometric ratio CHIBA/AlCl3. The excess is 6-23% of theoretical amount. In the synthesized component of the catalyst mass ratio CL/Al equal to 1.35-1.50 in (molar 1,03-1,14).

In accordance with the proposed method, the process is carried out in a reactor equipped with a stirrer and a jacket in the atmosphere of purified nitrogen. To 10-60% suspension of aluminum chloride in a hydrocarbon solvent under stirring served the calculated amount of concentrated CHIBA or 10-60% solution in hydrocarbon solvent for 20-25 minutes Mass ratio CHIBA: AlCl31.00:(0,357-0,415), molar 2,00: (1,06-1,23). In the process of mixing the components, the temperature of the reaction mass 30-60aboutWith supported by feed rate CHIBA, and the feed rate of the coolant in the jacket of the reactor. After adding CHIBA reaction mixture was stirred for 1.5-2 h at 50-70aboutC, is cooled to a temperature not exceeding 40aboutC and filtered. The filter is rinsed with a solvent, the yield of the final product 95-98% In the received component catalization-1,3 under the action of cobalt containing catalyst system using a component-based catalyst DIBAH, synthesized in accordance with the proposed method, with the release of 85-95% was obtained PB containing 96-97% of CIS-1,4-units and having 275000-320000.

Listed below are the test cases by the method similar to the prototype method, as well as examples illustrating the invention.

For the synthesis component of the catalyst based on DIBAH and polymerization of butadiene-1,3 used the following reagents and auxiliary materials: CHIBA concentrated and CHIBA technical. 10-60% solution in toluene, corresponding to THE 37.103-154-79, aluminium chloride anhydrous, technical THE 6-01-2-88, toluene, petroleum, brands And the highest and first category of quality GOST 14710-78, nitrogen, top grade GOST 8293-74, octoate cobalt TU 6-21-002-04151-88-92, cobalt naphthenate TU 6-09-07-76-78, hexane TU 6-09-3375-78, heptane TU 6-09-4520-77, cyclohexane TU 6-09-4357-47, Agidol-2 /2,2-methylene-bis-/4-methyl-6-tert.-the butylphenol// TU 38-1011617-76.

P R I m e R 1 (control by the method similar). In a reactor with a capacity of 0.2 l with jacket, equipped with a stirrer, thermometer, dropping funnel in an atmosphere of purified nitrogen is injected to 5.00 g (37,45 mmol) of aluminium chloride and 15 g of gasoline. With stirring from a dropping funnel over 20 min add 14.8 g (74,75 mmol) CHIBA, the molar ratio of CHIBA:AlCl3s, filtered, diluted with toluene and used in the polymerization of butadiene-1,3. The output of DIBAH is 93% mass ratio CL/Al in the final product of 1.27 (atomic 0,965).

Resulting from the polymerization of butadiene-1,3, using DIBAH synthesized as described in the method-analogue, PB (yield 85%) contains 92,0% CIS-1,4-units and has 149000.

P R I m m e R 2 (control method-prototype). In a reactor with a capacity of 0.2 l with jacket, equipped with a stirrer, thermometer, dropping funnel in an atmosphere of purified nitrogen, is injected 10,00 g (74,91 mmol) aluminium chloride, cooling the reactor to 15aboutWith and with stirring from a dropping funnel over 20 min add 29,70 g (150,0 mmol) CHIBA, the molar ratio CHIBA/AlCl32: 1, maintaining the temperature not above 60aboutC. the mixture is stirred for 2 h at 605aboutC, cooled, transferred to the apparatus for vacuum distillation and distilled under 120-123aboutAnd a residual pressure of 2-3 mm RT.article The output of DIBAH is 88% mass ratio CL/Al 1,30 (atomic 0,99). After dilution with toluene, DIBAH use in the polymerization of butadiene-1,3. Resulting from the polymerization of butadiene-1,3, using DIBAH, si is

P R I m e R 3. In a reactor with a capacity of 0.2 l, equipped with a jacket, stirrer, thermometer and addition funnel, in an atmosphere of purified nitrogen in place of 5.00 g (37,45 mmol) of aluminium chloride and 15 g of toluene. With stirring from a dropping funnel over 20 min added 12.3 g (62,12 mmol) of concentrated CHIBA, mass ratio CHIBA/AlCl3is 1,000:0,406, molar 2,000: 1,202 at 60aboutC. the mixture is stirred for 2 h at 605aboutC. the resulting solution is filtered, the filter washed and the final solution was diluted with toluene. The output component of the catalyst based on DIBAH is 98% mass ratio CL/Al in the final product is equal to 1.35 (atomic 1,03 G).

In the polymerization of butadiene-1,3 under the action of cobalt containing catalyst system using a component-based catalyst DIBAH obtained polymer (yield 92%) containing 97.2% of CIS-1,4-units and having = 275000.

P R I m e R 4. In a reactor with a capacity of 0.2 l, equipped with a jacket, stirrer, thermometer and dropping funnel in an atmosphere of purified nitrogen in place of 10.00 g (74,91 mmol) of aluminum chloride and 20 g of toluene. With stirring from a dropping funnel over 25 min add 27,70 g (139,90 mmol) CHIBA in the form of a 45% solution in Tolu is it the mixture is stirred for 2 h at 605aboutC. the resulting solution is filtered, the filter washed and the final product is diluted with toluene. The output component of the catalyst based on DIBAH is 95% of the mass ratio CL/Al in the final product is 1,50 (atomic -4 1,14).

In the polymerization of butadiene-1,3 under the action of cobalt containing catalyst system using a component-based catalyst DIBAH obtained polymer (yield 94%) containing 96.4% of CIS-1,4-units and having = 320000).

P R I m e R 5 (control). In a reactor with a capacity of 0.2 l, equipped with a jacket, stirrer, thermometer and dropping funnel in an atmosphere of purified nitrogen in place of 5.00 g (or 37.4 mmol) and 10 g of toluene. With stirring from a dropping funnel over 20 min add 16,00 g (80,81 mmol) of concentrated CHIBA, mass ratio CHIBA/AlCl31.00:0,312, molar 2,00: 0,927 at temperatures up to 60aboutC. the mixture is stirred for 2 h at 605aboutC. the resulting solution is filtered, the filter washed and the final solution was diluted with toluene. The output component of the catalyst based on DIBAH is 96% of the mass ratio CL/Al in the final product is equal to 1,25 (atomic 0,950).

In the polymerization of butadiene-1,3, under the action was cobal the EP (yield 89% ), containing 88% of CIS-1,4-units and having = 98000.

The analysis of these examples allows to conclude that the cobalt containing catalyst catalytic systems on the basis of DIBAH synthesized according to the proposed method allows to obtain the desired polymer microstructure and molecular weight in case of compliance with the conditions set forth in the characterizing part of the formula of the proposed invention.

When exceeding the lower limit of the ratio CL/Al in the component of the catalyst based on DIBAH during polymerization using it get PB containing 90% CIS-1,4-units (see example 5). When exceeding the upper limit of the ratio CL/Al in the component of the catalyst based on DIBAH during polymerization using it see the course side processes (alkylation solvent and chain transfer to polymer) used in the conditions.

Thus, the mapping is the subject of the invention is method for the synthesis of catalyst component with existing methods shows that the proposed method of synthesis allows for the increase of mass ratio CL/Al up to 1.35:1,50 (atomic 1,03:1,14) to abandon the stage distillation end prodaced with the formation of PB with the desired microstructure and molecular weight. Stage distillation is energy-intensive process, so the synthesis of DIBAH on the prototype method is carried out with concentrated CHIBA. The advantage of the proposed method is that it allows the synthesis of a component of the catalyst based on DIBAH as using concentrated CHIBA, which is convenient for transportation of the final product, and using 10-60% solution CHIBA, thereby enabling synthesis directly on the plants for production of synthetic rubber.

An additional advantage of the proposed method compared with the method of the prototype is a higher yield of the final product.

A method of OBTAINING a CATALYST COMPONENT FOR the POLYMERIZATION of BUTADIENE-1,3 interaction triisobutylaluminum (CHIBA) in a hydrocarbon solvent with a suspension of aluminum chloride AlCl3when 60 65o, Characterized in that the hydrocarbon solvent used toluene and the process is conducted at a molar ratio of CHIBA AlCl32,0 1,06 1,23.

 

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