SU492298A1 - Catalyst for the polymerization and copolymerization of ethylene, α-olefins and conjugated and non-conjugated dienes - Google Patents

Description

one

This invention relates to the field of catalysis in polymer chemistry, in particular to catalysts for the polymerization and copolymerization of ethylene, olefins and conjugated and unsupported dienes.

A catalyst is known, for example, for the polymerization and copolymerization of olefins, consisting of a metalloorganic compound of a metal of 1-III groups and a compound of a transition metal of one of the groups on a polymer carrier. As polymeric carrier, polyamide-type polyaerols, poly mines, polynitriles, polydienes are used. The use of polar homopolymers as carriers, which are insoluble or poorly soluble in hydrocarbon media, leads to the formation of heterogeneous catalysts that are insoluble in hydrocarbon,

I environment. Therefore, these catalysts are characterized by the following significant shortcomings: the reactions take place only on the catalyst surface, the polymer contains catalyst particles that are very difficult to remove and regenerate.

A catalyst has been proposed for the polymerization and copolymerization of ethylene with olefins and conjugated and non-conjugated dienes, in which a carrier rubber is a crosslinked rubber-type polymer containing 5-SO Bec. soluble in the reaction medium gel.

The proposed catalysts swell, but do not dissolve in hydrocarbons and their halide derivatives, and are characterized by increased chemical stability to the reactions of reduction and oxidation. The compounds of the transition metal of the 1st group are deposited on a polymeric carrier in an amount of 2–20 wt.%; I. Of the transition metal compounds, halides, alkonides, acetylacetonates, allyltic and other compounds are used, preferably 4 iVOCOCgHg), / Vi. The transition metal compounds can be bonded in the gel via electron-donating or electron-withdrawing groups that are part of the carrier polymer (5-20 wt.; D) and are located in the main chain or in the side branches of the polymer. Such groups can be groups containing elements Y – V1 of the periodic system, preferably iV, P, O, 5, various unsaturated bonds. Polymers and copolymers capable of swelling in the solvents used in the polymerization and copolymerization, for example, various synthetic and natural rubbers, are used as the main substance of the polymerase agent. The complexation reaction is carried out at 0-200 ° C (depending on the reactivity of the reactants) in hydrocarbons and / or their chlorine derivatives. But at the end of the reaction, the resulting catalysts are thoroughly washed with a solvent to remove traces of a metal compound that is not chemically bound to the polymer carrier. Under similar conditions, gelatinous catalysts are obtained, which also contain chemically bound compounds of the denisines of metals of the 1-W group, which play the role of cocatalyst. The polymerization and copolymerization of these ethylene olefins is carried out in aliphatic, alicyclic, aromatic hydrocarbons or their chlorine-containing derivatives at 0–200 ° C, preferably at 40–160 ° C and a pressure of 0100 at. The reaction can also be carried out in a monomer suspension. The applied catalyst is used in the form of pellets swollen in a solvent of 0.1–5 mm in size. 4 which, unlike heterogeneous catalysts, are easily permeable throughout the volume for monomer molecules and dissolved polymer. The resulting polymer is dissolved in the polymerization medium, during the reaction or, if the polymer is insoluble at low temperature, it is separated from the catalyst by heating in a solvent in a separate apparatus. The catalyst freed from the resulting polymer can be reused for polymerization. In contrast to solid catalysts, the gel catalyst is not crushed and can be repeatedly used when cocatalyst is added to it. The performance of catalysts per 1 g of transition metal is close to the performance of stationary catalysts. The polymerization rate is constant almost throughout the entire reaction time and decreases only after the consumption of the cocatalyst. 11 polymers do not contain transition metal. The properties of the polymer or copolymer can be controlled by changing the composition and concentration of the monomer mixture, the catalyst, the temperature and duration of the reaction, as well as adding special chain transmitters to the reaction system, for example, N. Pd catalysts obtained, for example, on the basis of (, V ( a) t are characterized by the presence in the reaction medium of living chains. Therefore, such catalysts can be used to obtain block type copolymers. Catalysts synthesized on the basis of compounds of vanadium and titanium make it possible to obtain polymers based on ethylene, propylene, and conjugated and non-conjugated dienes. Catalysts derived from transition metal compounds (including HG allyl), preferably Tt, Co, and Mn, commonly used to polymerize dienes, allow polymerization dienes.

Cooking media

Example I. hinge 5-g industrial siloxane rubber of General formula

containing

-Jirt

2 mol. unsaturated groups are dissolved in 75 ml of cyclohexane and placed in a 250 ml ampoule. 3 of them are loaded with 0.5 g of 4-vinylpyridine and 0.075 g of dinitrile (bis) oil oil. The solution is degassed under vacuum (a residual pressure of no more than 5-10 mm Hg) and heated for 10 hours at 70 ° C. then, 0.075 g of benzoyl peroxide is introduced into the solution, the mixture is kept at 70 ° C for another 10 hours, the solvent is distilled off and the remaining product is dried. A product containing 10% by weight of electron donor groups is obtained, the resulting product swells, but does not dissolve in hydrocarbons, chlorinated derivatives of hydrocarbons and does not swell in lower alcohols, acetone and other polar solvents.

Example 2. A weighed portion of 5 g of an industrial synthetic rubber — a copolymer of ethylene, propylene, and ethylidene norbornene containing 1.54 n0l; unsaturated groups, treated as described above and get a product that is well swelling, but insoluble in hydrocarbons. In the same way, products based on rubbers and acrylonitrile, methyl methacrylate, diethyl aminoethyl ethyl acrylate, pure amine 1ROSFINOV, methacrylic acid, etc. are obtained.

Catalyst preparation

Example 3. A weighed amount of 0.5 g of the product obtained in Example 2 and containing IO / J poly 4 vipilpyridine is placed in 50 ml amulula containing 20 ml of absolute heptane. 0.1 g of IVCt is distilled there, the ampoule is sealed, kept for 34 hours at room temperature and

2 hours at 120 C. Then the vial is opened, the catalyst is washed with heptane and 20 liters of triisobutl-aluminum solution (0.26 mol / l) are added to it. The mixture was kept at room temperature for 24 hours and washed again with n-heptyl.

Example 4. A weighed portion I g of the product obtained in Example 2 is placed in a heptane-dichloroethane mixture ST: 1) "To the swollen product add 0.24 g ()

dissolved in this mixture. After 30 hours (20 ° C), the complex formed is separated by filtration and washed thoroughly with heptane.

Example 5. To I g of the product obtained in Example 2 and swollen in heptane, 0.25 g of V are added in a stream of argon.

ft

The mixture was left for 3 days under argon. The resulting complex is separated by filtration, washed and stored.

In sealed ampoules.

Example 6

A. To the sample of 5 g of partially cross-linked polybutadiene of 1,2-structure, swollen in heptane, add 2 g (,

dissolved in heptanedichloroethane

mixes. 110 after 2 days (.20 ° C), the image of the ovum and the complex is separated by filtration and washed thoroughly with heptane. B. To a portion of 1 g of the product obtained according to p. A, swollen in heptane, 0.3 g of diisobutyl aluminum chloride are added under vacuum. The mixture is kept

at 60 C during the day. After that, the resulting complex is thoroughly washed with heptane to remove unbound

diisobutylaluminum chloride and stored in. sealed ampoules.

Example V. To a portion of 0.5 g of cross-linked rubber containing -lOJd grafted methacrylic acid, add a solution of Grignard reagent in dithyl ether (CgH.jjMyOH, 2 mol per 1 mole of methacrylic acid) and incubate for 24 hours. After that, the mixture is washed with ether and the ether is distilled off. To the residue are added 20 ml of a solution of TiC (0.3 mol / l) in normal decane and heated for 6 hours. The resulting catalyst is washed with heptane and stored in sealed ampoules. Example 8. To a portion of 0.5 g of rubber, containing 18 grafted vinyl diphenylphosphine, add 30Ni solution of nickel acetylacetonate (0.1 mol / L) in diethyl ether. The mixture was kept for 24 hours, washed with ether, heptane, and stored in sealed ampoules. In a similar way, catalysts containing transition metal compounds of U-VIII groups are obtained. The components are introduced as a solution in hydrocarbons or their chlorine derivatives. polymerization Example 9. A weighed portion of 0.22 g of the catalyst prepared in Example 3 was charged to a 50-milliliter glass reactor. EO ml of purified n heptane and 5.6 ml of a 0.23 mol / l solution of triisobutylaluminum are also added there. The reaction mixture was stirred with a magnetic stirrer for about an hour at, then ethylene was introduced at a pressure of 3 at. After 3 h the supply of ethylene is stopped. 5 ml of methanol is introduced into the reactor and stirred for 1 hour. The reaction products are separated from the solution, dried and extracted with n-dodecane. The hot polyethylene solution is separated from the catalyst by filtration, the solution is cooled, the polyethylene is filtered off and dried. Characteristic viscosity (here and in the following examples, measured at 135 ° C in decalin AC; b Example 10. A weighed portion of 0.3 g of the catalyst prepared in Example 5 was loaded into a 0 ml metal reactor. 20 ml of purified -octane and o ml solution of dicyclohexenyl aluminum chloride mol / l in heptane). The polymerization of ethylene is carried out at 20 ° C with a constant pressure of 5 at. The reaction is judged by the pressure drop in the intermediate temperature-controlled measuring capacitance. After 3 h, the supply of ethylene is stopped, the pressure is reduced and the temperature in the reactor is increased to 160 ° C. After 2 hours, the reactor is cooled until ethylene is fed in again, the wire is polymerized for another 2 hours. Then the reactor is heated to 160 ° C and the hot polymer solution is separated from the catalyst. Yield 30 g, / 2x Example I .. Using the apparatus described in the maintenance example, a continuous polymerization of ethylene on the catalyst obtained in example 3 is carried out for 73 hours at i60 ° C and 17 at. The ethylene consumption rate remains almost constant over the entire time, 1.5. When polymerization is carried out under these conditions in the presence of the following systems: + + tri-aluminum alkyl (A) and TiS + pyridine-g-triheptyl aluminum (B), the catalyst is deactivated after 2 and 10 hours, respectively. Sample € 2. A. To 0.13 g of the catalyst obtained in Example 4 in vacuo, i5 ml of absolute octane and 0.5 g of di (cyclohexenylethyl) aluminium chloride are added. After 3 hours, ethylene is fed into the system. Polymerization conditions: temperature 36 ° C, pressure 2 at. After 43 hours, during which the reaction rate is constant, the reaction is stopped, the polymer is removed and treated as in Example 9. The yield is 1.5 g. N. B. The catalyst, washed in hot air with dodecane from polyethylene, is again used for polymerization. To do this, 15 ml of absolute octane and 0.63 g of di- (cyclohexenylethyl) aluminum chloride are added to it. After 4 hours, ethylene is fed to the system. Polymerization conditions: temperature 2G ° C, pressure 1.6 at. After 20 hours, during which the reaction rate is constant, the reaction is stopped, the polymer is treated as described. Output 0.5 g