SU509208A3 - Method of producing polymerization catalyst - Google Patents

Description

following formula I, you can bring with: blowing; СНз-SO- (СН2) 4-SO-CHa ОНз-б02-Ъ 02-Шз CsHs-SO- (СН2) b-SO-CeHs ОНз-SOa- (СН2) 4-SO2-СНз and others. The concentration of the catalyst at the polymerization is from 0.001 to 5% relative to the g-loading of the molomer or monomers, preferably from 0.01 to 1%. Example 1. Getting O ° CH5 - $ - (CH2) o-8-Syz and the corresponding reaction products using butyll; itn (catalyst A). 4.6 g of NaH (170 mmol) was charged into a three-necked flask equipped with a stirrer, an allelic funnel, and an Argoda thermometer with a current of Argoda; 100 cm of dimethyl sulfoxide was slowly added dropwise with stirring. All contents are stirred for 6 hours at + 40 ° C, then from (filter and titrated. To the reaction mixture containing 95 mmol of Na-Chromo-SO-CH3 was added 48 mula Br - CHg-CH3-CH3- CHj-Br, diluted in liO cm of dimethyl sulfoxide. The weakly exothermic reaction is carried out for 8 hours at 60 ° C, dimethyl sulfoxide is removed by vacuum distillation, ether is added and the sylgma is filtered and washed with cold tetrahydrofuran (50 sl1). hot tetrahydroFluor.nom, an extract in tetrahydrofura is not precipitated with anhydrous ether, It is filtered and dried, yielding 5.6 g of CH 3 —SO— (CH 2) b — SO — CH 3 (yield 56%). A 250 ml three-neck flask, previously purged with argon, equipped with a cooling droplet funnel and a thermometer, 4.1 g (19.4 mmol) of CH 3 -SO- (CH 2) 6-30-CH 3 are placed, then 200 ml of anhydrous dioxane are added (dioxane is dried over LiAlH 4). The heating is carried out up to 40-50 ° C up to complete dissolution and slowly add 40 mmol of Li-butyl in a solution of hexane. A noticeable gas evolution is observed and the temperature is raised to + 55 ° C. At the end of the reaction, a white precipitate is observed. The mixture is filtered for another 3 hours at 50 ° C. The reaction mixture is filtered, washed again with warm tetrahydrofur "ohm" in order to free itself from excess Li-butyl and possible non-reactive products, and dried in vacuo for 1-2 hours. The product thus obtained was dissolved in hexamethylphosphoramide. Calculated,%: C 43; H 7.2; S 28; Li 6.4. Found,%: € 42; H 7.5; S 28; Li 6.4. In a three-necked flask, previously purged with argon, equipped with a stirrer, an addition funnel and a thermometer, 0.2 g of catalyst A (0.90 mmol) is placed, 50 cm of tetrahydrofuran is added, which leads to the formation of a white suspension. 6 mmol of C2H5Br are added and stirring is continued for another 15 hours at 30 ° C. A clear solution is obtained which is evaporated to dryness and a white hygroscopic solid is obtained. Analysis by mass spectroscopy gave an average molecular weight of 266, which corresponds to the addition of two CzNb groups to catalyst A. Example 2. Reaction of CH3-SO- (CH2) b- -SO-CPZ with NaNHg (catalyst C). In a flask equipped with a glass stirrer and a funnel for loading with a jacket, 0.39 g of NaNH2 (10 mmol}) is placed, all dissolved in 40 cm of liquid ammonia at -70 ° C. 5 mmol of CH 3 -SO- - ( CH2) b - SO-CH3, suspended in 40 cm of tetrahydrofuran. Stirring is carried out for 10 hours at -45 ° C, NHz is removed and the dried solid is used for polymerization. The properties of a part of this sample are determined as follows in Example 1, by reaction with CzNbBg. The resulting product is analyzed by mass spectroscopy. According to the obtained results, the structure of the anal preceded by the previous procedure Example 3. The reaction between Mg (C2H5) 2 and (CH2-SO- (CH2) b-SO-CH3 (catalyst C). In a flask equipped with a magnetic stirrer, an addition funnel and a condenser, 0.5 g of CH3 -SO- (CH2) b-SO-CH3 (2.4 mmol, all this dissolved at + 40 ° C in 70 cm THF. Then a solution of 4.8 mmol, Mg (C2H5) 2 V 20 cm is added tetrahydrofuran. In this case, the formation of a precipitate and the release of gas, which stops after 30 minutes. The temperature of + 40 ° C is maintained for 18 hours, the opalescent solution is concentrated and precipitated in hexane, filtered, washed with tetrahydrofuran and hexane to remove unreacted substance. The dried precipitate is used for polymerization. Example 4. Reaction between Zn (C2H5) 2 and CH3 -SO- (CH3) 6-SO-CH3 catalyst. According to the procedure of Example 3, 0.75 mmol of SPZ-SO- (CH3) 6-SO-CH3 is reacted with 0.75 mmol of 7n (C3H5) 2- The gas evolution and opalescence of the solution are observed. The temperature is maintained at -f 50 ° C for 16 hours, the solution is concentrated and precipitated with hexane, washed with THF and hexane, dried, the precipitates are used for polymerization.

Example 5. The reaction between A1H3M (CH3) C and CH3-SO- (CH2) b-SO-CH3 (catalyst E).

Following the procedure described in the previous nimers, 0.57 mmol of CH3-SO- (CH3) b- -SO-CH3 is reacted with 0.57 mol of AlH3 (CH3) 3 in 40 cm of toluene. The temperature is maintained at 60 ° C for 1 hour, the precipitate is filtered, washed with THF and toluene, dried, and used for polymerization.

Note 6. Preparation of CH3-SOj- - (CH2) b-S02-CH3 and its reaction with C4H9Li (catalyst F).

In a three-necked flask equipped with a stirrer, a Haiel funnel, and a cooler, 1 g (4.7 mmol) of CH 3 —S — SO (CH 2) b — —SO — CH 3 is placed and dissolved, in a minimum amount of glacial acetic acid.

Heat 70 ° C and add the required amount of H2O2 dropwise. The reaction is carried out at 70 ° C for 10 hours, after which the reaction mixture is left overnight. A white precipitate forms, which is recrystallized from alcohol. The product is thoroughly dried under vacuum.

1.05 g of the desired product is obtained (R 87%). According to the procedure described in Example 1, 1.05 g (4.1 mmol) of CH3-SOa- (CH2) b-SO-CH3 reacts with 8.2 mmol of LiCiHg. The product is dried and dissolved in hexamethylphosphorus.

Calculated,%: C 38.0; H 6.2; S 25.2; Вг 5,5.

Found,%: C 37.5; H 6.0; BG 5.7.

The reaction is described in Example 1.

Mass spectroscopic analysis is in agreement, is fussed by interconnection, and has MB 298.

Example 7. Preparation of CH3-SO-SbH4-SOCH3 and its reaction with C4H9Li (catalyst G), CH3-S-SbH4-S-CH3 are obtained according to a known procedure.

This product is subjected to the oxidation under controlled conditions of H2O2 in CH3COOH to obtain as the reaction product a white solid, crystallized from pure alcohol with a melting point of 188 ° C. Analysis of this compound by mass spectroscopy and nuclear magnetic resonance shows that that the compound has the formula CH3-SO-SbH4-SO-CH3 According to the procedure described in Example 1, 1.5 g (8.4 mmol) of CH3-SO-SbH4-SO-CH3 reacts with 17 mmol C4H9Li. The product is dried, dissolved in hexamethylphosphoramide and used for polymerization.

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Examples 8-13. Polymerizations were carried out in a 250-cm-long vessel, purged with argon; first, the catalyst of example 1 is charged with a solvent, and then the monomer. The experiments were carried out in a thermostated bath at 30 ° C.

The data obtained are shown in the table.

note. HMPA — hexamethylphosphoramide; THF - lactone of trimethylacetic anhydride.

Ex. IM. 14.: In accordance with the procedure described above, 0.05 mmol of the CH3-SO- (CH2) 6-SO-CH3 rea.product product with NaNHs (catalyst H) in 25 cm THF is loaded into the vessel from which the air is removed, and then filled with argon. Then 63 mmol of propylene sulfide is added. The experiment was carried out in a thermostatically controlled bath at 30 ° C. 4.65 g of polymer was obtained (yield 100%) with g, pa; v. 2, 10, measured in toluene e at 30 ° C.

Example 15. An iB vessel under argon was charged with 0.05 mol of a catalyst prepared from CH3-S02- (CH2) b-S02-CH3, with LiC4H9 (catalyst F) in 25 cm of solvent (5 HMPA + 20 THF). Then 63 mmol of propylene sulfide is added. The experiment was carried out in a thermostatically controlled bath at 30 ° C. 4.65 g of polymer was obtained (yield 100%) with a viscosity of 1.84 dl / g, measured in toluene at 30 ° C.

1 tetrahydrofuran; DMF - dimethylformad. Pivalolactin Example 16. In accordance with the described procedure, 25 mg of the reaction product between MgCsHs and CH3-SO- (CH2) b-SO-CH3 (catalyst C) was charged to a vessel under argon, then the reaction mixture was dissolved in 30 cm HMPA and 63 mmol was added prolyl sulfide. The polymerization was carried out at 30 ° C and 4.4 g of floor was obtained, imier (98% yield); t 1.32 dl1g, measuring in toluene at 30 ° C.

Example 17. A vessel under argon was loaded with 0.05 mmol of precipitate obtained by the reaction of Zn (.C2H5) 2 .n CH3ZO- (CH2) in - -SO-CH3 (catalyst D), dissolved in HMPA, and 76 mmol of propylene sulfide is added. The polymerization reaction is carried out at 30 ° C. 3.4 g of polymer are obtained (yield 61%); t 1.86 dlg, measured in toluene at 30 ° C.

Example 18. 0.05 mmol of the product, half-finished by reaction between A1Hz1 CH3 and CH3-SO- (CH2) b-SO-CH3 (catalyst E), is loaded into a vessel filled with argon. The reaction mixture is then suspended. At 20-time HMPA. And 57 mmol of propylene sulfide is added to it. The polymerization reaction is carried out at 30 ° C, and 3 g of polymer are obtained (yield 70%); t 1.80 for 1g, measured in toluene at 30 ° C.

Example 19. 0.05 mmol of the product obtained by the reaction (catalyst G) is loaded under the vessel iB arton. The mixture was dissolved in HMPA. 63 mmol of propylene sulfide was added. The polymerization reaction is carried out at 30 ° C and 3.2 g of polymer are obtained (yield 70%); t (1.79 dlg, measured in toluene at 30 ° C.

Formula I 3 about b r e-t e n i

1. A method of producing a catalyst for polymerization by reacting metal IA, PA, P1A of the group of the periodic system

elements or its hydride, alkyl or amide derivative with compounds containing a sulfonic or sulfoxide group, characterized in that, in order to obtain a catalyst with increased activity, compounds containing at least two groups are used as compounds containing a sulfonic or sulfoxide group. SO and SO2 selected from derivatives containing one or more repeating units in the molecule

R-fX- (R) "n-Y-R,

where X and Y are the same or different - SO or SO2-rpynnbi;

R and R are a methyl, alkyl group containing 2-10 carbon atoms, a cycloalkyl, aryl, arylalkyl, alkylcycloalkyl group or divalent radicals capable of reacting with the ring closure;

R is a divalent arylene, alkali metal, alkylene, alkyl arylene, alkylcycloalkylene radical or methylene chain containing from 0 to 20 carbon atoms;

t 0 or 1;

n is an integer equal to 1.2 or 3.

2. The method according to l. 1, characterized in that the reaction between the metal or its derivative and a compound containing at least two SO and SO2-rpynnbi is carried out at a molar ratio of 10 to 0.3, preferably at a molar ratio of 1: 1 between the metal or its derivative and a group of SO and (or) S02 in the presence of a solvent, selected from aliphatic or aromatic hydrocarbons, tetrahydrofuran, dioxane, hexamethylphosphoramide and liquid ammonia, at a temperature from -80 to + 80 ° C.