UA82874C2 - Process for the preparation of ion-exchange catalyst - Google Patents

Abstract

A process for the preparation ion-exchange catalyst, which contains sulfonated polyethylene and styrene copolymer with divinylbenzene, which is prepared by co-polymerizing styrene with divinylbenzene inside the granule of polyethylene, and then prepared copolymer is subjected to sulfurization. The ion-exchange catalyst with increased activity and strength is prepared.

Description

Description of the invention

The invention relates to ways of obtaining ion exchange catalysts. 2 A known method of manufacturing catalysts based on ion exchange resins and thermoplastic polymer materials by mixing them, heating to the melting temperature of the thermoplastic and forming the finished product by the extrusion method (1). However, the ion exchange capacity and activity of the catalyst obtained by this method is partially reduced during high-temperature treatment. In addition, during swelling in water, hydration of functional groups takes place, which is accompanied by an increase in the volume of the catalyst (by 2-3 times) and a decrease in its 70 mechanical strength.

The closest analogue of the proposed action is the method of preparing an ion exchange catalyst, which includes mixing powders of the copolymer of styrene and divinylbenzene with a thermoplastic polymer material, heating the mixture to the melting temperature of the thermoplastic, forming the mixture by the extrusion method, and chemically treating the formed material with a powerful sulfonating agent (2). 19 The catalyst obtained in this way is heterogeneous in its structure, not elastic enough and does not have the required activity and mechanical strength. There are great difficulties in grinding the copolymer of styrene with divinylbenzene.

The purpose of this invention is to obtain an ion exchange catalyst with increased activity and improved physicochemical properties.

The goal is achieved by the proposed method of obtaining a catalyst with ion-exchange properties, which contains swelling of granular thermoplastic polymer material in a reaction mixture of styrene, divinylbenzene, benzoyl peroxide with subsequent polymerization. In the process of copolymerization of styrene with divinylbenzene, a polymer spatially cross-linked structure is formed, integrated inside the granules of a thermoplastic polymer material in the "snake in a cage" type, with subsequent treatment of the resulting matrix with 22 chlorosulfonic or sulfuric acid. Gee)

The difference in the method is the change in the process of creating the initial matrix of the ion exchange catalyst itself. This method creates favorable conditions for the uniform distribution of one polymer structure in another.

In addition, there is a graft copolymerization of styrene and divinylbenzene on thermoplastic macromolecules, which forms a chemical bond between polymer structures in contrast to the mechanical mixture of solid particles of I copolymer of styrene with divinylbenzene and thermoplastic material in known methods. m.

All this contributes to obtaining an ion exchange catalyst with increased activity and strength.

Example 1 so

1.5 dm of desalted water is loaded into a three-necked glass flask and heated to 952C, then the prepared mixture of 1.5 g of starch is poured into 50 cm? desalinated water. The mixture is stirred in the reactor for 20 min., and then the temperature is increased to 98 °C and kept at this temperature for 30 min. A homogeneous solution of starch with a viscosity of 8-20 centipoise is obtained.

In another (5 dm) reactor, high-pressure polyethylene M 10703 - 020 is swollen in a monomer mixture consisting of 390 cm3 of styrene, 18 cm3 of divinylbenzene, and 4 g of benzoyl peroxide. The amount of polyethylene - 1 kg. Swelling is carried out with stirring at a temperature of 50 °C. In order to improve the conditions of transportation, desalinated water is added in the amount of 3 dm. Swelling is carried out for 5 hours. At the end of the swelling, stop the stirrer, stand for 0.5 hours to stratify and drain the water. After draining the water, the previously prepared starch solution at a temperature of 5526 is poured into the reactor.

Copolymerization is carried out with a working stirrer in the following mode: - raise the temperature to 702C for 0.5 hours and hold at this temperature for 2 hours; (ог) - raise the temperature to 802С in one hour and hold at this temperature for 6 hours; t - raise the temperature to 902C in 0.5 hours and hold at this temperature for 2 hours.

At the end of the copolymerization, the contents of the reactor are cooled, and the mother liquor is separated. The copolymer is washed with water and dried to a moisture content of no more than 0.5% by mass. -I 50 300 g of the obtained copolymer are loaded into a three-necked reactor for 2 dm, and 720 cm? of dichloroethane and kept for 5-10 hours at a temperature of 20-30oC for swelling. Then, with stirring, 380 cm3 of chlorosulfonic acid is added in small portions during an hour and sulfonation is carried out at 50 2C for 10-12 hours. Excess chlorosulfonic acid is decomposed with water, filtered from granules. dv Then the granules are treated with steam to remove dichloroethane and saponify chlorosulfo groups.

The resulting catalyst has an exchange capacity of 2.8 mmol/g, a moisture content of 47 9o, a swelling coefficient of 1.22, and a value (F) of mechanical strength of 25 kg/granule. from Example 2

The graft copolymer obtained in the amount of 300 g (as in example 1) is poured with 600 g of dichloroethane to cause swelling of the granules, and after 5 hours, 1500 g of sulfuric acid with a concentration of 96-100 95 is poured in. The mixture is kept for 15 hours at a temperature of 100-110 at mixing Then the acid is drained, the granules are washed with distilled water and dried. The resulting catalyst has an exchange capacity of 2.9 m-mol/g, a moisture content of 48 9o, a swelling coefficient of 1.20, and a mechanical strength of 20 kg/granule.

Example C 65 Preparation of ethyl tert-butyl ether.

The device consists of 2 three-liter flow-through reactors, into which 0.5 dm of the catalyst obtained in examples 1, 2 is loaded. The design and connection scheme of the reactors allow changing the contact time of the reagents, the volume velocity, and controlling the temperature and pressure in the system. Conversion of isobutylene into ethyl tertbutyl ether, the content of which in the butane - butylene fraction "- 14 95 wt. occurs under the following conditions:

The temperature is -60C

Pressure - 1l2mPa

Volume speed -10

The molar excess of alcohol is -1.5

The reaction product is freed from unreacted alcohol by washing with distilled water, then ethyl tert-butyl ether is distilled from it at a temperature of 69-722C.

The degree of conversion of isobutylene is 98.0 905

Example 4

The same as in example 3.

The temperature is -5296

Pressure - 1.0 mPpa

Volume speed -1.5

The molar excess of alcohol is -142

The degree of conversion of isobutylene is 95.0 95

Literature: sch 1. Author's certificate USSR Mo 459910 cl. In 01 | 31/08 1972 2. Author's certificate of the USSR Mo 1075499 cl. In 01 | 10/31/1982 Go)

Claims (1)

Formula of the invention "I Method of obtaining an ion exchange catalyst, which contains sulfonated polyethylene and a sulfonated copolymer of styrene with divinylbenzene, which differs in that the polymer base obtained by copolymerization of styrene with divinylbenzene inside a polyethylene granule is subject to sulfonation. so shi | | | that with the Official Bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2008, M 10, 26.05.2008. State Department of Intellectual Property of the Ministry of Education and Social Science of Ukraine. - with . and? so ko so - ch ko 60 b5