SU204592A1 - METHOD OF OBTAINING COPOLIMERS A-OXIDE ALKADIENES - Google Patents

Description

This invention relates to the field of producing copolymers of alkadien α-oxides.

The proposed method involves the production of copolymers of α-oxides of alkadiens with vinyl or divinyl. monomers, as well as ternary copolymers of α-oxides of alkadiens with vinyl (or divinyl) monomers and with α-oxides of the general formula

С-СНз, R / / О

where R and R-H, CH2 CH 2 SNO-, CI-L C-C00,

nn

alkyl, haloalkyl or aryl, by copolymerization of the corresponding monomers in the presence of aprotic acid or its ester as a catalyst.

The ratio of o-oxide of alkadiene and the unsaturated monomer varies from 0.05: 1 to 1: 0.05. In the preparation of terpolymers, the ratio of α-alkadiene, unsaturated monomer and other oxide varies from 0.05:: 0.05: 1 to 1: 0.05: 0.05 and from 0.05: 1: 1 to 1: 1: 0.05.

RIX

C —CH Rs,

Ra

where R, i CH2 CH-, CH3-CH, CH-, Rs and Ra can be H, CH3.

As unsaturated monomers, monomers used to obtain rubbers, plastics, fibers, such as vinyl alcohol esters and ethers, acrylic and methacrylic esters, nitriles and amides of these acids, styrene, vinyltoluene, α-methylstyrene, divinyl, can be used. , isoprene, piperylene and others.

The catalysts for the copolymerization of the above monomers are Friedl Crafts catalysts, such as FeCla, AlCl3, BFg, SnCli, and

their esters.

A change in the amount of catalyst (from 0.1 to lOVo) is an additional possibility of obtaining polymers with the desired properties, since the amount of catalyst affects

the best results are obtained when carrying out the reaction at 40-80 ° C. As solvents, substances or their mixtures, such as carbon tetrachloride, chloroform, heptane, dioxane, benzene, etc., can be used. At the same time, there are solvents in which no polymerization is observed. These include, in particular, alcohols and amines. However, more often, it is much more convenient to carry out the polymerization without using any solvents.

The yield of copolymers, depending on the reaction conditions (temperature, amount of catalyst, ratio of monomers and duration of the process), ranges from 25 to 97%.

The copolymerization can be carried out in an atmosphere of inert gases, such as nitrogen or argon, or in air at atmospheric pressure, under vacuum or at elevated pressure.

Copolymers contain reactive groups and can be used to produce rubber, plastics, etc.

Example 1. In a pre-washed nitrogen ampoule load of 1.17 ml of isoprene monoxide and 0.79 ml of acrylonitrile. 3 ml of dioxane are added to the mixture and the ampoule is frozen in a mixture of acetone and dry ice. 0.1 ml of boron trifluoride etherate is added to the cooled reaction mixture. The vial is sealed and placed in a thermostat with a temperature of 80 ° C and polymerization is carried out at this temperature for 40 hours. The vial is cooled and opened. The copolymer is purified by reprecipitation from benzene solution to n-heptane. The output of the copolymer 76 about / about. It contains 2.9 o / o. nitrogen.

Epoxy groups in the copolymer are not detected.

Example 2. In a nitrogen-washed ampoule load of 1.17 ml of isoprene oxide, 1.19 ml of methyl methacrylate and 0.5 ml of boron trifluoride etherate. After cooling in a mixture of dry ice and acetone, the ampoule is sealed. The copolymerization process is carried out in a water thermostat at a temperature of 40 ° C for 72 hours. The resulting copolymer is purified by reprecipitation from an acetone solution in petroleum ether. The output of copolymer 53%. Characteristic viscosity 0,54; ;

Epoxy groups in the copolymer are not detected.

Example 3. A nitrogen-washed ampoule was charged with 1.17 ml of divinyl oxide, 0.6 ml of ethylene oxide and 1.37 ml of freshly distilled styrene, then 3 ml of carbon tetrachloride and 0.1 ml of CBS were added. After cooling, the ampoule is sealed and placed in a thermostat with a temperature of 65 ° C. After holding at this temperature for 38 hours, the ampoule is opened. The copolymer is purified by reprecipitation in n-heptane. The output of the copolymer 560/0. Characteristic viscosity 0.41.

The copolymer contains 31 ° / o double bonds.

Subject invention

A method for producing copolymers of alkadien α-oxides, characterized in that, in order to expand the range of polymeric materials, α-alkadiene oxide is copolymerized with vinyl or divinyl monomers in the presence of aprotic acid or its ester as a catalyst.

2. A method according to claim 1, characterized in that, in order to obtain ternary copolymers, a-oxide of the general formula is introduced into the initial polymerization mixture

g, c-ca, k /

40 where R and R H, CH, CHCOO-, CHO C-COO-,

SNS

alkyl, haloalkyl or aryl.