SU1060622A1 - Process for producing butylacrylate rubbers with epoxy groups - Google Patents

Abstract

The method of producing butyl acrylate rubbers with EPOXY GROUPS by treating a copolymer of butyl acrylate, acrylonitrile and methacrylic acid with an epoxy-containing modifying agent in cjpejcie organic solvent at 80-100 & With the aim of reducing the synthesis time while maintaining a high degree of substitution to the arboxyl groups, simplifying the process and improving working conditions, vinyloxyethyl ester of hl is used as an epoxy-containing modifying agent. | Tsidola molar ratio; .karboksilnyh ether groups with "a polymer 5-7: 1, and as a catalyst - perftorI organic acid.

Description

The invention relates to chemical technology, in particular, to methods for producing butyl acrylate rubbers with reactive groups that can be used in the paint industry for the manufacture of combined coatings, as well as in the automotive industry for the manufacture of various seals and gaskets. Acrylic copolymers are known which contain reactive epoxy group CH-C-OS-4-C10 CH-CH-C in the side chain. o The reaction mass is purified from sodium chloride and the crude, containing a small amount of chlorine, the esters are distilled in vacuo. To obtain chemically pure products that are used in copolymerization processes, additional purification and subsequent distillation in vacuum is necessary. Under industrial conditions, the thus obtained unsaturated glycidol esters are difficult. In addition, they are toxic substances. Therefore, the preparation of acrylic copolymers containing reactive glycide groups in the side chain by methods that exclude the steps of the preparation and isolation of unsaturated glycidol ethers is of great practical importance. One of these methods is the chemical modification of acrylic copolymers on the reaction groups present in the side chains. The closest to the invention according to its technical essence and achieved 11. CC С1СН, Ш-СН At a mol of MAK, at least 7–9 mol of ECG must fall, since a decrease in the ECG content in the reaction mixture leads to its gelation. Dehydrochlorination (the next stage of the synthesis) is carried out with 1 mol mol of NaOH in the amount of 1 basis mole of MAK, the temperature is slowly raised from 20-25 ° C to 90 ° C during the reaction, the reaction time is. The oscillations range from 5 to 6 h. The polymer solution in the ECG is separated from the salt, cent, and which is obtained mainly by radical copolymerization in a block, solution, emulsion or suspension of acrylic or vinyl monomers with unsaturated glycidyl glycidyl ether , glycidyl methacrylate, allyl glycidyl ether, etc. l. Unsaturated glycidol esters can be prepared by reacting the sodium salts of the corresponding acids, for example acrylic, methacrylic, with epichlorohydrin. СН2 С-С-0-СНгСНсн, the second result is a method of producing butyl acrylate rubbers with epoxy groups by treating a copolymer of butyl acrylate, acrylonitrile and methacrylic acid with an epoxy-containing modifying agent in an organic solvent at 80-100 ° С in the presence of a catalyst 2. Conducted chemical modification-. copolymers based on butyl methacrylate (BMA) and methacrylic acid (MAK) with different contents of MAC in the starting system (14.3-33 33.3 mol.%). Epichlorohydrin (ECH) is used as a modifying agent. . The first stage of modification is the preparation of chlorohydrin esters of polymers at 90 ° C, using tri-, ethylamine (TEA) - (0.0144 mol of TEA per 1 basis-mole of MAC) as a catalyst. The reaction proceeding at the same time can be schematically depicted as follows: Qt. {C2H5) 3 I 1:,., / ,, - C- (ns-one H2C-C1 by refluxing or filtration, distilled off under vacuum, the resulting polymer is dried in vacuum. The yield of the glycidyl-containing copolymer is 8090% depending on the molar ratio of BMA: MAC In the initial copolymer (2: 1-gb: 1). The maximum yield (96%) is achieved with a molar ratio of BMA: MAC in copolymer f equal to 4: 1. This method is two-stage, long enough. The presence of impurities (NaCC, ECH) in the final product requires In addition, special conditions are required for fc highly toxic ECG. The purpose of the invention is to reduce the synthesis time while maintaining a high degree of substitution of carboxyl groups, simplifying the process and improving working conditions. that according to the method of producing butyl acrylate rubbers with epoxy groups by treating a copolymer of butyl acrylate, acrylonitrile and methacrylic acid with an epoxy-containing modifying agent c de organic solvent under vOgYuO C in the presence of a catalyst in .kachestve epoxide; Containing th modifying agent using viniloksietilovy glycidol ester with a molar ratio of ether to the carboxyl groups and the copolymer 5-7: 1, and as the organic perfluoroacids catalyst.

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It is the reaction temperature of 80-100 ° C, the reaction time is 3 hours. The degree of substitution of the carboxyl groups is 96%. Polymer yield 95–97%. When using organic perfluoric acids in the amount of (5.07 / 0) 10 mol / l, the reaction time is 15 minutes. The degree of substitution of COOH groups is 98%. The polymer yield is 96%. The introduction of epoxy groups into the polymer is proved by chemical methods and IR spectroscopy data. In addition, evidence of epoxidation is the ability of the polymers to be cured by the action of amines to form solid, insoluble in organic solvents products. Example 1: 20 g of rubber (BA: AN: MAC 70: 25: 5) are dissolved in 200 ml of toluene. 7.9 g (5.0 mol per 1 basic mole of MAC in the original rubber) of vinyloxyethyl is added.

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Y Glycidol Vinyloxyethyl Ester is a colorless liquid with the following physicochemical components: Tt n 76-77, (6 mm Nd); P 1.4480, df 1.0333, is a product of pilot production. As an object of modification, they take a triple sopo: limer of butyl acrylate (BA), acrylonitrile (AH) and methacliric acid (MAK) of the following composition, mac.h : BA: AN (65-70): (25-30): 5 with a molecular mass of 10. Toluene, benzene are used as solvents. The use of perfluorocarboxylic acids, for example, trifluoroacetic and perfluorobutyric, as catalysts allows,: along with acceleration, to increase the selectivity of the process and to avoid a whole number of side-transformations of both the initial reagents and the target product (hydrolysis, opening-oxide cycle and etc.). The reaction is carried out by heating a mixture of rubber and glycidol vinyloxyethyl ether in an aromatic solvent. A schematic reaction can be represented as follows: glycidol ester. The reaction mixture is thoroughly stirred for 3 hours. The polymer obtained is precipitated from toluene solution into hexane and washed with hexane. The subsequent reprecipitation from the acetone solution to hexane is used to wash the polymer from the unreacted glycidol vinyloxyethyl ester. The polymer is dried to constant weight in vacuo at 60 ° C. Analyze the content in the polymer-COOH and-CH -, CH2 groups The results of the analysis-COOH O, 1 wt.% -Hq-pHj 2.3 wt.%. The degree of substitution of COOH groups: 96%. The polymer yield (19.9 g) 96%. Example 2. Modification of rubber (BA: AN: MAC 70: 25: 5) is carried out analogously to example 1, only in

Claims (1)

METHOD FOR PRODUCING BUTYL ACRYLATE RUBBERS WITH EPOXY GROUPS by treating a copolymer of butyl acrylate, acrylonitrile and methacrylic acid with an epoxy-containing modifying agent in an organic solvent at 80-100 ° C in the presence of a catalyst, as a result of which to reduce the synthesis time, while maintaining a high degree of substitution of carboxyl groups, simplifying -__ scheniya process and improving the working conditions in an epoxy-modifying agent is _a glyceryl ester viniloksietilovy tsidola When the molar ratio © ester and carboxyl groups in the copolymer is 7.5: 1, and as a catalyst - a perfluoro organic acid!. g