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Method for preparing fluorine-containing nitrile rubber with low-temperature emulsion polymerization

An emulsion polymerization, fluorine-containing nitrile technology is applied in the field of preparation of nitrile rubber, which can solve the problems of not specifying the preparation method of ternary copolymer rubber, and achieve the effects of good elasticity, good wear resistance and high tensile strength

Active Publication Date: 2018-10-02
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] JP Hei 1-242643A provides a rubber composition with improved cold resistance, a ternary copolymer rubber of acrylonitrile, butadiene and trifluoroethyl acrylate prepared by conventional emulsion polymerization and then hydrogenated to form a highly saturated hydrogenated Rubber, in order to achieve the effect of improving the cold resistance of rubber, and does not specify the preparation method of its ternary copolymerization rubber

Method used

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  • Method for preparing fluorine-containing nitrile rubber with low-temperature emulsion polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] In the reaction kettle, first add 25 parts of acrylonitrile, 2 parts of hexafluorobutyl acrylate, 3 parts of hexafluorobutyl methacrylate mixed monomer and 0.075 parts of tm-200s, 75 parts of butadiene, 150 parts of water, 3 Part sodium dodecylbenzenesulfonate, 2 parts emulsifier A, 0.50 part tertiary dodecyl mercaptan, 0.2 part sodium carbonate, 0.01 part ferrous sulfate, 0.1 part sodium formaldehyde sulfoxylate, 0.05 part EDTA disodium salt , pre-emulsified for 40 minutes, then added 0.2 parts of cumene hydroperoxide, and controlled the temperature to carry out copolymerization at a polymerization temperature of 5°C. When reaching 80%, 0.4 part of diethylhydroxylamine was added to terminate the polymerization. The properties of the obtained fluorine-containing nitrile rubber are shown in Table 1.

Embodiment 2

[0054] In the reaction kettle, first add 20 parts of acrylonitrile and 10 parts of dodecylfluoroheptyl methacrylate mixed monomer and 0.48 parts of tm-200s, 80 parts of butadiene, 250 parts of water, 2 parts of dodecylbenzenesulfonate sodium nitrate, 5 parts of synthetic fatty acid potassium, 2.5 parts of emulsifier B, 1 part of emulsifier C, 1 part of n-dodecyl mercaptan, 0.5 part of sodium carbonate, 0.09 part of EDTA iron sodium salt, 0.36 part of glucose, 0.2 part of amino tris Sodium acetate, pre-emulsified for 50 minutes, then added 0.4 parts of dicumyl hydroperoxide, and controlled the temperature to carry out copolymerization at a polymerization temperature of 8°C, and then added 0.2 parts of n-dodecyl mercaptan when the conversion rate reached 40%. When the conversion rate reached 75%, 0.3 parts of hydroquinone and 0.3 parts of diethylhydroxylamine were added to terminate the polymerization. The properties of the obtained fluorine-containing nitrile rubber are shown i...

Embodiment 3

[0058] In the reaction kettle, first add 45 parts of acrylonitrile and 1 part of hexafluorobutyl acrylate mixed monomer and 0.0013 parts of tm-200s, 55 parts of butadiene, 300 parts of water, 1 part of synthetic fatty acid potassium, 4 parts of disproportionated abietic acid Potassium, 0.5 part of emulsifier C, 0.34 part of tertiary dodecyl mercaptan, 1.1 part of dithiodiisopropyl xanthate, 0.1 part of sodium acetate, 0.001 part of cuprous sulfate, 0.006 part of sodium formaldehyde sulfoxylate, 0.01 part of EDTA disodium salt, pre-emulsified for 30 minutes, then added 0.007 part of hydrogen peroxide p-menthane, and controlled the temperature to carry out copolymerization at a polymerization temperature of 14°C. When the conversion rate reached 84%, added 0.04 part of diethylhydroxylamine and 0.07 parts of hydroquinone terminated the polymerization. The properties of the obtained fluorine-containing nitrile rubber are shown in Table 1.

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Abstract

The invention provides a method for preparing fluorine-containing nitrile rubber with low-temperature emulsion polymerization. The method utilizes a fluorine-containing monomer emulsion polymerizationmethod to prepare the fluorine-containing nitrile rubber. In the polymerization process, a chelating titanate coupling agent is adopted, so that the ternary polymerization efficiency of a fluorine-containing monomer, acrylonitrile and butadiene can be remarkably improved. For the fluorine-containing nitrile rubber prepared by the method, the comprehensive properties of the nitrile rubber can be improved to a relatively large degree. For prepared fluorine-containing nitrile rubber, the oil resistance is good, the tensile strength is high, the oil resistance is improved by 20 percent or above compared with the fluorine-containing nitrile rubber prepared by an ordinary method, the Mooney viscosity is 50-100, the tensile strength is 30MPa or above, the elongation at break is 500 percent or above, meanwhile, the high-low temperature resistance is outstanding, the ageing-resistant performance is excellent, the glass-transition temperature is lowered by 10 DEG C or above, and the fluorine-containing nitrile rubber also has the characteristics of good elasticity, high stretching strength, low compression permanent deformation, good abrasive resistance, good weather ability, good pollutionresistance and narrow molecular weight distribution.

Description

technical field [0001] The invention relates to the field of preparation of nitrile rubber, in particular to a method for preparing fluorine-containing nitrile rubber by using a low-temperature emulsion polymerization method using a fluorine-containing monomer. Background technique [0002] Nitrile rubber (NBR) has the advantages of excellent oil resistance, good tensile properties, heat resistance, air tightness, compression deformation, etc., but it is mostly used in ordinary oil-resistant products, and it is rarely used in fields with harsh environmental requirements , mainly due to the limited application temperature range and weather resistance. [0003] Fluorine-containing polymers have excellent weather resistance, high temperature resistance, stain resistance, electrical insulation, durability, and chemical resistance due to fluorine-containing bonds. Fluorine is the most electronegative element, the covalent radius of the fluorine atom is very small, the bond energ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F236/12C08F220/44C08F220/22C08F2/26C08F2/30C08L15/02
CPCC08F2/26C08F2/30C08F236/12C08L15/02C08F220/44C08F220/22
Inventor 桂强刘鹏龚光碧郑聚成郑红兵钟启林张元寿张志强田力梁滔李晶李树毅陈建刚于奎李晓艳魏绪玲丛日新朱晶王锋史工昌
Owner PETROCHINA CO LTD
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