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It is used as monomer and organic synthetic intermediate of polymer and resin; It is mainly used to produce synthetic resin, synthetic fiber, synthetic rubber, plastic, coating, adhesive, etc.; Acrylic acid and its esters are widely used in industry. In the process of use, acrylate is often synthesized into polymers or..
The production methods of acrylate include acrylic nitrile hydrolysis method, β-propiolactone method, repe method and modified repe method, cyanoethanol method and propylene direct oxidation method. 1. Cyanoethanol method uses chloroethanol and sodium cyanide as raw materials to react to generate cyanoethanol and cyanoethanol in the presence of sulfuric acid to form acrylic acid. Acrylic nitrile hydrolysis method due to the abundant sources of acrylonitrile, the method of producing acrylate with acrylic nitrile as raw material has been developed. Now the industrialized methods include Societe Ugine method and Standard Oil Co(O-hio) method. Acrylic nitrile and sulfuric acid are heated together to 90℃ to hydrolyze acrylic nitrile into the sulfate of acrylamide, and the sulfate is further transesterified to form acrylate. In recent years, it has been reported that the yield of Ester can reach 95% by using acrylonitrile as raw material and one-step production. 3.β-propionolactone method uses acetic acid (or acetone) as raw material and triethyl phosphate as catalyst to cleave and generate ethenone at 625-730 ℃. Then gaseous phase reaction with anhydrous methyl vinegar in the presence of AICI3 or BF3 catalyst at 25℃ to generate β-propiolactone: if the target product is acrylic acid, then the propiolactone is contacted with the hot 100% phosphoric acid to form acrylic acid. If the target product is acrylate, the crude propiolactone can directly react with the corresponding alcohol and sulfuric acid without purification. 4. During the second world war of repe method and modified repe method, Reppe found two methods in the research work to make acetylene, carbon monoxide react with water or alcohol to synthesize acrylic acid or propylene ester. Namely, "chemometric method" and "catalytic method", which were later developed into the improved repe method adopted by Rohm & Hass Company in production and the high pressure repe method adopted by Dow-Badiche company. (1) stoichiometry this method is to react acetylene, nickel carbonyl (providing carbon monoxide) with water or alcohol under relatively mild conditions (40℃,0.101MPa) to generate acrylic acid or acrylate: (2) reaction of acetylene, carbon monoxide and alcohol in the presence of nickel carbonyl catalyst at 150℃ and 1.50-3MPa to obtain acrylate: (3) modified repe method this method is the combination of the above two methods. After the start of the stoichiometry reaction, carbon monoxide and acetylene are introduced, and the reaction can proceed continuously, 80% of the carbon monoxide required for the reaction is available gas carbon monoxide, while nickel carbonyl only needs to provide 20%. (4) the characteristic of this method is to use tetrahydrofuran as solvent to dissolve acetylene required by the reaction in tetrahydrofuran first, which can reduce the risk of high-pressure treatment of acetylene, at the same time, nickel carbonyl is not needed, only nickel salt is used as catalyst, and the reaction is carried out at 200-225 ℃ and 8.11-10.13MPa. (5) propylene direct oxidation propylene gas phase Air catalytic oxidation is the latest method to produce acrylic acid and its esters. Raw material consumption quota: 770kg/t acrylic acid and 610kg/t n-butyl alcohol. 5. Preparation Method: Add 371g(5.0mol) of n-butyl alcohol and methyl acrylate into the reaction bottle equipped with wechner fractional distillation column (with distillation device), agitator and ventilation duct. (2)861G (10.0mol), 20g hydroquinone and 10g p-toluenesulfonic acid are introduced into carbon dioxide gas, and the oil bath is heated and refluxed with stirring. Firstly, the azeotrope of methanol-methyl acrylate (62 ~ 63℃) is steamed out, and the temperature of distilling head is controlled not to exceed 65℃. About 8~10 hours when the production of methanol is very slow, the excess methyl acrylate is distilled off under reduced pressure, and then the fraction of 39℃/1.33kPa is collected under reduced pressure, which can get n-butyl acrylate ① (1)500~600g, yield 78%~ 94%. Note: ① this method adopts the method of Ester excess for transesterification, which can be recycled after ester recovery. Using this method, various esters can be synthesized as follows (table I-9- 1 Reference book 485 pages).
S16-S25-S37-S61-S9
R10;R36/37/38;R43
UN19933/PG2
GHS02,GHS07
Complete packaging, light loading and unloading, ventilation in the warehouse, away from open flame, high temperature, and separate storage from oxidant
P261;P273;P280;P305+P351+P338
III
Warning
H226;H302+H312+H332;H315;H317;H319;H335;H412
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