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ChemicalBook CAS DataBase List VINYL FLUORIDE
75-02-5

VINYL FLUORIDE synthesis

12synthesis methods
Vinyl fluoride may be obtained from acetylene by either of the two following routes:


In the first method, acetylene is heated with hydrogen fluoride in the presence of a catalyst of mercuric chloride on charcoal at about 40°C to yield vinyl fluoride directly. In the second method, acetylene is treated with an excess of hydrogen fluoride to form difluoroethane which is then pyrolysed at about 700°C in a platinum tube to give vinyl fluoride, which is separated by distillation under pressure.
Vinylidene fluoride is obtained from vinylidene chloride by the following route:


In the first stage, vinylidene chloride undergoes addition with hydrogen chloride at about 30°C and atmospheric pressure in the presence of a FriedelCrafts type catalyst. The resulting trichloroethane is then treated with hydrogen fluoride at about 180°C and 3 MPa (30 atmospheres) in the presence of antimony pentachloride to give chlorodifluoroethane. Pyrolysis of this product yields vinylidene fluoride. Vinylidene fluoride is a gas, b.p. -84°C.
-

Yield:-

Reaction Conditions:

with hydrogen fluoride at 200 - 250;

Steps:

7; 8
Example 7; Preparation Example of Crude 1,1-Difluoroethane (Raw Material Example 3); 1,1-Dichloroethane and hydrogen fluoride were introduced into an inconel-made reactor filled with a catalyst (mainly comprising trivalent chromium oxide) and reacted at a reaction temperature of 200°C, the resulting reaction gas mainly comprising 1,1-difluoroethane, hydrogen chloride and unreacted hydrogen fluoride was introduced into a first distillation tower, hydrogen chloride which is a low boiling fraction was mainly separated from the top and a side-cut fraction mainly comprising crude 1,1-difluoroethane was separated and withdrawn from a stage upper than the middle portion of the distillation tower. The obtained crude 1,1- difluoroethane had the following composition. CH3CHF2 99.1938 CH2=CH2 0. 0004 CH2=CHF 0.0019 CH2=CClF 0.0005 CH2=CHC1 0.0018 CH3CHClF 0.0002 CH3CH2Cl 0.0002 CH2=CCl2 0.0004 HC1 0. 2188 HF 0.5820 unit: vol%; Example 8; Preparation Example of Crude 1,1-Difluoroethane (Raw Material Example 4); 1,1-Dichloroethane and hydrogen fluoride were introduced into an inconel-made reactor filled with a catalyst (mainly comprising trivalent chromium oxide) and reacted at a reaction temperature of 250°C, the resulting reaction gas, mainly comprising 1,1-difluoroethane, hydrogen chloride and unreacted hydrogen fluoride, was introduced into a first distillation tower, hydrogen chloride which is a low boiling fraction was mainly separated from the top, and hydrogen fluoride, 1,1- difluoroethane, 1,1-dichloroethane and 1-chloro-1- fluoroethane were mainly separated from the bottom and introduced into a second distillation tower. In the second distillation tower, crude 1,1-difluoroethane mainly comprising 1,1-difluoroethane was obtained from the top and hydrogen fluoride, 1,1-dichloroethane and 1- chloro-fluoroethane were mainly separated from the bottom and recirculated to the above-described reaction step. The obtained crude 1,1-difluoroethane had the following composition. [0031] CH3CHF2 99.7098 CH2=CH2 0.0002 CH2=CHF 0.0011 CH2=CC1F 0. 0010 CH2=CHC1 0. 0008 CH3CHClF 0.0002 CH3CH2Cl 0.0001 CH2=CC12 0.0002 HC1 trace amount HF 0.2866 unit: vol%

References:

SHOWA DENKO K.K. WO2005/44765, 2005, A2 Location in patent:Page/Page column 20-22

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