Patent GB-810536-A (GB)
Title: Improvements in the production of acrylic acid and its esters
IPC: C07C51/14
Filed: 1957-07-04
Abstract: Catalyst compositions comprise a complex compound which contains a nickel halide and an organic complex-forming compound X-CH2-(CH2)n-Y where X is a nitrile, imino ether or acid amide group, Y is a nitrile, imino ether, acid amide, hydroxy, alkoxy, aryloxy, acyl, alkylmercapto, arylmercapto, secondary amino or tertiary amino group, and n is an integer from 0-5.  Complex forming compounds specified are malonodinitrile, succinodinitrile, adipodinitrile, b  - ethoxypropionitrile, b  - ethylmercaptopropionitrile, dimethylaminoacetonitrile, 3 - formylaminopropionitrile, 1 - cyanobutanone-3, succinic acid diamide, adipic acid diamide, 1 - cyano - 3 - methylaminopropane, acetylaminoacetonitrile, acetylaminopropionitrile, malonic acid di-N,N1-methylamide and levulinic acid nitrile.  Nickel bromides and iodides are preferred halides but chlorides may be used.  The complex compounds may be formed by heating or vigorously mixing the components.  They may be added to the reaction mixture as such or in solution in, for example, the initial materials or organic solvents such as hydrocarbons, ketones or ethers, or they may be formed in situ.  Generally 0.05 to 3 per cent of nickel halide and 0.5 to 1 per cent of the complex-forming organic compound are used with reference to the weight of reaction mixture.  The ratio of nickel halide to organic compound may vary within wide limits, e.g. 1:20 to 20:1.  Inert solvents may be used, e.g. tetrahydrofuran, acetone, dimethylformamide, N-methylpyrrolidone or butyrolactam.  Examples describe the preparation of acrylic acid and methyl, ethyl and butyl acrylates using complex catalysts derived from NiBr2 or NiI2 and various complex-forming compounds included in the list above.ALSO:Acrylic acid and its esters are produced from acetylene, carbon monoxide and water or alcohols at 100-250 DEG  C. and 5 to about 100 atmospheres pressure in the presence of catalysts comprising a complex compound which contains a nickel halide and an organic complex-forming compound X-CH2-(CH2)n-Y, where X is a nitrile, imino ether or acid amide group, Y is a nitrile, imino ether, acid amide, hydroxy, alkoxy, aryloxy, acyl, alkylmercapto, arylmercapto, secondary amino or tertiary amino group, and n is an integer from 0-5.  Complex forming compounds specified are malonodinitrile, succinodinitrile, adipodinitrile, b -ethoxypropionitrile, b  - ethylmercaptopropionitrile, dimethylaminoacetonitrile, 3 - formylaminopropionitrile, 1 - cyanobutanone - 3, succinic acid diamide, adipic acid diamide, 1-cyano-3 - methylaminopropane, acetylaminoacetonitrile, acetylaminopropionitrile, malonic acid di - N,N1 - methylamide and levulinic acid nitrile.  Nickel bromides and iodides are preferred halides but chlorides may be used.  The complex compounds may be formed by heating or vigorously mixing the components.  They may be added to the reaction mixture as such or in solution in, for example, the initial materials or organic solvents such as hydrocarbons, ketones or ethers, or they may be formed in situ.  Generally 0.05 to 3 per cent of nickel halide and 0.5 to 1 per cent of the complex-forming organic compound are used with reference to the weight of reaction mixture.  The ratio of nickel halide to organic compound may vary within wide limits, e.g. 1 : 20 to 20 : 1.  The volume ratio of CO : C2H2 is preferably 1 : 1 but may be from 5 : 1 to 1 : 5.  The gases may be added consecutively or simultaneously in admixture.  Other gases such as N2, CO2 or H2 may be present. Inert solvents may be used, e.g. tetrahydrofuran, acetone, dimethylformamide, N - methylpyrrolidone or butyrolactam. Examples describe the preparation of acrylic acid and methyl, ethyl and butyl acrylates using complex catalysts derived from NiBr2 or NiI2 and various complex-forming compounds included in the list above.