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Dimerisation of ethylene catalyzed by nickel catalyst supported on porous polymers
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Dimerisation of Ethylene Catalyzed by Nickel Catalyst Supported on Porous Polymers J . C . C a r l u a n d C. C a z e , Universit~ des Sciences et Techniques de Lille Flandres Artois, Villeneuve d'Ascq, France Macroporous phosphinated styrene-divinylbenzene copolymers were used as a support of a catalyst based on reduced nickel and used in heterogeneous conditions. The dimerization of ethylene thus catalyzed showed good selectivity with a yield of butene of up to 90%. The effect of the chemical structure of the polymer support, its texture (surface area and pore volume) and the experimental conditions (pressure, temperature) on the selectivity and activity was determined. Publication details unknown.
Cation Exchangers as Catalysts for an Industrial Scale p-Cumylphenol Process W . R a t a j c z a k , K . Z i e b o r a k , Industrial Chemistry Research Institute, Warsaw, Poland, J. M a r s z y c k i a n d W . J a n k o w s k i , Chemical Works Blachownia, Kedzierzyn-Kozle, Poland A plant has been out on stream, capable of making up to 2000 t p-cumylphenol by alkylation of phenol with c~-methylstyrene obtained from the cumene phenol process. Sulphonic acid cation exchangers having a gel (Wofatit KPS) or a macroporous structure (Amberlyst 15, Wofatit OK-80) were used as catalysts in the alkylation process, the latter being more active. Selectivity of the alkylation reaches 90-92% and is not related to the network type. p-Cumylphenol of purity of minimal 85% is used as a fungicide in timber impregnants. It is relatively low toxic for mammals. To produce 1 t p-cumylphenol, it is necessary to use 0.5 t phenol and about 1.6 t of the fraction containing 40% a-methylstyrene and 50% cumene. Cumene, which is useful as a feedstock for the phenol process, is produced as a by-product. To be published in
PrzernyslChemicznv (1989).
Sulphonic Acid Cation Exchangers as Catalysts for Synthesis of 2-tert-Butyl-4-(ct,~-dimethylbenzyl)phenol A . M i l c z a r e k a n d W . R a t a j c z a k , Research Institute of Industrial Chemistry, Warsaw, Poland 2-tert-Butyl-4-(a,c~-dimethylbenzyl)phenol is a phenolic antioxidant for polymer stabilisation. The following two types of synthesis of this compound were investigated: (1) alkylation of phenol with a-methylstyrene followed by alkylation of the resulting p-cumylphenol with isobutylene; (2) alkylation of phenol with isobutylene followed by alkylation of the resulting 2-tert-butylphenol with a-methylstyrene. Optimum conditions were established when the reaction was run in two stages. In the first stage, isobutylene gas or a fraction containing isobutylene is charged with phenol at about 100°C in the presence of aluminium phenoxide. 2-tert-Butylphenol is isolated from the reaction mixture by distillation under reduced pressure after the catalyst has been decomposed. In the second stage a-methylstyrene or a fraction containing a-methylstyrene is added dropwise to a solution of 2-tert-butylphenol in hexane or heptane at about 70 °C in the presence of a strong-acid cation exchanger (e.g., Amberlyst 15). The resulting 2-tert-butyl-4-(c~, c~-dimethylbenzyl)phenol is isolated from the reaction mixture by distillation under reduced pressure. To be published in
PrzemyslCherniczny (1989).
The Use of Modified AcrylonitrUe-Divinylbenzene Copolymers in Phase Transfer Catalysis A n d r z e j T r o c h i m c z u k , J i f i H r a d i l , B o 2 e n a N . K o l a r z a n d F r a n t i ~ e k Svec, Technical University of Wroctaw, Wroclaw, Poland a n d Czechoslovak Academy of Sciences, Prague, Czechoslovakia Until now low molecular weight compounds as well as amine-modified macroporous and gel-type copolymers of styrene-divinylbenzene, vinylpyridine-divinylbenzene and glycidyl methacrylate-ethylene dimethacrylate have been used as catalysts in phase transfer catalysis.
Dimerisation of Ethylene Catalyzed by Nickel Catalyst Supported on Porous Polymers J . C . C a r l u a n d C. C a z e , Universit~ des Sciences et Techniques de Lille Flandres Artois, Villeneuve d'Ascq, France Macroporous phosphinated styrene-divinylbenzene copolymers were used as a support of a catalyst based on reduced nickel and used in heterogeneous conditions. The dimerization of ethylene thus catalyzed showed good selectivity with a yield of butene of up to 90%. The effect of the chemical structure of the polymer support, its texture (surface area and pore volume) and the experimental conditions (pressure, temperature) on the selectivity and activity was determined. Publication details unknown.
Cation Exchangers as Catalysts for an Industrial Scale p-Cumylphenol Process W . R a t a j c z a k , K . Z i e b o r a k , Industrial Chemistry Research Institute, Warsaw, Poland, J. M a r s z y c k i a n d W . J a n k o w s k i , Chemical Works Blachownia, Kedzierzyn-Kozle, Poland A plant has been out on stream, capable of making up to 2000 t p-cumylphenol by alkylation of phenol with c~-methylstyrene obtained from the cumene phenol process. Sulphonic acid cation exchangers having a gel (Wofatit KPS) or a macroporous structure (Amberlyst 15, Wofatit OK-80) were used as catalysts in the alkylation process, the latter being more active. Selectivity of the alkylation reaches 90-92% and is not related to the network type. p-Cumylphenol of purity of minimal 85% is used as a fungicide in timber impregnants. It is relatively low toxic for mammals. To produce 1 t p-cumylphenol, it is necessary to use 0.5 t phenol and about 1.6 t of the fraction containing 40% a-methylstyrene and 50% cumene. Cumene, which is useful as a feedstock for the phenol process, is produced as a by-product. To be published in
PrzernyslChemicznv (1989).
Sulphonic Acid Cation Exchangers as Catalysts for Synthesis of 2-tert-Butyl-4-(ct,~-dimethylbenzyl)phenol A . M i l c z a r e k a n d W . R a t a j c z a k , Research Institute of Industrial Chemistry, Warsaw, Poland 2-tert-Butyl-4-(a,c~-dimethylbenzyl)phenol is a phenolic antioxidant for polymer stabilisation. The following two types of synthesis of this compound were investigated: (1) alkylation of phenol with a-methylstyrene followed by alkylation of the resulting p-cumylphenol with isobutylene; (2) alkylation of phenol with isobutylene followed by alkylation of the resulting 2-tert-butylphenol with a-methylstyrene. Optimum conditions were established when the reaction was run in two stages. In the first stage, isobutylene gas or a fraction containing isobutylene is charged with phenol at about 100°C in the presence of aluminium phenoxide. 2-tert-Butylphenol is isolated from the reaction mixture by distillation under reduced pressure after the catalyst has been decomposed. In the second stage a-methylstyrene or a fraction containing a-methylstyrene is added dropwise to a solution of 2-tert-butylphenol in hexane or heptane at about 70 °C in the presence of a strong-acid cation exchanger (e.g., Amberlyst 15). The resulting 2-tert-butyl-4-(c~, c~-dimethylbenzyl)phenol is isolated from the reaction mixture by distillation under reduced pressure. To be published in
PrzemyslCherniczny (1989).
The Use of Modified AcrylonitrUe-Divinylbenzene Copolymers in Phase Transfer Catalysis A n d r z e j T r o c h i m c z u k , J i f i H r a d i l , B o 2 e n a N . K o l a r z a n d F r a n t i ~ e k Svec, Technical University of Wroctaw, Wroclaw, Poland a n d Czechoslovak Academy of Sciences, Prague, Czechoslovakia Until now low molecular weight compounds as well as amine-modified macroporous and gel-type copolymers of styrene-divinylbenzene, vinylpyridine-divinylbenzene and glycidyl methacrylate-ethylene dimethacrylate have been used as catalysts in phase transfer catalysis.