| 摘要 |
1,131,640. Hexadienes. TOYO RAYON K.K. 20 April, 1966 [22-April, 1965; 4 Sept., 1965; 19 Nov., 1965], No. 17361/66. Heading C5E. Hexadienes are obtained by codimerizing an alpha-olefin with a conjugated di-olefin in the presence of a two-component catalyst comprising (1) a cobalt compound COH[R 2 P-(-R<SP>1</SP>-) n -PR 2 ] m wherein R is alkyl or aryl, R<SP>1</SP> is alkylene, alkenylene or arylene, n is 0 or 1, and m is 1 or 2, and (2) one of the compounds (a) R<SP>2</SP> p AlX 3-p , wherein R<SP>2</SP> is monovalent hydrocarbon, X is H or halogen, and p is 1, 2 or 3; (b) R<SP>3</SP>OH wherein R<SP>3</SP> is alkyl, cycloalkyl, aryl or substituted aryl; or (c) a Friedel-Crafts catalyst. The α-olefin may be ethylene or propylene (preferred), butene-1, pentene-1, hexene-1 or heptene-1, and the diene a 1,3-butadiene, or a C 1 -C 20 alkyl- or aryl-substituted 1,3-butadiene, particularly isoprene. Preferred cobalt compounds (1) are CoH[(C 6 H 5 ) 2 P(CH 2 ) 2 P(C 6 H 5 ) 2 )] 2 and CoH[(C 6 H 5 ) 2 P(CH 2 ) 3 P(C 6 H 5 ) 2 ] 2 used in an amount 10<SP>-5</SP>-10<SP>-1</SP> mol./mol. diene, and in a ratio to 2(a), (b) or (c) of 1-100 : 1, 10-200 : 1 and 0À1-50 : 1 respectively. The Friedel-Crafts catalyst (c) may be AlCl 3 , SnCl 4 , ZrCl 4 , WCl 6 , BF 3 (OEt) 2 , TiCl 4 , or Al 2 Br 6 . Reaction is effected at 20-250‹ C., and atmospheric to 300 kg./sq. cm. pressure, optionally in the presence of a hydrocarbon or halogenated hydrocarbon solvent. |
