Process for producing unsaturated hydrocarbon compound

Abstract

Disclosed is a method for producing an unsaturated hydrocarbon compound wherein an α-olefin is dimerized by using a catalyst system composed of a metallocene compound (A) and an oxygen-containing organometallic compound modified with a halogen-containing compound (B). By this method, an unsaturated hydrocarbon compound having unsaturated double bonds in a high ratio, in particular the one having a terminal vinylidene group can be produced efficiently.

1 . A method of producing an unsaturated hydrocarbon compound, comprising:
 dimerizing an α-olefin in the presence of a catalyst,   wherein the catalyst comprises a metallocene compound (A) and an oxygen-containing organometallic compound modified with a halogen-containing compound (B).   
     
     
         2 . The method of  claim 1 , wherein the compound (B) is a compound of formula (2), a compound of formula (3), or a mixture thereof: 
       
         
           
           
               
               
           
         
         wherein R 8  to R 14  are each independently an alkyl group having 1 to 8 carbon atoms, 
         A 1  to A 5  are each independently a metal element of Group 13 of the periodic table, 
         each of h to k is independently from 0 to 50, and 
         each of (h+i) and (j+k) are greater than 1. 
       
     
     
         3 . The method of  claim 1 , wherein the halogen-containing compound is a halogenated alkylaluminum compound, a halogenated hydrocarbon compound, or a mixture thereof. 
     
     
         4 . The method of  claim 3 , wherein the halogenated alkylaluminium compound is of formula (4):
   R 15   n AlX 1   3-n   (4)
   wherein R 15  is a hydrocarbyl group having 1 to 20 carbon atoms or an organometalloid group,   X 1  is a halogen atom, and   n satisfies a relation 0<n<3.   
     
     
         5 . The method of  claim 3 , wherein the halogen-containing compound comprises a halogenated hydrocarbon compound comprising a hydrocarbon group having from 1 to 20 carbon atoms, and wherein from 1 to 4 hydrogen atoms of the hydrocarbon group are each substituted with a halogen atom. 
     
     
         6 . The method of  claim 1 , wherein the compound (A) is a compound of formula (1):
   Qa(C 5 H 5-a-b R 1   b )(C 5 H 5-a-c R 2   c )M 1 XY  (1)
   wherein Q is a connecting group for crosslinking two conjugated 5-membered ring ligands (C 5 H 5-a-b R 1   b ) and (C 5 H 5-a-c R 2   c );   each R 1  and R 2  are independently a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group, and may form a ring structure by bonding with each other;   a is 0, 1, or 2;   b and c are each independently an integer of 0 to 5 when a=0, an integer of 0 to 4 when a=1, or an integer of 0 to 3 when a=2;   M 1  is a transition metal of Group 4 of the periodic table; and   X and Y are each independently a covalent bond ligand or an ionic bond ligand, and may be bonded with each other.   
     
     
         7 . The method of  claim 6 , wherein M 1  is zirconium. 
     
     
         8 . The method of  claim 1 , wherein the α-olefin is dimerized in the presence of hydrogen. 
     
     
         9 . The method for producing an unsaturated hydrocarbon compound according to any of claims of  claim 1 , wherein the ratio of unsaturated double bonds contained in the unsaturated hydrocarbon compound is at least 80 mol % or more of hydrocarbon compound obtained by the method comprises an unsaturated double bond.