Catalytic component for trimerization and trimerization catalyst

Abstract

Disclosed is a catalytic component for trimerization containing a transition metal complex with which 1-hexene can be produced efficiently with excellent selectivity, even under high temperature conditions, by means of an ethylene trimerization reaction. Also disclosed is a trimerization catalyst that is obtained by bringing an olefin copolymerization catalyst and an activating co-catalytic component into contact with one another. Said transition metal complex is represented by the following general formula (1), wherein M 1 represents a Group 4 transition metal atom, and R 1 through R 11 and X 1 through X 3 each independently represent a hydrogen atom, a halogen atom, or a specific organic group.

1 . A catalytic component for trimerization comprising a transition metal complex represented by general formula (1): 
       
         
           
           
               
               
           
         
       
       wherein
 M 1  represents a transition metal atom of Group 4 of the Periodic Table of the Elements; R 1 , R 2 , R 3  and R 4  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an alkoxy group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryloxy group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyloxy group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20, or 
 a disubstituted amino group represented by —N(R 13 ) 2 , wherein the two R 13  groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13  groups is 2 to 20, and 
 at least one of R 1 , R 2 , R 3  and R 4  is a halogen atom, the alkyl group, the alkoxy group, the aryl group, the aryloxy group, the aralkyl group, the aralkyloxy group, the substituted silyl group or the disubstituted amino group; 
 R 5  and R 9  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, or 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20; 
 R 6 , R 7  and R 8  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an alkoxy group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryloxy group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyloxy group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20, or 
 a disubstituted amino group represented by —N(R 13 ) 2 , wherein the two R 13  groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13  groups is 2 to 20; 
 R 10  and R 11  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an alkoxy group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryloxy group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyloxy group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20, or 
 a disubstituted amino group represented by —N(R 13 ) 2 , wherein the two R 13  groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13  groups is 2 to 20; 
 X 1 , X 2  and X 3  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20, or 
 a disubstituted amino group represented by —N(R 13 ) 2 , wherein the two R 13  groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13  groups is 2 to 20; 
 of R 1 , R 2 , R 3  and R 4 , two groups bonded to two adjacent carbon atoms are optionally bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; 
 of R 5 , R 6 , R 7 , R 8  and R 9 , two groups bonded to two adjacent carbon atoms are optionally be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; and R 10  and R 11  are optionally bonded to each other to form a ring together with the silicon atom to which R 10  and R 11  are bonded. 
 
     
     
         2 . The catalytic component for trimerization according to  claim 1 , wherein M 1  in the general formula (1) is a titanium atom. 
     
     
         3 . The catalytic component for trimerization according to  claim 2 , wherein each of R 10  and R 11  in the general formula (1) is a hydrogen atom,
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent,   an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, or   an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent.   
     
     
         4 . The catalytic component for trimerization according to  claim 2 , wherein both R 10  and R 11  in the general formula (1) are the same and are
 alkyl groups having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, or   aryl groups having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent   
     
     
         5 . The catalytic component for trimerization according to  claim 2 , wherein each of R 6  and R 8  in the general formula (1) is
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, or   an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent,   and each of R 10  and R 11  in the general formula (1) is an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent.   
     
     
         6 . The catalytic component for trimerization according to  claim 2 , wherein each of R 1 , R 2 , R 3  and R 4  in the general formula (1) is
 a hydrogen atom, a halogen atom,   an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,   an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, or   an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent.   
     
     
         7 . The catalytic component for trimerization according to  claim 2 , wherein the cyclopentadienyl moiety represented by the general formula (2) in the general formula (1) 
       
         
           
           
               
               
           
         
       
       is selected from among methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl, and octahydrofluorenyl. 
     
     
         8 . The catalytic component for trimerization according to  claim 2 , wherein each of R 1 , R 2 , R 3  and R 4  in the general formula (1) is a methyl group. 
     
     
         9 . A trimerization catalyst which is obtainable by bringing a transition metal complex into contact with an activating co-catalytic component, wherein the transition metal complex is one represented by general formula (1): 
       
         
           
           
               
               
           
         
       
       wherein
 M 1  represents a transition metal atom of Group 4 of the Periodic Table of the Elements; R 1 , R 2 , R 3  and R 4  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an alkoxy group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryloxy group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyloxy group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20, or 
 a disubstituted amino group represented by —N(R 13 ) 2 , wherein the two R 13  groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13  groups is 2 to 20, and 
 at least one of R 1 , R 2 , R 3  and R 4  is a halogen atom, the alkyl group, the alkoxy group, the aryl group, the aryloxy group, the aralkyl group, the aralkyloxy group, the substituted silyl group or the disubstituted amino group; 
 R 5  and R 9  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, or 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20; 
 R 6 , R 7  and R 8  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an alkoxy group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryloxy group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyloxy group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20, or 
 a disubstituted amino group represented by —N(R 13 ) 2 , wherein the two R 13  groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13  groups is 2 to 20; 
 R 10  and R 11  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an alkoxy group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aryloxy group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 an aralkyloxy group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent, 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20, or 
 a disubstituted amino group represented by —N(R 13 ) 2 , wherein the two R 13  groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13  groups is 2 to 20; 
 X 1 , X 2  and X 3  each independently represent 
 a hydrogen atom, a halogen atom, 
 an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, 
 an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, 
 a substituted silyl group represented by —Si(R 12 ) 3 , wherein the three R 12  groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 12  groups is 1 to 20, or 
 a disubstituted amino group represented by —N(R 13 ) 2 , wherein the two R 13  groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 13  groups is 2 to 20; 
 of R 1 , R 2 , R 3  and R 4 , two groups bonded to two adjacent carbon atoms are optionally bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; 
 of R 5 , R 6 , R 7 , R 8  and R 9 , two groups bonded to two adjacent carbon atoms are optionally be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded; and R 10  and R 11  are optionally bonded to each other to form a ring together with the silicon atom to which R 10  and R 11  are bonded. 
 
     
     
         10 . The trimerization catalyst according to  claim 9 , wherein M 1  in the general formula (1) is a titanium atom. 
     
     
         11 . The trimerization catalyst according to  claim 10 , wherein each of R 10  and R 11  in the general formula (1) is a hydrogen atom,
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent,   an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent, or   an aralkyl group having 7 to 20 carbon atoms which optionally have a halogen atom as a substituent.   
     
     
         12 . The trimerization catalyst according to  claim 10 , wherein both R 10  and R 11  in the general formula (1) are the same and are
 alkyl groups having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, or   aryl groups having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent   
     
     
         13 . The trimerization catalyst according to  claim 10 , wherein each of R 6  and R 8  in the general formula (1) is
 an alkyl group having 1 to 20 carbon atoms which optionally have a halogen atom as a substituent, or   an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent,   and each of R 10  and R 11  is an aryl group having 6 to 20 carbon atoms which optionally have a halogen atom as a substituent.   
     
     
         14 . The trimerization catalyst according to  claim 10 , wherein each of R 1 , R 2 , R 3  and R 4  in the general formula (1) is a hydrogen atom, a halogen atom,
 an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,   an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, or   an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent.   
     
     
         15 . The trimerization catalyst according to  claim 10 , wherein the cyclopentadienyl moiety represented by the general formula (2) in the general formula (1) 
       
         
           
           
               
               
           
         
       
       is selected from the following: methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl, and octahydrofluorenyl. 
     
     
         16 . The trimerization catalyst according to  claim 10 , wherein each of R 1 , R 2 , R 3  and R 4  in the general formula (1) is a methyl group. 
     
     
         17 . The trimerization catalyst according to  claim 9 , wherein the activating co-catalytic component comprises the following compound (A):
 compound (A): one or more aluminum compounds selected from the compound group consisting of the following compounds (A1) to (A3):   (A1): an organic aluminum compound represented by a general formula (E 1 ) a Al(G) 3-a ,   (A2): a cyclic aluminoxane having a structure represented by a general formula {—Al(E 2 )-O—} b , and   (A3): a linear aluminoxane having a structure represented by a general formula E 3 {-Al(E 3 )-O—} c Al(E 3 ) 2 , wherein   E 1 , E 2  and E 3  each represent a hydrocarbyl group having 1 to 8 carbon atoms; G represents a hydrogen atom or a halogen atom; a represents an integer of 1 to 3; b represents an integer of 2 or more; c represents an integer of 1 or more; in the case that more than one E 1  groups exist, the E 1  groups may be the same or different from each other; in the case that more than one G groups exist, the G groups may be the same or different from each other; in the case that more than one E 2  groups exist, the E 2  groups may be the same or different from each other; and in the case that more than one E 3  groups exist, the E 3  groups may be the same as or different from each other.   
     
     
         18 . The trimerization catalyst according to  claim 9 , wherein the activating co-catalytic component comprises the following compound (B):
 compound (B): one or more boron compounds selected from the compound group consisting of the following compounds (B1) to (B3):   (B1): a boron compound represented by a general formula BQ 1 Q 2 Q 3 ,   (B2): a borate compound represented by a general formula T + (BQ 1 Q 2 Q 3 Q 4 ) − , and   (B3): a borate compound represented by a general formula (L-H) + (BQ 1 Q 2 Q 3 Q 4 ) − , wherein   B represents a trivalent boron atom; Q 1 , Q 2 , Q 3  and Q 4  are the same as or different from each other and each represent a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms which is optionally substituted by a halogen atom, a hydrocarbylsilyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a dihydrocarbylamino group having 2 to 20 carbon atoms; T +  represents an inorganic or organic cation; and (L-H) +  represents a Brønsted acid.