Process for oligomerization of olefins that uses a catalytic composition that comprises an organometallic complex that contains an alkoxy ligand that is functionalized by a heteroatom

Abstract

The invention describes a process for oligomerization of olefins into compounds or into a mixture of compounds of general formula CpH2p with 4≦p≦80 that employs a catalytic composition that comprises at least one organometallic complex of an element of group IV that is selected from among titanium, zirconium, or hafnium, whereby said organometallic complex contains at least one alkoxy-type ligand that is functionalized by a heteroatom that is selected from among nitrogen, oxygen, phosphorus or sulfur, or by an aromatic group.

1 . Catalytic composition comprising at least one organometallic complex of an element of group IV that is selected from among titanium, zirconium or hafnium, whereby said organometallic complex contains at least one alkoxy-type ligand that is functionalized by a heteroatom that is selected from among nitrogen, oxygen, phosphorus or sulfur or by an aromatic group, and has the following for a general formula:
   [M(OR) n Y (4-n) ]   in which:
 M is an element from group IV that is selected from among titanium, zirconium, and hafnium, 
 Y is an atom of chlorine or bromine, a hydrocarbyl radical that comprises 1 to 30 carbon atoms, or a radical that is selected from the group that is formed by the alkoxies R′O—, the amidos R′2N—, or the carboxylates R′COO—, where R′ is a hydrocarbyl radical that comprises 1 to 30 carbon atoms, 
 n can assume the integer values of 1 to 4, 
 The ligand —OR is an organic compound that is selected from the family of alkoxy ligands whose general structure is as follows:
   O—(CR 10 R 11 ) n —X-L
 
 
   in which:
 The functional group L is a group that comprises a heteroatom or an aromatic group, whereby said group that comprises a heteroatom is selected from among the groups —NR 1 R 2 , —OR 3 , —PR 4 R 5 , and —SR 6 , 
 The group X represents a hydrocarbon group (CR 7 R 8 ), an oxygen atom, or a group that comprises a nitrogen atom —NR 9 , 
 The groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and R 11  represent a hydrogen atom or a hydrocarbon chain that may or may not be cyclic, comprising 1 to 30 carbon atoms, 
 n can assume the integer values of 0 to 30. 
   
     
     
         2 . Catalytic composition according to  claim 1 , in which said catalytic composition comprises a hydrocarbyl aluminum compound, called an activating agent, selected from the group that is formed by the tris(hydrocarbyl)aluminum compounds, the chlorinated or brominated hydrocarbyl aluminum compounds, and the aluminoxanes. 
     
     
         3 . Catalytic composition according to  claim 1 , in which said group (CR 10 R 11 ) n  is selected from among the following groups: —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —C(CH 3 ) 2 —, —C(CH 3 ) 2 —CH 2 —, —C(CH 3 ) 2 —CH 2 —CH 2 —, —C(CF 3 ) 2 —, —C(CF 3 ) 2 —CH 2 — and —C(CF 3 ) 2 —CH 2 —CH 2 —. 
     
     
         4 . Catalytic composition according to  claim 1 , in which said functional group L is selected from among the following groups: methoxy (—OMe), butoxy (—OBu), dimethylamino (—NMe 2 ), pyrrolidino (C 4 H 8 N), pyridino (—C 5 H 4 N), phosphino (—PR 2 ), in which R is an alkyl or aryl group that may or may not be substituted, thiofene (—C 4 H 3 S), tetrahydrofuran (—C 4 H 7 O), furan (—C 4 H 3 O), and phenyl (—C 6 H 5 ), whereby said groups may or may not be substituted. 
     
     
         5 . Catalytic composition according to  claim 4 , in which said group L is the phosphino group (—PR 2 ), in which R is an alkyl or aryl group that may or may not be substituted. 
     
     
         6 . Catalytic composition according to  claim 1 , in which M is an element of group IV that is selected from among titanium and zirconium. 
     
     
         7 . Catalytic composition according to  claim 1 , in which Y is a radical that is selected from the group that is formed by the alkoxies R′O—, where R′ is a hydrocarbyl radical that comprises 1 to 30 carbon atoms. 
     
     
         8 . Process for oligomerization of olefins into compounds or into a mixture of compounds of general formula CpH2p with 4≦p≦80 that employs a catalytic composition according to  claim 1 . 
     
     
         9 . Process for oligomerization of olefins according to  claim 8 , in which p is between 4 and 14. 
     
     
         10 . Process for oligomerization of olefins according to  claim 8 , in which the feedstock is ethylene. 
     
     
         11 . Process for oligomerization of olefins according to  claim 8 , in which the process is a process for dimerization of ethylene, in the case where the element M of group IV is titanium. 
     
     
         12 . Process for oligomerization of olefins according to  claim 11 , in which the process is a process for selective dimerization of ethylene into butene-1, in the case where the element M of group IV is titanium. 
     
     
         13 . Process for oligomerization of olefins according to  claim 11 , in which titanium is used as a metal, triethyl aluminum is used as an activating agent, and an activating agent to organometallic complex molar ratio of between 1 and 5 is used for the dimerization of ethylene. 
     
     
         14 . Process for oligomerization of olefins according to  claim 1 , in which zirconium is used as metal, ethyl aluminum sesquichloride is used as an activating agent, and an activating agent to organometallic complex molar ratio of between 6 and 30 is used for the oligomerization of ethylene.