Process for the preparation of a metaloorganic compound comprising at least one imine ligand

Abstract

The invention relates to a process for the preparation of a metalorganic compound, comprising at least one imine ligand, characterized in that an imine ligand according to formula 1, or the HA adduct thereof, wherein HA represents an acid, of which H represents its proton and A its conjugate base, is contacted with a metal-organic reagent of formula 2 in the presence of at least 1, respectively 2 equivalents of an inorganic or metal-organic base, wherein Y═N—R (formula 1), Y is selected from a substituted carbon, nitrogen or phosphorous atom, R represents a proton, a protic or an aprotic substituent, and the metal organic compound is: M v (L 1 )k(L 2 )I(L 3 ) m (L 4 ) n X (formula 2) wherein: M represents a group 4 or group 5 metal ion, V represents the valency of the metal ion, being 3, 4 or 5, L 1 , L 2 , L 3 , and L 4 represent ligands on M and may be equal or different, X represents a group 17 halogen atom, and k, l, m, n=0, 1, 2, 3, 4 with k+l+m+n+1=V. The invention further relates to a process for the preparation of a polyolefin by making a metal-organic compound according to the process of the invention, wherein the base is an olefin polymerisation compatible base, which metal-organic compound is activated anywhere in, or before a polymerisation reactor.

1 . A process for the preparation of a metal-organic compound, comprising contacting the HA adduct of at least one imine ligand according to formula 1, wherein HA represents an acid, of which H represents its proton and A its conjugate base, is contacted with a metal-organic reagent of formula 2 in the presence of at least 1, respectively 2 equivalents of an inorganic or metal-organic base, wherein
   Y═N—R  (formula 1)   wherein Y is selected from a substituted phosphorous atom and R represents a proton, a protic or an aprotic substituent, and:
   M V (L 1 ) k (L 2 ) l (L 3 ) m (L 4 ) n X  (formula 2) 
   wherein:   M represents a group 4 or group 5 metal ion   V represents the valency of the metal ion, being 3, 4 or 5   L 1 , L 2 , L 3 , and L 4  represent ligands on M and may be equal or different   X represents a group 17 halogen atom   k, l, m, n=0, 1, 2, 3, 4 with k+l+m+n+1=V   
     
     
         2 . A process according to  claim 1  wherein R represents a hydrogen atom and wherein Y is:
 a phosphorus substituent defined by the formula:   
       
         
           
           
               
               
           
         
         wherein each R 1j , with j=1-3 is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C 1-8  alkoxy radical, a C 6-10  aryl or aryloxy radical, an amido radical, a C 1-20  hydrocarbyl radical unsubstituted or substituted by a halogen atom, a C 1-8  alkoxy radical, a C 6-10  aryl or aryloxy radical, an amido radical, a silyl radical of the formula: 
       
       
         
           
           
               
               
           
         
         and a germanyl radical of the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 2j  is independently selected from the group consisting of hydrogen, a C 1-8  alkyl or alkoxy radical, C 6-10  aryl or aryloxy radicals, provided 
         each substituent R 1j  or R 2j  may be linked with another R 1  or R 2  to form a ring system. 
       
     
     
         3 . A process according to  claim 1 , wherein the inorganic base is a carboxylate, or a fluoride, or a hydroxide, or a cyanide, or an amide, or a carbonate of Li, Na, K, Rb, Cs, or a group 2 metal salt selected from Mg, Ca, or Ba, or an alkali metal selected from Li, Na, K, Rb, or Cs of phosphate or a phosphate ester alkoxide of Li, Na, K, Rb or Cs, or phenoxide of Li, Na, K, Rb or Cs, or thallium hydroxide, or a hydrocarbanion of any of the group 1, group 2, group 12 or group 13 elements, or an alkali metal, group 1 hydride or group 2 hydride. 
     
     
         4 . A process according to  claim 3 , wherein the inorganic base is selected from sodium hydride, or calciumhydride. 
     
     
         5 . A process according to  claim 1 , wherein the metal-organic base is selected from organolithium compounds, or organomagnesium compounds. 
     
     
         6 . A process according to  claim 1 , wherein the reaction is carried out in an aprotic solvent. 
     
     
         7 . A process according to  claim 1 , wherein the process is carried out in the presence of a phase transfer reagent. 
     
     
         8 . Process for the preparation of a polyolefin by making a metal-organic compound according to the process of  claim 1 , wherein the base is an olefin polymerisation compatible base, which metal-organic compound is activated anywhere in, or before a polymerisation reactor. 
     
     
         9 . Process according to  claim 8 , wherein the metal-organic compound is formed used without purification. 
     
     
         10 . Process according to  claim 8 , wherein the metal-organic compound is formed in the polymerisation equipment.