Bis-imine pyridine complex of lanthanides catalytic system comprising said bis-imine pyridine complex and process for the (co)polymerization of conjugated dienes

Abstract

A bis-imine pyridine complex of lanthanides having general formula (I): Said bis-imine pyridine complex of lanthanides having general formula (I) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

1 . A bis-imine pyridine complex of lanthanides having general formula (I): 
       
         
           
           
               
               
           
         
         wherein: 
         Ln represents a metal of the series of lanthanides; 
         R 1  and R 2 , equal to or different from each other, represent a hydrogen atom; or they are selected from linear or branched C 1 -C 20  alkyl groups, cycloalkyl groups optionally substituted, aryl groups optionally substituted; 
         R 3  and R 4 , equal to or different from each other, represent a hydrogen atom; or they are selected from linear or branched C 1 -C 20  alkyl groups, cycloalkyl groups optionally substituted, aryl groups optionally substituted; 
         or R 2  and R 4  can be optionally bound to each other so as to form, together with the other atoms to which they are bound, a saturated, unsaturated or aromatic cycle containing from 3 to 6 carbon atoms, optionally substituted with linear or branched C 1 -C 20  alkyl groups, said cycle optionally containing other heteroatoms such as oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; 
         or R 1  and R 3  can be optionally bound to each other so as to form, together with the other atoms to which they are bound, a saturated, unsaturated or aromatic cycle containing from 3 to 6 carbon atoms, optionally substituted with linear or branched C 1 -C 20  alkyl groups, said cycle optionally containing other heteroatoms; and 
         X 1 , X 2  and X 3 , equal to or different from each other, represent a halogen atom; or they are selected from linear or branched C 1 -C 20  alkyl groups, —OCOR 5  or —OR 5  groups wherein R 5  is selected from linear or branched C 1 -C 20  alkyl groups. 
       
     
     
         2 . The bis-imine pyridine complex of lanthanides having general formula (I) according to  claim 1 , wherein Ln represents neodymium (Nd), lanthanum (La), praseodymium (Pr), gadolinium (Gd), europium (Eu), terbium (Tb), samarium (Sm), erbium (Er), or ytterbium (Yb). 
     
     
         3 . The bis-imine pyridine complex of lanthanides having general formula (I) according to  claim 1 , wherein:
 Ln is neodymium (Nd), praseodymium (Pr), gadolinium (Gd), or lanthanum (La);   R 1  and R 2 , the same as each other, are a hydrogen atom; or they are selected from linear or branched C 1 -C 20  alkyl groups; or they are selected from cycloalkyl groups optionally substituted;   R 3  and R 4 , equal to or different from each other, are selected from phenyl groups, optionally substituted; or they are selected from cycloalkyl groups optionally substituted;   X 1 , X 2  and X 3 , the same as each other, are a halogen atom.   
     
     
         4 . A catalytic system for the (co)polymerization of conjugated dienes comprising:
 (a) at least one bis-imine pyridine complex of lanthanides having general formula (I) according to  claim 1 ;   (b) at least one co-catalyst selected from:
 (b1) aluminium alkyls having general formula (II):
   Al(X′) n (R 6 ) 3-n   (II)
 
 
   wherein X′ represents a halogen atom; R 6  is selected from linear or branched C 1 -C 20  alkyl groups, C 3 -C 20  cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more atoms of silicon or germanium; and n is an integer ranging from 0 to 2;
 (b2) aluminium oxanes having general formula (III):
   (R 7 ) 2 —Al—O—[—Al(R 8 )—O—] p —Al—(R 9 ) 2   (III)
 
 
   wherein R 7 , R 8  and R 9 , equal to or different from each other, represent a hydrogen atom, a halogen atom; or they are selected from linear or branched C 1 -C 20  alkyl groups, C 3 -C 20  cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more atoms of silicon or germanium; and p is an integer ranging from 0 to 1,000; and
 (b3) compounds having general formula (IV):
   D + E −   (IV)
 
 
   wherein D +  represents a Brønsted acid capable of releasing a proton and of reacting irreversibly with the substituent X of the bis-imine pyridine complex of lanthanides having general formula (I); E −  represents a compatible anion capable of stabilizing the active catalytic species generated by the reaction of the two components and which is sufficiently labile as to be removed by an olefin monomer, or an anion having general formula B(Ar) 4   (−)  wherein the substituents Ar, equal to or different from each other, are selected from aryl groups.   
     
     
         5 . The catalytic system for the (co)polymerization of conjugated dienes according to  claim 4 , wherein said co-catalyst (b) is selected from: tri-iso-butyl-aluminum (TIBA), di-iso-butyl-aluminium hydride (DIBAH), methylaluminumoxane (MAO), or tetra-iso-butyl-aluminumoxane (TIBAO). 
     
     
         6 . The catalytic system for the (co)polymerization of conjugated dienes according to  claim 4 , wherein in said catalytic system the molar ratio between the lanthanide present in the bis-imine pyridine complex of lanthanides (a) having general formula (I) and the aluminium present in the co-catalyst (b) selected from aluminium alkyls (b 1 ) or aluminumoxanes (b2), ranges from 5 to 5,000. 
     
     
         7 . The catalytic system for the (co)polymerization of conjugated dienes according to  claim 4 , wherein in said catalytic system the molar ratio between the lanthanide present in the bis-imine pyridine complex of lanthanides (a) having general formula (I) and the boron present in the co-catalyst (b) selected from compounds (b 3 ) having general formula (IV), ranges from 0.1 to 15. 
     
     
         8 . (canceled) 
     
     
         9 . The catalytic system according to  claim 1 , wherein said conjugated dienes are 1,3-butadiene, isoprene. 
     
     
         10 - 12 . (canceled)