Heterogeneous catalyst components for olefins polymerization, preparation process and use thereof

Abstract

It is shown metallocenes with functionalized bridge of formula wherein M represents a transition metal of groups 3, 4, 5 or 6, L represents cyclopentadieliyl-type ligands, Y represents a halogen and which can own one or various bridges between uritics L. At least one of these bridges is functionalized through a group constituted by the union between a halogen atom and a silicon, germanium or tin atom. It is also shown a method for the synthesis of these metallocene compounds starting from the corresponding metallic halure and a precursor of the ligand which has leaving groups. These metallocene compounds are used as catalyst precursors for the homopolymerization and copolymerization of olefins. It is also shown methods for supporting these metallocenes on inorganic solids in order to obtain solid catalyst systems for olefins polymerization processes in a heterogeneous phase.

1 . A metallocene catalyst component for olefin polymerization comprising a metallocene compound characterized by the following formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 Y is halogen;  
 M is a transition metal of groups 3-6 of the periodic table;  
 each L is independently selected from a cyclopentadienyl-type unity, including indenyl or fluorenyl, substituted or not and the substituents being equal or different, united to M through a π bond;  
 Z is a group that forms a union bridge between the two unities L, which can have between 0 and 20 carbon atoms and between 0 and 5 oxygen, sulfur, nitrogen, phosphorus, silicon, germanium, tin or boron atoms;  
 E is a spacer group that unites Z and Y and can have between 0 and 20 carbon atoms and between 0 and 5 oxygen, sulfur, nitrogen, phosphorus, silicon, germanium, tin or boron atoms. It is characterized for having in its skeleton at least one silicon, germaniun) or tin atom, which  
 the substituent Y is united to;  
 o is a number of value 0 or 1;  
 k is a nunber ofvalue 1, 2 or 3;  
 m is a number equal to or higher than 2 and coinciding with the oxidation state of the transition metal;  
 j is a number of value 0 or 1 with the condition that its value is 1 at least once; when j is 1 and o is 0, Z is characterized by having at least one silicon, germanium or tin atom which Y is directly united to;  
 with the proviso that the compound does not have general formula 
 X m -M 1 (L′-M 2 (R 1 R 2 )-A′-Z′R 3   o -Hal p -) n , 
 wherein M 1  is a metal of group 4, 5 or 6 of the periodic table, each X is independently selected from hydrogen, halogen or a C 1 -C 40  carbon-containing rest; m′ is equal to 1, 2 or 3; n′ is equal to 1 or 2; each L′ is independently a n ligand, which coordinates to the central atom M 1 ; each M 2  is independently selected from silicon, germanium or tin; R 1  is a C 1 -C 20  carbon-containing group; R 2  is a C 1 -C 20  carbon-containing group or a π ligand, which coordinates to the central atom M 1 ; each A′ is independently a divalent C 1 -C 40  carbon-containing rest; each Z′ is independently selected from boron, silicon, germanium or tin; each R 3  is independently selected from hydrogen or a C 1 -C 20  carbon-containing rest; o′ is equal to 0, 1 or 2; each Hal is independently selected from a halogen atom; p′ is equal to 1, 2 or 3.  
 
     
     
         2 . A catalyst component according to  claim 1 , characterized in that the metallocene compound has formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 Y is halogen;  
 M is a transition metal of groups 3, 4, 5 or 6 of the periodic table;  
 each L is independently selected from a cyclopentadienyl-type unity, including indenyl or fluorenyl, substituted or not and the substituents being equal or different, united to M through a π bond;  
 Q is an element of group 13, 14 or 15;  
 E is a spacer group that unites Q and Y and can have between 0 and 20 carbon atoms and between 0 and 5 oxygen, sulfur, nitrogen, phosphorus, silicon, germanium, tin or boron atoms and it is characterized by having in its skeleton at least one silicon, germanium or tin atom, which the substituent Y is united to;  
 R is an atom of hydrogen, halogen, halocarbon, substituted halocarbon, C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 6 -C 20  aryl, C 7 -C 40  alkylaryl, C 7 -C 40  arylalkyl, C 8 -C 20  arylalkenyl, alkoxy, siloxy and combinations thereof;  
 A, equal to or different from each other, is a bridge group between unities L and Q constituted either by only one divalent atom of gorup 16, preferably —O—, or by a trivalent monosubstituted element of group 15, preferably >N—R, R being define above, or a tetravalent disubstituted element of group 14, preferably >C(R) 2  or >Si(R) 2 , R being define above, or by a chain of 2 or more atoms substituted or not, this chain being preferably of type —C—C—, —C—Si—, —Si—Si—, —Si—O—, —C—O—, —C—N—, —C—C—C, —C—Si—C—, —si—O—Si—;  
 o is a number of value 0 or 1;  
 k is a number of value 1, 2 or 3;  
 m is a number equal to or higher than 2 and coinciding with the oxidation state of the transition metal;  
 p, n, l are numbers of value 0 or 1,  
 j is a number of value 0 or 1 with the condition that its value is 1 at least once; when J is 1 and o is 0, Q is a silicon, germanium or tin atom;  
 with the proviso that the compound does not have general formula 
 X m -M 1 (L′-M 2 (R 1 R 2 )-A′-Z′R 3   o -Hal p -) n ,  
 wherein M 1  is a metal of group 4, 5 or 6 of the periodic table, each X is independently selected from hydrogen, halogen or a C 1 -C 40  carbon-containing rest; m′ is equal to 1, 2 or 3; n′ is equal to 1 or 2; each L′ is independently a π ligand, which coordinates to the central atom M 1 ; each M 2  is independently selected from silicon, germanium or tin; R 1  is a C 1 -C 20  carbon-containing group; R 2  is a C 1 -C 20  carbon-containing group or a π ligand, which coordinates to the central atom M 1 ; each A′ is independently a divalent C 1 -C 40  carbon-containing rest; each Z′ is independently selected from boron, silicon, germanium or tin; each R 3  is independently selected from hydrogen or a C 1 -C 20  carbon-containing rest; o′ is equal to 0, 1 or 2; each Hal is independently selected from a halogen atom; p′ is equal to 1, 2 or 3.  
 
     
     
         3 . A catalyst component according to claims  1 - 2 , characterized in that the metallocene compound has formula:  
       
         
           
           
               
               
           
         
       
       Wherein: 
 L, M, m, Y, R, l, n and A have already been defined;  
 T is selected from: silicon, germanium or tin.  
 
     
     
         4 . A catalyst component according to claims  1 - 2 , characterized in that the metallocene compound has formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 L, M, m, Y, R, E, l, n and A have already been defined;  
 T is selected from: silicon, germanium or tin.  
 
     
     
         5 . A heterogeneous catalyst component for the polymerization of olefins obtained from an inorganic solid that contains hydroxy groups and a catalyst component according to claims  1 - 4 .  
     
     
         6 . A heterogeneous catalyst component for the polymerization of olefins according to  claim 5  consisting of: an inorganic solid that contains hydroxy groups and that has been previously modified through reaction with a compound of formula:  
       
         
           
           
               
               
           
         
       
       being: 
 R: atom of hydrogen, halogen, halocarbon, substituted halocarbon, C 1-20  alkyl, C 2-20  alkenyl, C 6-20  aryl, C 7-40  alkylaryl, C 7-40  arylalkyl, C 8-20  arylalkenyl, alkoxy, siloxy and combinations thereof;  
 X: halogen or group OR 4  wherein R 4  has the same meaning given above;  
 P: NH 2 , NHR, SH, OH or PHR;  
 v+z+w=3, v being different from 0;  
 t and u are comprised between 0 and 10;  
 and a catalyst component according to claims  1 - 4 .  
 
     
     
         7 . A heterogeneous catalyst component for the polymerization of olefins according to claims  5 - 6  characterized in that the inorganic solid is selected from the group comprising: silica, silicates, carbonates, phosphates, clays, metal oxides and mixtures thereof.  
     
     
         8 . A catalyst system comprising: a catalyst component according to claims  1 - 7  in combination with a cocatalyst selected from the group comprising: non-coordinatinig compounds of alumoxane-type, modified alumoxane-type, boron compounds and combinations thereof.  
     
     
         9 . A catalyst system according to  claim 8  characterized in that the cocatalyst is selected from the group comprising: methylalumoxane, dimethylaniline tetrakis(pentafluorophenyl)boron or trispentafluorophenylborane.  
     
     
         10 . A process for the preparation of the heterogeneous catalyst component characterized in that the compound of claims  1 - 4  and the inorganic support are put in contact by using tetrahydrofurane as solvent.  
     
     
         11 . A process for the polymerization of alpha-olefins, optionally in combination with a cyclic olefin and/or a diene, characterized by the presence of a catalyst component according to claims  1 - 7 .  
     
     
         12 . A process according to  claim 11  characterized in that the monomers are selected from the group comprising: ethylene, propene, 1-butene, 1-hexene, 4-methyl-1-pentene, 4-octene and mixtures thereof.  
     
     
         13 . A process according to claim  11 - 12  for the copolymerization of ethylene in combination with a comonomer selected from the group comprising: propene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, cyclic olefins and mixtures thereof.