Resumen
[0001] The present invention relates to metallocene compounds characterized by the following formulas: (LR<k>)<z>[LR<k-f>(R<I>OH)<f>]<x>MX<y> I <img class="EMIRef" id="582434922-ia01" /> <img class="EMIRef" id="582434922-ia02" /> wherein: L, equal to or different from each other, is selected from the group comprising: cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl or benzoindenyl; each R is independently selected from hydrogen, C<1>-C<20> alkyl, C<3>-C<20> cycloalkyl, C<6>-C<20> aryl, C<3>-C<20> alkenyl, C<7>-C<20> arylalkyl, C<7>-C<20> alkylaryl, C<8>-C<20> arylalkenyl, linear or branched, optionally substituted by 1 to 10 halogen atoms, or a group SiR<II>3 ; each RI equal to or different from each other, is a group SiR<II>2 or a divalent aliphatic or aromatic hydrocarbon group containing from 1 to 20 carbon atoms, optionally containing from 1 to 5 heteroatoms of groups 14 to 16 of the periodic table of the elements and boron; each Q is independently selected from B, C, Si Ge, Sn; M is a metal of group 3, 4 or 10 of the Periodic Table, Lanthanide or Actinide; each X is independently selected from: hydrogen, chlorine, bromine, OR<II>, NR<II>2 , C<1>-C<20> alkyl or C<5>-C<20> aryl; each RII is independently selected from C<1>-C<20> alkyl , C<3>-C<20> cycloalkyl C<6>-C<20> aryl, C<3>-C<20> alkenyl, C<7>-C<20> arylalkyl, C<7>-C<20> arylalkenyl or alkylaryl, linear or branched; R<II> is methyl, ethyl, isopropyl; L' is N or O; when L is cyclopentadienyl k is equal 5, when L is indenyl k is equal to 7, when L is fluorenyl or benzoindenyl k is equal to 9, when L is tetrahydroindenyl k is equal to 11 and when L is octahydrofluorenyl, k is equal to 17; z is equal to 0, 1 or 2; x is equal to 1, 2 or 3; y is equal to 1, 2 or 3; x + y + z is equal to the valence of M; m is an integer which can assume the values 1, 2, 3 or 4; a and b are integers whose value ranges from 0 to k-1; f is an integer whose value ranges from 1 to k; g is 0 or 1; c and e are equal to 0 or 1; a + b + c is at least 1 ; a + g + c is at least 1; d is equal to 0, 1 or 2; when Q is B, then c + d = 1 ; when Q is C, Si, Ge or Sn, then c + d = 2; when L' is N, then g + e = 1; when L' is O, then g = 0 and e = 0.
Reivindicaciones
1. Metallocene compound characterized by the following formulas: (LR<k>)<z>[LR<k-f>(R<I>OH)<f>]<x>MX<y> I <img class="EMIRef" id="582434924-ib0027" /> <img class="EMIRef" id="582434924-ib0028" /> wherein: L, equal to or different from each other, is selected from the group comprising: cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl or benzoindenyl; each R is independently selected from hydrogen, C<1>-C<20> alkyl, C<3>-C<20> cycloalkyl, C<6>-C<20> aryl, C<3>-C<20> alkenyl, C<7>-C<20> arylalkyl, C<7>-C<20> alkylaryl, C<8>-C<20> arylalkenyl, linear or branched, optionally substituted by 1 to 10 halogen atoms, or a group SiR<II>3 ; each RI , equal to or different from each other, is a group SiR<II>2 or a divalent aliphatic or aromatic hydrocarbon group containing from 1 to 20 carbon atoms, optionally containing from 1 to 5 heteroatoms of groups 14 to 16 of the periodic table of the elements and boron ; each Q is independently selected from B, C, Si, Ge, Sn; M is a metal of group 3, 4 or 10 of the Periodic Table, Lanthanide or Actinide; each X is independently selected from: hydrogen, chlorine, bromine, OR<II>, NR<II>2 , C<1>-C<20> alkyl or C<6>-C<20> aryl; each RII is independently selected from C<1>-C<20> alkyl , C<3>-C<20> cycloalkyl, C<6>-C<20> aryl, C<3>-C<20> alkenyl, C<7>-C<20> arylalkyl, C<7>-C<20> arylalkenyl or alkylaryl, linear or branched; R<II> is methyl, ethyl, isopropyl; L' is N or O; when L is cyclopentadienyl k is equal to 5, when L is indenyl k is equal to 7, when L is fluorenyl or benzoindenyl k is equal to 9, when L is tetrahydroindenyl k is equal to 11 and when L is octahydrofluorenyl, k is equal to 17; z is equal to 0, 1 or 2; x is equal to 1, 2 or 3; y is equal to 1, 2 or 3; x + y + z is equal to the valence of M; m is an integer which can assume the values 1, 2, 3 or 4; a and b are integers whose value ranges from 0 to k-1; f is an integer whose value ranges from 1 to k; g is 0 or 1 ; c and e are equal to 0 or 1; a + b + c is at least 1; a + g + c is at least 1; d is equal to 0, 1 or 2; when Q is B then c + d = 1; when Q is C, Si, Ge or Sn, then c + d = 2; when L' is N, then g + e = 1; when L' is ○, then g = 0 and e = 0. 2. Metallocene compound according to claim 1, wherein RI is: C<1>-C<20> alkylene, C<3>-C<20>cycloalkylene, C<6>-C<20> arylene, C<7>-C<20> alkenyl, C<7>-C<20> arylalkylene, or alkylarylene, linear or branched, or a group SiR<II>2 ; 3. Metallocene according to claim 1 wherein R<I>OH is selected from; CH<2>-CH<2>-OH, CH<2>-CH<2>-CH<2>-OH, O-CH<2>-CH<2>-OH, SiMe<2>-CH<2>-CH<2>-OH or SiMe<2>-CH<2>- CH<2>-CH<2>-OH. 4. Metallocene according to claims 1-3 wherein M is titanium, zirconium or hafnium. 5. Metallocene compound according to claims 1-4 wherein at least one L is a fluorenyl or octahydrofluorenyl ring. 6. Process for obtaining metallocene compounds of formula I according to claims 1-5 by reacting a compound of general formula [(LR<k-f>(R<I>OJ)<f>)]M', wherein M' is an alkali metal, preferably Li, Na or K and J is a protective group that masks the OH group, with a transition metal compound of general formula (LR<k>)<z>MX<n>(E)<q>, wherein E is a linear or cyclic ether, q is a number ranging from 0 to 4 and n is an integer number ranging from 2 to 4 and L, R, k, z and X have been already defined, followed by a cleavage of the group O-J. 7. Process for obtaining metallocene compounds of formulas II and III according to claims 1-5 by reacting a transition metal compound of general formula MX<n>(E)<q>, wherein E is a linear or cyclic ether, q is a number between 0 and 4 and n is 3 or 4, with another compound of general formula <img class="EMIRef" id="582434924-ib0029" /> wherein M' is an alkali metal, preferably Li, Na or K and J is a protective group that masks the OH group, followed by a cleavage of the group O-J. 8. Process according to claim 6, wherein the compound of formula MX<n>(E)<q> is selected from the group consisting of TiCl<4>, ZrCl<4> HfCl<4>, TiCl<3>, TiCl<3>• 2THF. 9. Process according to claims 6-8, wherein J is SiR<II>3 and the group O-SiR<II>3 is cleaved by controlled hydrolysis reactions.
