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Catalytic systems for the polymerization and copolymerization of alpha-olefinsCM Patents

[0001] The invention relates to heterogeneous catalytic systems obtainable by reacting a porous inorganic support with an alumoxane and subsequently supporting at least one metallocene compound thereon, characterized in that the metallocene compound is defined by the following general formulas: (LR<k>)<z>[LR<k-f>(R<I>OSiR<II> <3>)<f>]<x>MX<y> I <img class="EMIRef" id="582232125-ia01" /> <img class="EMIRef" id="582232125-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 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 ; preferably it 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 ; 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<8>-C<20> arylalkenyl or C<7>-C<20> alkylaryl, linear or branched; preferably R<II> is methyl, ethyl, isopropyl; 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; preferably it is titanium, zirconium or hafnium; 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; L' is N or O; 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 an integer whose value ranges from 0 to 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. [0002] The invention also relates to the polymerization process making use of the above defined catalytic

Datos clave

CategoríaInvención

Índice de la ficha

Updated at
05/11/2026
Numero publicacion
EP.0953581.A1
Fecha publicacion
03/11/1999
Anio publicacion
1999
Numero solicitud
EP19990500063

En detalle

Reivindicaciones

1. Heterogeneous catalytic system obtainable by reacting a porous inorganic support with an alumoxane and subsequently supporting at least one metallocene compound thereon, characterized in that the metallocene compound is defined by the following general formulas: (LR<k>)<z>[LR<k-f>(R<I>OSiR<II> <3>)<f>]<x>MX<y> I <img class="EMIRef" id="582232127-ib0028" /> <img class="EMIRef" id="582232127-ib0029" /> 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 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 ; preferably it 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 ; 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<8>-C<20> arylalkenyl or C<7>-C<20> alkylaryl, linear or branched; preferably R<II> is methyl, ethyl or isopropyl; 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; 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 an integer whose value ranges from 0 to 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. 2. Heterogeneous catalytic system according to claim 1 wherein the group R<I>OSiR<II>3 is selected from CH<2>-CH<2>-OSiMe<3>, CH<2>-CH<2>-CH<2>-OSiMe<3>, CH<2>-O-CH<2>-OSiMe<3>, O-CH<2>-CH<2>-OSiMe<3>, SiMe<2>-CH<2>-CH<2>-OSiMe<3>, SiMe<2>-OSiMe<3> or SiMe<2>-CH<2>-CH<2>-CH<2>-0SiMe<3>. 3. Heterogeneous catalytic system according to claims 1-3 wherein M is titanium, zirconium or hafnium. 4. Heterogeneous catalytic system according to claims 1-4 wherein the alumoxane is represented by the formulas: (RAIO)<n> R(R-Al-O)<m>AlR<2> wherein R is alkyl or aryl group containing from 1 to 20 carbon atoms; n ranges from 1 to 40, and m ranges from 3 to 40. 5. Heterogeneous catalyst system according to claims 1-5 wherein the inorganic support is selected from silica, alumina, silica alumina, aluminium phosphates and mixtures thereof. 6. Heterogeneous catalyst system according to claims 1-6 wherein the content in transition metal is comprised between 0.01 and 3% by weight. 7. Heterogeneous catalyst system according to claim 7 wherein the content in transition metal is comprised between 0.1 and 1% by weight. 8. Process for the polymerization of alpha olefins in slurry or in gas phase characterized by the use of the heterogeneous catalyst system of claims 1-8. 9. Metallocene compounds according to the following formulas: (LR<k>)<z>[LR<k-f>(R<I>OSiR<II> <3>)<f>]<x>MX<y> I <img class="EMIRef" id="582232127-ib0030" /> <img class="EMIRef" id="582232127-ib0031" /> wherein: L, equal to or different from each other, is selected from the group comprising: cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl and 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 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 ; preferably it 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 ; 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<8>-C<20> arylalkenyl or C<7>-C<20> alkylaryl, linear or branched; preferably R<II> is methyl, ethyl or isopropyl; 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; preferably it is titanium, zirconium or hafnium; 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; 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 an integer whose value ranges from 0 to 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. characterized in that at least one L is a fluorenyl, benzoindenyl or octahydrofluorenyl ring, optionally substituted by 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<8>-C<20> arylalkenyl or C<7>-C<20> alkylaryl.

Etiquetas

Inventores
Munoz-Escalona Lafuente, AntonioMunoz-Escalona Lafuente AntoniLafuente Canas, PilarLafuente Canas PilarSancho Royo, JoseSancho Royo JosePena Garcia BegonaPena Garcia, BegonaMartinez Nunez, Ma FranciscaMartinez Nunez Ma FranciscaMartin Marcos CarlosMartin Marcos, Carlos
Solicitantes
Repsol Química S.A.
Clasificacion ipc
C08F 10/ 00 A IC08F 4/ 602 A I
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