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ORGANOMETALLIC COMPOUND CATALYST FOR POLYMERIZATION OR COPOLYMERIZATION OF ALPHA-OLEFINCM Patents

Índice de la ficha

Updated at
24/07/2026
Numero publicacion
EP.0839833.A2
Fecha publicacion
06/05/1998
Numero solicitud
EP19970500184

En detalle

Resumen

PROBLEM TO BE SOLVED: To obtain a new compound (catalyst) useful for (co)polymerization of an α-olefin, capable of forming a polymer having a high molecular weight. SOLUTION: The catalytic component for polymerization of an α-olefin is shown by formula I [M is a transition metal of the group III of the periodic table; X is H, etc.; (n) is the residual free valence of the metal M and is 1-3; L is a neutral Lewis base; (z) is 1-3; A is a ring directly coordinated to the transition metal M, containing a nonlocalized π electron; E is BR<11> (R<11> is H, etc.); D is O, etc.] such as [2-(cyclopentadienyl)1-oxo-ethanediyl] titanium dichloride. The catalyst is obtained by reacting a compound of the formula HA-E-E- DH with 2 equivalent of an alkyl alkali metal salt to give a compound of formula II (M' is Li, etc.) and reacting the compound with a compound of the formula MX4 . A catalytic system comprising the catalytic component of the formula I and a promoter component (methylaluminoxane) is especially suitable for copolymerization of ethylene and propylene. The polymerization can be carried out in a solution, in a suspension, in a vapor-phase of a bulky state at a high temperature under high pressure.

Reivindicaciones

1. Catalyst component for the polymerisation of alpha-olefins of general formula (I) <img class="EMIRef" id="579442586-ib0010" /> wherein: M is a transition metal of groups 3, 4-10 of the periodic table of the elements, lanthanide or actinide; each X group, equal to or different from each other, is hydrogen, halogen, alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl with 1 to 20 carbon atoms, branched or not, the hydrogens of these groups are optionally substituted by SiR<3>, GeR<3>, OR , NR<2>, OSiR<3> groups or any combination thereof wherein R is selected from the group comprising: hydrogen, C<1>-C<20> alkyl, C<3>-C<20>cycloalkyl, C<6>-C<20> aryl, C<7>-C<20> alkenyl, C<7>-C<20> arylalkyl, C<7>-C<20> arylalkenyl or alkylaryl, branched or linear; n is a number whose value is: 0, 1, 2 or 3, in order to fill the remaining free valences of the metal M; L is a neutral Lewis base; z is a number whose value is: 0, 1, 2 or 3; A is a ring with delocalized π electrons, that directly coordinates to the transition metal M; each E group, equal to or different from each other, is BR<II>, CR<III>2 , SiR<II>2 , GeR<II>2 ; each R<II>, equal to or different from each other, is hydrogen, alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl with 1 to 20 carbon atoms, linear or branched, whose hydrogens are optionally substituted by SiR<3>, GeR<3>, OR , NR<2>, OSiR<3> groups or any combination thereof wherein R is above defined; R<III> has the same meaning of R<II> or it is halogen; besides two groups selected from R<II> and R<III> belonging to different E optionally form a cyclic structure; D is selected from the group comprising: O, S, PR<IV> or a neutral ligand selected from the group comprising: OR<IV>, SR<IV>, PR<IV>2 ; each R<IV>, equal to or different from each other, is hydrogen, alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl from 1 to 20 carbon atoms, branched or not, whose hydrogens are substituted by SiR<3>, GeR<3>, OR, NR<2>, OSiR<3> groups or any combination thereof wherein R is above defined; or it moreover forms a condensed ring through another bond with E. 2. Catalyst component according to claim 1 wherein A is a cyclopentadienyl type of ring of formula C<5>R<I>4 , wherein each R<I> group, equal to or different from each other, is hydrogen, C<1>-C<20> alkyl, C<3>-C<20> cycloalkyl, C<6>-C<20> aryl, C<7>-C<20> alkenyl, C<7>-C<20> arylalkyl, C<7>-C<20> arylalkenyl or alkylaryl, branched or linear, the hydrogens of these groups are optionally substituted by SiR<3>, GeR<3>, OR, NR<2>, OSiR<3> groups or any combination thereof wherein Ris described in claim 1; R<I> is also selected from the group comprising SiR<3>, GeR<3>, OR, NR<2>, OSiR<3> groups or any combination thereof; two adjacent R<I> optionally unite in order to form a saturated or unsaturated polycyclic cyclopentadienyl ring, optionally substituted with R<I> groups. 3. Catalyst component according to claim 1-2, wherein M of general formula (I) is selected from the group consisting of zirconium, titanium or hafnium. 4. Catalyst component according to claims 1-3 , wherein the bridging group E-E is CR<III>2 -CR<III>2 . 5. Catalyst system comprising a cocatalyst selected from the group consisting of alkylaluminoxane, modified aluminoxane, boron compounds and a catalyst component according to claims 1-4. 6. Catalyst system according to claim 5 wherein the cocatalyst is selected from the group comprising: methylaluminoxane, ethylaluminoxane, N,N-dimethylaniliniumtetrakys (pentafluorophenyl) borate, and trispentafluorophenylborane. 7. Process for obtaining polyolefins in solution, in suspension, in gas phase at low and high pressure and temperature or in mass at high pressures and high or low temperatures, characterized by the use of the catalyst according to claims 5-6. 8. Process for obtaining polyolefins according to claim 7, wherein the polymerization temperature varies between -60°C and 300°C, the pressure varies between 1 and 4000 atmospheres, the transition metal concentration varies between 10<-7> and 10<-3> M, the cocatalyst is an aluminium organocomplex and the cocatalyst/transition metal molar ratio varies between 10 and 10000. 9. Process for obtaining polyolefins according to claim 7, wherein the polymerization temperature varies between -60°C and 300°C, the pressure varies between 1 and 4000 atmospheres, the transition metal molar concentration varies between 10<-7> and 10<-3>, the cocatalyst is a boron compound and the cocatalyst/transition metal molar ratio varies between 0.5 and 10. 10. Process for obtaining polyolefins according to claim 8, characterized in that the polymerization temperature varies between -40°C and 220°C, the pressure varies between 1 and 4000 atmospheres, the transition metal concentration varies between 10<-6> and 10<-4> M, the cocatalyst is an aluminium organocomplex and the cocatalyst/transition metal molar ratio varies between 500 and 1500 11. Process for obtaining polyolefins according to claim 9, characterized in that the polymerization temperature varies between 40°C and 220°C, the pressure varies between 1 and 4000 atmospheres, the transition metal molar concentration varies between 10<-6> and 10<-4>, the cocatalyst is a boron compound and the cocatalyst/transition metal molar ratio varies between 0.9 and 5 12. Process for obtaining polyolefins according to claims 7-11, wherein the monomer is ethylene. 13. Process for obtaining ethylene copolymers according to claims 7-12, wherein the comonomer is selected from the group comprising: propene, 1-butene, 1-hexene, 1-octene, 1-hexadecene, 4-methyl-1-pentene, hexadiene and styrene or mixtures thereof. 14. Process for obtaining the compound of formula: <img class="EMIRef" id="579442586-ib0011" /> wherein E is CR<III>2 and A, M, L, X, z and n are defined in claims 1-4 characterized by the following steps: a) contacting the compound (II) with the alkali metal salt of the cyclic organic compound HA, according to the following scheme: <img class="EMIRef" id="579442586-ib0012" /> b) treating the reaction product of step a) with water <img class="EMIRef" id="579442586-ib0013" /> Wherein R<III> is above defined and M' is selected from the group comprising Li, Na or K. c) treating the compound of formula: <img class="EMIRef" id="579442586-ib0014" /> with two equivalents of an alkyl or aryl alkali metal compound, or with an alkali metal hydride or an alkali metal according the following scheme: <img class="EMIRef" id="579442586-ib0015" /> Wherein R<c> is C<1>-C<20> alkyl or C<6>-C<20> aryl. d) contacting the compound of formula M'A- CR<III>2 -CR<III>2 -OM' with a metal M compound, of formula MX<4> or with an adduct of formula MX<4>. 2L, or MX<3>. 3L, wherein L is a linear or cyclic ether 15. Process for obtaining a compound of formula: <img class="EMIRef" id="579442586-ib0016" /> according to claims 12 wherein E is CR<III> <2> and A, M, L, X, z and n are defined in claims 1-4 characterized by the following steps: a) reacting a compound of formula HA- CR<III> <2>-CR<III>2 -OH obtained by step b) of the process of claims 12 or its lithium salt with an alkyl- or aryl-sulphonates according to the scheme: HA- CR III 2 -CR III 2 -OJ + ClSO 2 R a → HA- CR III 2 -CR III 2 -OSO 2 R a <img class="EMIRef" id="579442586-ib0017" /> wherein J is lithium or hydrogen R<a> is C<1>-C<20> alkyl, perfuoralkyl or C<6>-C<20> aryl radical; b) contacting the recovered product of step a) with an excess of an amine of formula NR<IV>H<2> according to the scheme: HA-CR III 2 -CR III 2 -OSO 2 R a + H 2 NR IV → HA-CR III 2 -CR III 2 -NHR IV + HNR IV -OSO 2 R a <img class="EMIRef" id="579442586-ib0018" /> c) treating the compound of formula HA-CR<III> <2>-CR<III> <2>-NHR<IV> with two equivalents of an alkyl or aryl alkali metal salt, or with an alkali metal hydride or an alkali metal according the following scheme: <img class="EMIRef" id="579442586-ib0019" /> Wherein R<c> is C<1>-C<20> alkyl or C<6>-C<20> aryl. d) contacting the compound of formula M'A-CR<III>2 -CR<III>2 -NR<IV>M' with a metal M compound, of formula MX<4> or with an adduct of formula MX<4>. 2L, or MX<3>. 3L, wherein L is a linear or cyclic ether.

Etiquetas

Inventores
Sancho Royo JoseMunoz-Escalona Lafuente AntoniPena Garcia BegonaMartin Marcos CarlosMunoz-Escalona Lafuente, AntonioRoyo Jose SanchoLafuente Antonio Munoz-EscalonGarcia Begona PenaMarcos Carlos MartinLafuente Antonio Munoz-EscalonaCarlos Martin MarkosJose Sancho RoyoAntonio Munoz-Escalona LafuenteBegona Pena GarciaCarlos Martin MarcosRoyoJose SanchoLafuenteAntonio Munoz-EscalonaGarciaBegona PenaMarcosCarlos Martin
Solicitantes
Repsol Quimica SaRepsol Quimica SA, MadridRespol Quimica S A
Clasificacion ipc
B01J 31/ 14 A IB01J 31/ 16 A IB01J 31/ 18 A IB01J 31/ 22 A IC07F 17/ 00 A IC08F 10/ 00 A IC08F 10/ 02 A IC08F 4/ 60 A IC08F 4/ 642 A IC08F 4/ 643 A IC08F 4/ 645 A IC08F 4/ 6592 A IC08F 4/ 659 A I
Clasificacion cpc
4H050/AA024H050/AA034H050/AB404H050/BE624H050/WB114H050/WB124H050/WB134H050/WB144H050/WB154H050/WB164H050/WB174H050/WB214J028/AC104J128/AA014J128/AB014J128/AC014J128/AC024J128/AC034J128/AC084J128/AC094J128/AC104J128/AC224J128/AC234J128/AC264J128/AC274J128/AC284J128/AC314J128/AC374J128/AC384J128/AC394J128/AC414J128/AC454J128/AC494J128/AC504J128/AD014J128/AD024J128/AD114J128/AE004J128/BA02A4J128/BB01A4J128/BC12A4J128/BC14A4J128/BC15A4J128/BC25A4J128/BC32A4J128/BC39A4J128/CA24A4J128/CA27A4J128/CA28A4J128/CA29A4J128/CA30A4J128/CA36A4J128/CA51A4J128/CA54A4J128/CB61A4J128/CB62A4J128/CB81A4J128/CB82A4J128/CB91A4J128/CB94A4J128/DB02A4J128/DB03A4J128/DB06A4J128/DB08A4J128/EB014J128/EB024J128/EB034J128/EB044J128/EB054J128/EB064J128/EB074J128/EB084J128/EB094J128/EB104J128/EC014J128/EC024J128/EC034J128/FA014J128/FA024J128/FA034J128/FA044J128/FA064J128/FA074J128/FA094J128/GA014J128/GA044J128/GA064J128/GB044J128/GB06C07F17/00C08F10/00C08F10/00&510C08F4/642C08F4/645C08F4/659C08F4/65924J128/AB004J128/AD134J128/BA01A4J128/BA01B4J128/BB00A4J128/BB00B4J128/BB01B4J128/BC01B4J128/BC12B4J128/BC25B4J128/BC31A4J128/BC42A4J128/BC43A4J128/CA07A4J128/CB63A4J128/CB64A4J128/EA014J128/EB114J128/EB214J128/GB014J128/BA00A4J128/BC13B4J128/BC14B502/103502/117502/120502/152526/127526/130526/134526/160526/943534/11534/15556/11556/136556/137556/140556/146556/20556/21556/43556/46556/52556/58556/7556/8
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