Source: http://www.google.es/patents/US7163907
Timestamp: 2013-05-19 23:49:57
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Patente US7163907 - Aluminum-free monocyclopentadienyl metallocene catalysts for olefin ... - Google PatentesB�squeda Im�genes Maps Play YouTube Noticias Gmail Drive M�s » B�squeda avanzada de patentes | Historial web | Iniciar sesi�n B�squeda avanzada de patentesPatentesThis invention relates to a catalyst system for the production of polyolefins comprising: (A) a Group IV B transition metal component represented by one of the two general formulae wherein (C5H5-y-xRx) is a cylopentadienyl ring (JR′z-l-y) is a heteroatom ligand in which J is an element with a coordination...http://www.google.es/patents/US7163907?utm_source=gb-gplus-sharePatente US7163907 - Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization N�mero de publicaci�nUS7163907 B1Tipo de publicaci�nConcesi�n N�mero de solicitud07/542,236 Fecha de publicaci�n16 Ene 2007 Fecha de presentaci�n22 Jun 1990 Fecha de prioridad30 Ene 1987 InventoresJo Ann Marie CanichGregory George HlatkyHoward William Turner Cesionario originalExxonmobil Chemical Patents Inc. Clasificaci�n de EE.UU.502/152502/155 Clasificaci�n internacionalB01J31/00 Clasificaci�n cooperativaC07F17/00C08F110/02C08F10/00 Clasificaci�n europeaC08F10/00C07F17/00ReferenciasCitas de patentes (35)Otras citas (17) Citada por (21)Enlaces externosUSPTO Cesi�n de USPTO EspacenetAluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerizationUS 7163907 B1 Resumen This invention relates to a catalyst system for the production of polyolefins comprising:
each Q is independently, hydride, C1�C20 hydrocarbyl radicals, substituted hydrocarbyl radials wherein one or more hydrogen atoms is replaced by an electron withdrawing group, or C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of germanium and silicon, provided that Q is not a substituted or unsubstituted cyclopentadienyl ring, or both Q together may be an alkylidene, olefin, acetylene or a cyclometallated hydrocarbyl;
�y� is 0 or 1; when �y� is 1, T is a covalent bridging group containing a Group IV-A or V-A element;
L is a neutral Lewis base; and �w� is a number from 0 to 3;
(C5H5-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five radical R groups, �x� is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent R group is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals, substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of germanium and silicon, and halogen radicals; or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R groups are joined forming a C4�C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
(JR′z-l-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V-A or an element with a coordination number of two from Group VI-A of the Periodic Table of Elements, each R′ is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals and substituted C1�C20 hydrocarbyl radicals, wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
each Q is independently, hydride, C1�C20 hydrocarbyl radicals, substituted hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by an electron withdrawing group, or C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of germanium and silicon, provided that Q is not a substituted or unsubstituted cyclopentadienyl ring, or both Q together may be an alkylidene, olefin, acetylene or a cyclometallated hydrocarbyl;
L is a neutral Lewis base; and �w� is a number from 0 to 3; wherein M′ has the same meaning as M and Q′ has the same meaning as Q; and
(C5H4-xRx) is a cyclopentadienyl ring which is substituted with from zero to four radical R groups, �x� is 0, 1, 2, 3, or 4 denoting the degree of substitution, and each substituent R group is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals and substituted C1�C20 hydrocarbyl radicals, wherein one or more hydrogen atoms are replaced by a halogen atom, C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of germanium and silicon, and halogen radicals; or (C5H4-xRx) is a cyclopentadienyl ring in which two adjacent R groups are joined forming a C4�C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
(JR′2-2) is a heteroatom ligand in which J is an element with a coordination number of three from Group V-A or an element with a coordination number of two from Group VI-A of the Periodic Table of Elements, each R′ is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals and substituted C1�C20 hydrocarbyl radicals, wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element ∫;
each Q is independently hydride, C1�C20 hydrocarbyl radicals, substituted hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by an electron withdrawing group, or C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of silicon and germanium, provided that Q is not a substituted or unsubstituted cyclopentadienyl ring, or both Q together may be an alkylidene, olefin, acetylene or a cyclometallated hydrocarbyl;
L is a neutral Lewis base; and �w� is a number from 0 to 3; and
[(L′H)+]d[(M′)m+ Q 1 Q 2 . . . Q n]d− wherein:
L′ is a neutral Lewis base; H is a hydrogen atom; [L′−H] is a Bronsted acid; M′ is a metal or metalloid selected from the group consisting of Groups V-B, VI-B, VII-B, VIII, I-B, Il-B, III-A, IV-A, and V-A of the Periodic Table of the Elements; Q1 to Qn are independently, hydride, dialkylamido, alkoxide, aryloxide, hydrocarbyl, and substituted-hydrocarbyl and any one, but not more than one of Q1 to Q11 may be halide radical; �m� is an integer from 1 to 7; �n� is an integer from 2 to 8; and n−m=�D�.
[L′−H] + p[BAr 1Ar2X3X4] wherein:
[L′H] + [B(C 6 F 5)4] − 9. The catalyst system of claim 7 wherein the heteroatom ligand group J element is nitrogen.
11. The catalyst system of claim 7 wherein �x� is 4.
[L′−H] c[(CX)a(BX′)m X″ b]c−or [L′−H] d[[[(CX 3)a′(BX 4)m′(X 5)b′]c′−]2 M n+]d− wherein [L′-H] is a cation selected from the group consisting of a H+; an ammonium; a substituted ammonium wherein the substituted ammonium cation has up to three hydrogen atoms replaced with a radical selected from a group consisting of a hydrocarbyl radical containing from 1 to about 20 carbon atoms and a substituted-hydrocarbyl radical containing from 1 to 20 carbon atoms wherein one or more of the hydrogen atoms is replaced by a halogen atom; a phosphonium; and a substituted-phosphonium wherein the substituted phosphonium cation has up to three hydrogen atoms replaced with a radical selected from a group consisting of a hydrocarbyl radical containing from 1 to about 20 carbon atoms and a substituted-hydrocarbyl radical containing from 1 to 20 carbon atoms wherein one or more of the hydrogen atoms is replaced by a halogen atom; C is carbon; B is boron; each of X, X′, X″, X3 X4 and X5 are radicals selected, independently, from the group consisting of hydride radicals, halide radicals, hydrocarbyl radicals containing from 1 to about 20 carbon atoms, substituted-hydrocarbyl radicals containing from 1 to 20 carbon atoms wherein one or more of the hydrogen atoms is replaced by a halogen atom, organometalloid radicals wherein each hydrocarbyl substitution in the organo portion contains from 1 to about 20 carbon atoms, and said metalloid is selected from the group consisting of silicon; M is a transition metal; �a� and �b� are integers≧0; �c� is an integer≧1; a+b+c=an even-numbered integer from 2 to 8; and �m� is an integer ranging from 5 to 22; �a′�and �b′� are the same or a different integer≧0; �c� is an integer≧2; a′+b′+c′=an even-numbered integer from 4 to 8; �m′� is an integer from 6 to 12; �n� is an integer such that 2c′−n=d; and �d� is an integer greater than or equal to 1.
21. The catalyst system of claim 20, wherein �y� is 1 and �T� is a linear, branched or cyclic alkylene group having from 1 to 6 carbon atoms, an alkyl substituted silylene group having from 1 to 2 silicon atoms in place of carbon atoms in the bridge, or a Si1�Si2 alkyl substituted silylene group.
23. The catalyst system of claim 22 wherein �T� is an alkyl substituted silylene group having from 1 to 2 silicon carbon atoms in the bridge, or a Si1�Si2 alkyl substituted silylene group.
(C5H5-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five substituent R groups, �x� is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals, and substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of silicon and germanium, and halogen radicals, or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R groups are joined forming a C4�C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
(JR′z-l-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V-A or an element with a coordination number of two from Group VI-A of the Periodic Table of Elements, and each R′ is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals, and substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
Q is a hydride, C1�C20 hydrocarbyl radical, substituted hydrocarbyl radical wherein one or more hydrogen atoms are replaced by an electron-withdrawing group, or C1�C20 hydrocarbyl-substituted metalloid radical wherein the metalloid is selected from the group consisting of germanium and silicon, provided that Q is not a substituted or unsubstituted cyclopentadienyl ring;
�y� is 0 or 1; when �y� is 1, T is a covalent bridging group containing a Group IV A or V A element;
L is a neutral Lewis base; and �w� is a number from 0 to 3,
[M′) m+Q1Q2 . . . Qn]d− wherein M′ is a metal or metalloid selected from the group consisting of Groups V-B, VI-B, VII-B, VIII, I-B, II-B, III-A, IV-A, and V-A of the Periodic Table of the Elements;
30. The composition of matter of claim 29 wherein [A]′ is [B(C6F5)4]′. 31. The composition of matter of claim 28 wherein [A]′ is represented by the following general formula:
[(CX)n(BX′)m X″ b]c− or [[[(CX 3)n′(BX 4)m′(X 5)b′]C′]2 M n+]d− C is carbon; B is boron; each of X, C′, X″, X3X4 and X5 are radicals selected, independently, from the group consisting of hydride radicals, halide radicals, hydrocarbyl radicals containing from 1 to about 20 carbon atoms, substituted-hydrocarbyl radicals containing from 1 to 20 carbon atoms, wherein one or more of the hydrogen atoms is replaced by a halogen atom, or organometalloid radicals wherein each hydrocarbyl substitution in the organo portion contains from 1 to about 20 carbon atoms and said metalloid is selected from the group consisting of silicon; M is a transition metal; �a� and �b� are integers≧0; �c� is an integer≧1; a+b+c=an even-numbered integer from 2 to 8; and �m� is an integer ranging from 5 to 22; �a′� and �b′� are the same or a different integer≧0; �c′� is an integer≧2; a′+b′+c′=an even-numbered integer from 4 to 8; �m′� is an integer from 6 to 12; �n� is an integer such that 2c′−n=d; and �d� is an integer greater than or equal to 1.
(C5H5-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five R groups, �x� is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each R group is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals and substituted C1�C20 hydrocarbyl radicals, wherein one or more hydrogen atoms are replaced by a halogen atom, C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of germanium and silicon, and halogen radicals; or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R groups are joined forming a C4�C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
(JR′z-l-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V-A or an element with a coordination number of two from Group VI-A of the Periodic Table of Elements, each R′ is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals and substituted C1�C20 hydrocarbyl, wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
each Q is, independently, hydride, C1�C20 hydrocarbyl radicals and substituted hydrocarbyl radicals, wherein one or more hydrogen atoms is replaced by an electron withdrawing group, or C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of germanium and silicon, provided that Q is not a substituted or unsubstituted cyclopentadienyl ring, or both Q together may be an alkylidene, olefin, acetylene or a cyclometallated hydrocarbyl;
L is a neutral Lewis base; and �w� is a number from 0 to 3; wherein M′ has the same meaning as M and Q′ has the same meaning as Q;
[(L′−H)+]d[(M′)m+ Q 1 Q 2 . . . Q n]d− wherein
[L′−H] c[(CX)a(BX′)m X″ b]c− or [L′−H] d[[[(CX 3)a′(BX4)m′(X5)b]c′]2 M+]d− wherein [L′−H] is a cation selected from the group consisting of a H+; an ammonium; a substituted ammonium wherein the substituted ammonium cation has up to three hydrogen atoms replaced with a radical selected from a group consisting of a hydrocarbyl radical containing from 1 to about 20 carbon atoms and a substituted-hydrocarbyl radical containing from 1 to 20 carbon atoms wherein one or more of the hydrogen atoms is replaced by a halogen atom; a phosphonium; and a substituted-phosphonium wherein the substituted phosphonium cation has up to three hydrogen atoms replaced with a radical selected from a group consisting of a hydrocarbyl radical containing from 1 to about 20 carbon atoms and a substituted-hydrocarbyl radical containing from 1 to 20 carbon atoms wherein one or more of the hydrogen atoms is replaced by a halogen atom; C is carbon; B is boron; each of X, X′, X″, X3 X4 and X5 are radicals selected, independently, from the group consisting of hydride radicals, halide radicals, hydrocarbyl radicals containing from 1 to about 20 carbon atoms, substituted-hydrocarbyl radicals containing from 1 to 20 carbon atoms wherein one or more of the hydrogen atoms is replaced by a halogen atom, organometalloid radicals wherein each hydrocarbyl substitution in the organo portion contains from 1 to about 20 carbon atoms, and said metalloid is selected from the group consisting of silicon; M is a transition metal; �a� and �b� are integers≧0; �c� is an integer≧1, a+b+c=an even-numbered integer from 2 to 8; and �m� is an integer ranging from 5 to 22; �a′� and �b′� are the same or a different integer≧0; �c′� is an integer≧2; a′+b′+c′=an even-numbered integer from 4 to 8; �m′� is an integer from 6 to 12; �n� is an integer such that 2c′−n=d; and �d� is an integer greater than or equal to 1.
(C5H5-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five substituent R groups, �x� is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from the group consisting of methyl, ethyl, propyl, butyl, cyclohexyl, octyl, benzyl, phenyl, trimethylgermyl, trimethylstannyl, triethylplumbyl, trifluoromethyl, trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, and triphenylgermyl, or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R groups are joined forming an indenyl or tetrahydroindenyl ligand;
(JR′z-l-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V-A or an element with a coordination number of two from Group VI-A of the Periodic Table of Elements, and each R′ is, independently, a radical selected from the group consisting of C1�C20 hydrocarbyl radicals and substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
�y� is 0 or 1; when �y� is 1, T is a linear, branched or cyclic alkylene group having from 1 to 6 carbon atoms or a silylene group having from 1 to 2 silicon atoms;
[BAr 1 Ar 2 X 3 X 4] − wherein:
(C5H4-xRx) is a cyclopentadienyl ring which is substituted with from zero to five substituent R groups, �x� is 0, 1, 2, 3 or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from the group consisting of methyl, ethyl, propyl, butyl, cyclohexyl, octyl, benzyl, phenyl, trimethylgermyl, trimethylstannyl, triethylplumbyl, trifluoromethyl, trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, and triphenylgermyl, or (C5H4-xRx) is a cyclopentadienyl ring in which two adjacent R groups are joined forming an indenyl or tetrahydroindenyl ligand;
(JR′z-2) is a heteroatom ligand in which J is an element with a coordination number of three from Group V-A or an element with a coordination number of two from Group VI-A of the Periodic Table of Elements, and R′ is a radical selected from the group consisting of C1�C20 hydrocarbyl radicals and substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
L is a neutral Lewis base, and �w� is a number from 0 to 3;
[BAr 1 Ar 2 X 3 X 4]− wherein:
(C5H5-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five R groups, �x� is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each R group is, independently, a radical selected from the group consisting of methyl, ethyl, propyl, butyl, cyclohexyl, octyl, benzyl, phenyl, trimethylgermyl, trimethylstannyl, triethylplumbyl, trifluoromethyl, trimethylsilyl, triethylsilyl, ethyldimethylsilyl, metiyldietlhylsilyl, and triphenylgermyl, or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R groups are joined forming an indenyl or tetrahydroindenyl ligand;
(JRK′z-l-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V-A or an clement with a coordination number of two from Group VI-A of the Periodic Table of Elements, and each R′ is, radicals and substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
�y� is 0 or 1; when �y� is 1, T is a linear, branched or cyclic alkylene group having from 1 to 6 carbon atoms, or a silylene group having from 1 to 2 silicon atoms;
L is a neutral Lewis base; and �w� is a number from 0 to 3, wherein M′ has the same meaning as M and Q′ has the same meaning as Q;
[L′−H] + [A] − wherein L′ is dimethylphenylamine. H is a hydrogen atom and [A]− is [B(C6F5)4]−.
FIELD OF THE INVENTION This invention relates to certain transition metal compounds of the Group IV-B metals of the Periodic Table of Elements, to a catalyst system comprising such Group IV-B transition metal compounds and an ion-exchange activator compound, and to a process using such catalyst system for the production of polyolefins, particularly polyethylene, polypropylene, and ethylene-α-olefin copolymers.
BACKGROUND OF THE INVENTION As is well known, various processes and catalysts exist for the homopolymerization or copolymerization of olefins. Traditional Ziegler-Natta catalyst systems�a transition metal compound cocatalyzed by an aluminum alkyl�are capable of producing polyolefins having a high molecular weight but a broad molecular weight distribution. Traditional types of Ziegler-Natta catalysts have very high activities, and the polyolefins produced therewith have low catalyst residues and do not require a subsequent catalyst residue deashing treatment.
More recently a �metallocene� type catalyst system has been developed�one wherein the transition metal compound has cyclopentadienyl ring ligands, preferably at least two; such transition metal compound being referred to as a �metallocene��which catalyzes the production of olefin monomers to polyolefins. Accordingly, metallocene compounds of the Group IV-B-metals, particularly bis(cyclopentadienyl) titanocenes and zirconocenes, have been utilized as the transition metal component in such �metallocene� containing catalyst system for the production of polyolefins and ethylene-α-olefin copolymers. When such metallocenes are cocatalyzed with an aluminum alkyl�as is the case with a traditional type Ziegler-Natta catalyst system�the catalytic activity of such metallocene catalyst system is generally too low to be of any commercial interest.
It has since become known that such metallocenes may be cocatalyzed with an alumoxane�rather than an aluminum alkyl�to provide a metallocene catalyst system of high activity for catalyzing the production of moderately high molecular weight polyolefins. Unfortunately, the amount of alumoxane cocatalyst required to provide the metallocene component with high activity is generally high, generally expressed as a molar ratio of Al to transition metal, hence a polyolefin produced from such metallocene-alumoxane catalyst may contain an undesirable amount of catalyst residue (or ash content, measured as the nonvolatile aluminum and transition metal content).
SUMMARY OF THE INVENTION The catalyst system of this invention comprises a transition metal component from Group IV B of the Periodic Table of the Elements (CRC Handbook of Chemistry and Physics, 68th ed. 1987�1988) and an ion-exchange reagent which may be employed in solution, slurry, gas phase or bulk phase polymerization procedure to produce a polyolefin of high weight average molecular weight and relatively narrow molecular weight distribution.
The �Group IV B transition metal component� of the mono-cyclopentadienyl catalyst system is represented by the general formula:
(C5H5-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, �x� is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1�C20 hydrocarbyl radicals, substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements, and halogen radicals; or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming a C4�C20 ring to give a polycyclic cyclopentadienyl ligand such as indenyl and fluorenyl derivatives.
(JR′x-l-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur, and each R′ is, independently a radical selected from a group consisting of C1�C20 hydrocarbyl radicals, substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
each Q may be independently, hydride, C1�C50 hydrocarbyl radicals, substituted hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by an electron-withdrawing group such as a halogen atom, or alkoxide radical, or C1�C50 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV-A of the Period Table of Elements, provided that were any Q is a hydrocarbyl such Q is different from (C5H5-y-xRx), or both Q together may be an alkylidene, olefin, acetylene or a cyclometallated hydrocarbyl.
�y� is 0 or 1; when �y� is 1, T is a covalent bridging group containing a Group IV A or V A element such as, but not limited to, a dialkyl, alkylaryl or diaryl silicon or germanium radical, alkyl or aryl phosphine or amine radical, or a hydrocarbyl radical such as methylene, ethylene and the like;
L is a neutral Lewis base such as diethylether, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and �w� is a number from 0 to 3; L can also be a second transition metal compound of the same type such that the two metal centers M and M′ are bridged by Q and Q′, wherein M′ has the same meaning as M and Q′ has the same meaning as Q. Such compounds are represented by the formula:
Catalyst systems of the invention may be prepared by placing the �Group IV B transition metal component� and the ion-exchange component in common solution in a normally liquid alkane or aromatic solvent, which solvent is preferably suitable for use as a polymerization diluent for the liquid phase polymerization of an olefin monomer. Suitable catalysts can also be prepared by reacting the components and adsorbing on a suitable support material (inorganic oxides or polymers, for example) or by allowing the components to react on such support.
A typical polymerization process of the invention such as for the polymerization or copolymerization of ethylene comprises the steps of contacting ethylene alone, or with other unsaturated monomers including C3�C20 α-olefins, C5�C20 diolefins, and/or acetylenically unsaturated monomers either alone or in combination with other olefins and/or other unsaturated monomers, with a catalyst comprising, in a suitable polymerization diluent, the Group IV B transition metal component illustrated above; and the ion-exchange activator component in an amount to provide a molar transition metal to activator ratio of from about 1:10 to about 200:1 or more; and reacting such monomer in the presence of such catalyst system at a temperature of from about −100� C. to about 300� C. for a time of from about 1 second to about 10 hours to produce a polyolefin having a weight average molecular weight of from about 1,000 or less to about 5,000,000 or more and a molecular weight distribution of about 1.5 or greater.
DESCRIPTION OF THE PREFERRED EMBODIMENT Ionic Catalyst System�General Description
(C5H5-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, �x� is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1�C20 hydrocarbyl radicals, substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, C1�C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements, and halogen radicals; or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming a C4�C20 ring to give a polycyclic cyclopentadienyl ligand such as indenyl and fluorenyl derivatives;
(JR′z-l-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur with nitrogen being preferred, and each R′ is, independently a radical selected from a group consisting of C1�C20 hydrocarbyl radicals, substituted C1�C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
each Q may be independently, hydride, C1�C50 hydrocarbyl radicals, substituted hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by an electron-withdrawing group such as a halogen atom, or alkoxide radical, or C1�C50 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV-A of the Periodic Table of Elements, provided that where any Q is a hydrocarbyl such Q is different from (C5H5-y-xRx), or both Q together may be an alkylidene olefin, acetylene or a cyclometallated hydrocarbyl;
�y� is 0 or 1; when �y� is 1, T is a covalent bridging group containing a Group IV A or V A element such as, but not limited to, a dialkyl, alkylaryl or diaryl silicon or germanium radical, alkyl or aryl phosphine or amine radical, or a hydrocarbyl radical such as methylene, ethylene and the like. Examples of the T group which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in Column 1 of Table 1 under the heading �T�.
L is a neutral Lewis base such as diethylether, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and �w� is a number from 0 to 3; L can also be a second transition metal compound of the same type such that the two metal centers M and M′ are bridged by Q and Q′, wherein M′ has the same meaning as M and Q′ has the same meaning as
Exemplary hydrocarbyl radicals for the Q are methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like, with methyl being preferred. Exemplary substituted hydrocarbyl radicals include trifluoromethyl, pentafluorphenyl, trimethylsilylmethyl, and trimethoxysilylmethyl and the like. Exemplary hydrocarbyl substituted metalloid radicals include trimethylsilyl, trimethylgermyl, triphenylsilyl, and the like. Exemplary alkyldiene radicals for both Q together are methylidene, ethylidene and propylidene. Examples of the Q group which are suitable as a constituent group or element of the Group IV B transition metal component of the catalyst system are identified in Column 4 of Table 1 under the heading �Q�.
Table 1 depicts representative constituent moieties for the �Group IV B transition metal component�, the list is for illustrative purposes only and should not be construed to be limiting in any way. A number of final components may be formed by permuting all possible combinations of the constituent moieties with each other. Illustrative compounds are: dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconium dimethyl, dimethylsilyltetramethylcyclopentadienyl-tert-butylamido hafnium diethyl, dimethylsilyl-tert-butylcyclopentadienyl-tert-butyl-amido zirconium dihydride, dimethylsilyl-tert-butylcyclopentadienyl-tert-butylamido hafnium diphenyl, dimethylsilyltrimethylsilylcyclopentadienyl-tert-butylamido zirconium dihydride, dimethylsilyltetramethylcyclopentadienylphenylamido titanium dimethyl, dimethylsilyltetramethylcyclopentadienylphenylamido hafnium ditolyl, methylphenylsilyltetramethylcyclopentadienyltert-butylamido zirconium dihydride, methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilylfluorenyl-cyclohexylamido titanium dimethyl, diphenylgermylindenyl-t-butyl phosphido titanium dihydride methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilyltetramethylcyclopentadienyl-p-n-butylphenylamido zirconium dihydride, dimethylsilyltetramethyl-ocyclopentadienyl-p-n-butylphenylamido hafnium dihydride. For illustrative purposes, the above compounds and those permuted from Table 1 do not include the neutral Lewis base ligand (L). The conditions under which complexes containing neutral Lewis base ligands such as ether or those which form dimers is determined by the steric bulk of the ligands about the metal center. Similarly, due to the decreased steric bulk of the trimethylsilylcyclopentadienyl group in [Me2Si(Me3SiC5H3)(N-t-Bu)ZrH2]2 versus that of the tetramethylcyclopentadienyl group in Me2Si(Me4C5)(N-t-Bu)-ZrH2, the former compound is dimeric and the latter is not.
Generally the bridged species of the Group IV B transition metal compound (�y�=1) are preferred. A preferred method of preparing these compounds is by reacting a cyclopentadienyl lithium compound with a
TABLE 1 T (when y = 1) (C5H3−y−xRx) (JR′x−1−y) Q M dimethylsilyl cyclopentadienyl t-butylamide hydride zirconium diethylsilyl methylcyclopentadienyl phenylamide methyl hafnium di-n-propylsilyl 1,2-dimethylcyclopentadienyl p-n-butylphenylamide ethyl titanium diisopropylsilyl 1,3-dimethylcyclopentadienyl cyclohexylamide phenyl di-n-butylsilyl indenyl perflurophenylamide n-propyl di-t-butylsilyl 1,2-diethylcyclopentadienyl n-butylamide isopropyl di-n-hexylsilyl tetramethylcyclopentadienyl methylamide n-butyl methylphenylsilyl ethylcyclopentadienyl ethylamide amyl ethylmethylsilyl n-butylcyclopentadienyl n-propylamide isoamyl diphenylsilyl cyclohexylmethylcyclopentadienyl isopropylamide hexyl di(p-t-butylphenethylsilyl) n-octylcyclopentadienyl benzylamido isobutyl n-hexylmethylsilyl β-phenylpropylcyclopentadienyl t-butylphosphide heptyl cyclopentamethylenesilyl tetrahydroindenyl ethylphosphide actyl cyclotetramethylenesilyl propylcyclopentadienyl phenylphosphide nonyl cyclotrimethylenesilyl t-butylcyclopentadienyl cyclohexylphosphide decyl dimethylgermanyl benzylcyclopentadienyl oxo (when y = 1) cetyl diethylgermanyl diphenylmethylcyclopentadienyl sulfide (when y = 1) methylidene (both Q) phenylamide trimethylgermylcyclopentadienyl methoxide (when y = 0) ethylidene (both Q) t-butylamide trimethylstearylcyclopentadienyl ethoxide (when y = 0) propylidene (both Q) methylamide triethylplumbylcyclopentadienyl methylthio (when y = 0) t-butylphosphide trifluromethylcyclopentadienyl ethylthio (when y = 0) ethylphosphide trimethylsilylcyclopentadienyl phenylphosphide pentamethylcyclopentadienyl (when y = 0) methylene fluorenyl dimethylmethylene methylfluorenyl diethylmethylene octahydrofluorenyl ethylene dimethylethylene diethylethylene dipropylethylene propylene dimethylpropylene diethylpropylene 1,1-dimethyl-3,3-dimethylpropylene tetramethyldisiloxane 1,1,4,4-tetramethyldisilylethylene dihalo-compound whereupon a lithium halide salt is liberated and a monohalo substituent becomes covalently bound to the cyclopentadienyl compound. The so substituted cyclopentadienyl reaction product is next reacted with a lithium salt of a phosphide, oxide, sulfide or amide (for the sake of illustration, a lithium amide) whereupon the halo element of the monohalo substituent group of the reaction product reacts to liberate a lithium halide salt and the amine moiety of the lithium amide salt becomes covalently bound to the substituent of the cyclopentadienyl reaction product. The resulting amine derivative of the cyclopentadienyl product is then reacted with an alkyl lithium reagent whereupon the labile hydrogen atoms, at the carbon atom of the cyclopentadienyl compound and at the nitrogen atom of the amine moiety covalently bound to the substituent group, react with the alkyl of the lithium alkyl reagent to liberate the alkane and produce a dilithium salt of the cyclopentadienyl compound. Thereafter the bridged species of the Group IV B transition metal compound is produced by reacting the dilithium salt cyclopentadienyl compound with a Group IV B transition metal preferably a Group IV B transition metal halide. This procedure yields the dichloro-derivative of the monocyclopentadienyl-amido Group IV-B compound. The dichloride complex is then converted into the appropriate hydrocarbyl derivative using the corresponding Grignard, lithium, sodium or potassium salt of the hydrocarbyl ligand. The procedures used are analogous to those developed for alkylating the Group IV-B metallocene complexes (i.e., the bis-cyclopentadienyl systems).
Suitable, but not limiting, Group IV B transition metal compounds which may be utilized in the catalyst system of this invention include those bridged species (�y�=1) wherein the T group bridge is a dialkyl, diaryl or alkylaryl silane, or methylene or ethylene. Examples of the more preferred species of bridged Group IV B transition metal compounds are dimethylsilyl, methylphenylsilyl, diethylsilyl, ethylphenylsilyl, diphenylsilyl, ethylene or methylene bridged compounds. Most preferred of the bridged species are dimethylsilyl, diethylsilyl and methylphenylsilyl bridged compounds.
Suitable Group IV B transition metal compounds which are illustrative of the unbridged (�y�=0) species which may be utilized in the catalyst systems of this invention are exemplified by pentamethylcyclopentadienyldi-t-butylphosphinohafnium dimethyl; pentamethylcyclopentadienyldi-t-butylphosphinohafnium methylethyl; cyclopentadienyl-2-methylbutoxide titanium dimethyl.
L′ is a neutral Lewis base; H is a hydrogen atom; [L′−H] is a Bronsted acid; M′ is a metal or metalloid selected from the Groups subtended by Groups V-B to V-A of the Periodic Table of the Elements; i.e., Groups V-B, VI-B, VII-B, VIII, I-B, II-B, III-A, IV-A, and V-A; Q1 to Qn are selected, independently, from the Group consisting of hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted-hydrocarbyl radicals and organometalloid radicals and any one, but not more than one, of Q1 to Qn may be a halide radical, the remaining Q1 to Qn being, independently, selected from the foregoing radicals;
L′ is a neutral Lewis base; H is a hydrogen atom; [L′−H]+ is a Bronsted acid; B is boron in a valence state of 3; Ar1 and Ar2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from about 6 to about 20 carbon atoms and may be linked to each other through a stable bridging group; and X3 and X4 are radicals selected, independently, from the group consisting of hydride radicals, halide radicals, with the proviso that X3 and X4 will not be halide at the same time, hydrocarbyl radicals containing from 1 to about 20 carbon atoms, substituted-hydrocarbyl radicals, wherein one or more of the hydrogen atoms is replaced by a halogen atom, containing from 1 to about 20 carbon atoms, hydrocarbyl-substituted metal (organometalloid) radicals wherein each hydrocarbyl substitution contains from 1 to about 20 carbon atoms and said metal is selected from Group IV-A of the Periodic Table of the Elements and the like. In general, Ar1 and Ar2 may, independently, be any aromatic or substituted-aromatic hydrocarbon radical containing from about 6 to about 20 carbon atoms. Suitable aromatic radicals include, but are not limited to, phenyl, naphthyl and anthracenyl radicals. Suitable substituents on the substituted-aromatic hydrocarbon radicals, include, but are not necessarily limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy radicals, alkylamido radicals, fluoro and fluorohydrocarbyl radicals and the like such as those useful as X3 and X4. The substituent may be ortho, meta or para, relative to the carbon atoms bonded to the boron atom. When either or both X3 and X4 are a hydrocarbyl radical, each may be the same or a different aromatic or substituted-aromatic radical as are Ar and Ar2, or the same may be a straight or branched alkyl, alkenyl or alkynyl radical having from 1 to about 20 carbon atoms, a cyclic hydrocarbon radical having from about 5 to about 8 carbon atoms or an alkyl-substituted cyclic hydrocarbon radical having from about 6 to about 20 carbon atoms. X3 and X4 may also, independently, be alkoxy or dialkylamido radicals wherein the alkyl portion of said alkoxy and dialkylamido radicals contain from 1 to about 20 carbon atoms, hydrocarbyl radicals and organometalloid radicals having from 1 to about 20 carbon atoms and the like. As indicated above, Ar1 and Ar may be linked to each other. Similarly, either or both of Ar1 and Ar2 could be linked to either X3 or X4. Finally, X3 or X4 may also be linked to each other through a suitable bridging group.
[L′−H] c[(CX)a(BX′)m X″ b]c− 6.[L′−H] d[[[(CX 3)a′(BX 4)m′(X 5)b′]c′−]2 M n+]d−7.
wherein [L′−H] is either H+, ammonium or a substituted ammonium cation having up to 3 hydrogen atoms replaced with a hydrocarbyl radical containing from 1 to about 20 carbon atoms or a substituted-hydrocarbyl radical, wherein one or more of the hydrogen atoms is replaced by a halogen atom, containing from 1 to about 20 carbon atoms, phosphonium radicals, substituted-phosphonium radicals having up to 3 hydrogen atoms replaced with a hydrocarbyl radical containing from 1 to about 20 carbon atoms or a substituted-hydrocarbyl radical, wherein 1 or more of the hydrogen atoms is replaced by a halogen atom, containing from 1 to about 20 carbon atoms and the like; C is carbon; B″ is boron each of X, X′, X″, X3 X4 and X5 are radicals selected, independently, from the group consisting of hydride radicals, halide radicals, hydrocarbyl radicals containing from 1 to about 20 carbon atoms, substituted-hydrocarbyl radicals, wherein one or more of the hydrogen atoms is replaced by a halogen atom, containing from 1 to 20 carbon atoms, organometalloid radicals wherein each hydrocarbyl substitution in the organo portion contains from 1 to about 20 carbon atoms and said metal is selected from Group IV-A of the Periodic Table of the Elements and the like; M is a transition metal; �a� and �b� are integers≧0; �c� is an integer>1; a+b+c=an even-numbered integer from 2 to about 8; and �m� is an integer ranging from 5 to about 22; �a′� and �b′� are the same or a different integer≧0; �c′� is an integer≧2; a′+b′+c′=an even-numbered integer from 4 to about 8; �m′� is an integer from 6 to about 12; �n� is an integer such that 2c′−n=d; and �d� is an integer greater than or equal to 1.
The catalyst system may be conveniently prepared by placing the selected Group IV-B transition metal component and the selected activator component, in any order of addition, in an alkane or aromatic hydrocarbon solvent�preferably toluene. The catalyst system may be separately prepared, in concentrated form, and added to the polymerization diluent in a reactor. Or, if desired, the components of the catalyst system may be prepared as separate solutions and added to the polymerization diluent in a reactor, in appropriate ratios, as is suitable for a continuous liquid polymerization reaction procedure. Alkane and aromatic hydrocarbons suitable as solvents for formation of the catalyst system and also as a polymerization diluent are exemplified by, but are not necessarily limited to, straight and branched chain hydrocarbons such as isobutene, butane, pentane, hexane, heptane, octane and the like, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and the like, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and the like. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butene, 1-hexene and the like.
The catalyst system ingredients�that is, the Group IV-B transition metal and activator components, and polymerization diluent can be added to the reaction vessel rapidly or slowly. The temperature maintained during the contact of the catalyst components can vary widely, such as, for example, from −100� to 300� C. Greater or lesser temperatures can also be employed. Preferably, during formation of the catalyst system, the reaction is maintained within a temperature of from about 25� to 100� C., most preferably about 25� C.
The reaction of the two catalyst components can be viewed as a simple acid-base reaction where the Q−-ligand bound to the transition metal center of (CN)MQ2 (where (CN)=the Cp and J-ligands) reacts with the acidic cation of the second component, [L′H+][A]− (where A− is the non-coordinating anion), to give the ionic catalyst [(CN)MQ]+[A]′ and neutral biproducts Q−H and L′. The overall catalytic performance of the catalyst depends on the choice of metal, the specific (CN)-ligand set, the structure and stability of A−, and the coordinating ability of the Lewis base L′. For conventional applications where a high productivity homopolymerization or random copolymerization catalyst is desired, the Q-ligand of the transition metal component is chosen so that: 1) the metal complex is easy to prepare and is low cost, 2) (CN)MQ2 is sufficiently basic to deprotonate the acidic cation of the activator component, and 3) Q−H is an unreactive biproduct such as an alkane so that the activation reaction is irreversible. For a particular (CN)M-system the L′ and A− portions of the activator component �tune� the stability and overall performance of the catalyst system. The ability of L′ and A− to modify the behavior of a catalyst site increases the versatility of the polymerization system which is an important advantage over conventional methods of activation (e.g. methylalumoxane, and other aluminum alkyl cocatalysts).
Several new compositions of matter have been identified using high field NMR spectroscopy. The reaction between Me2Si(Me4C5)(N-t-Bu)ZrMe2 and [DMAH][B(pfp)4] (where DMAH=PhMe2NH+ and pfp C6F5) in d8-toluene produces a two phase system. The top layer is largely d8toluene with only a very small amount of DMA (DMA�PhNMe2) present. The lower layer Got contains the ionic catalyst and d8-toluene. The high field 13C NMR spectrum of the lower layer shows the action proceeds to give the DMA-adduct as shown below in Roman Numeral I.
The NMR data clearly demonstrates that the amine is indeed coordinated to the zirconium atom, but that it is fluxional and probably has two orientations of coordination, most likely in the form of rotational isomers. The ionic catalysts species can be crystallized out at −40� C. giving a pale blue power. The solid state NMR spectrum of this material revealed amine coordination to the zirconium atom with more than one orientation. Addition of d8-thf (thf=tetrahydrofuran) to the catalyst solution or solid produces the d8-thf adduct, Me2Si(Me4C5)(N-t-Bu)ZrMe(d8-thf)x][B(pfp)4] and free DMA. This was expected since d8-thf is a much stronger base than DMA.
The monomer for such process may comprise ethylene alone, for the production of a homopolyethylene, or ethylene in combination with an α-olefin having 3 to 18 carbon atoms for the production of an ethylene-α-olefin copolymer. Conditions most preferred for the homo- or copolymerization of ethylene are those wherein ethylene is submitted to the reaction zone at pressures of from about 0.019 psi to about 50,000 psi and the reaction temperature is maintained at from about −100� C. to about 300� C., preferably −10� to 220� C. The mole ratio of transition metal component to activator component is preferably from about 1:1 to about 200:1. The reaction time is preferably from about 1 second to about 1 hour.
EXAMPLES In the examples which illustrate the practice of the invention the analytical techniques described below were employed for the analysis of the resulting polyolefin products. Molecular weight determinations for polyolefin products were made by Gel Permeation Chromatography (GPC) according to the following technique. Molecular weights and molecular weight distributions were measured using a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector and a Chromatix KMX-6 on-line light scattering photometer. The system was used at 135� C. with 1,2,4-trichlorobenzene as the mobile phase. Shodex (Showa Denko America, Inc.) polystyrene gel columns 802, 803, 804 and 805 were used. This technique is discussed in �Liquid Chromatography of Polymers and Related Materials III�, J. Cazes, Editor, Marcel Dekker, 1981, p. 207 which is incorporated herein by reference. No corrections for column spreading were employed; however, data on generally accepted standards, e.g. National Bureau of Standards Polyethylene 1484 and anionically produced hydrogenated polyisoprenes (an alternating ethylene-propylene copolymer) demonstrated that such corrections on Mw/Mn (MID) were less than 0.05 units. Mw/Mn was calculated from elution time. The numberical analyses were performed using the commercially available Beckman/CIS customized LALLS software in conjunction with the standard Gel Permeation package, run on a HP 1000 computer.
EXAMPLES Synthesis of Mono-Cyclopentadienyl Complexes 1. Me2Si(C5Me4)(N-t-Bu)ZrMe2 Part 1. Me4HC5Li (10.0 g, 0.078 mol) was slowly added to a Me2SiCl2 (11.5 ml, 0.095 mol, in 225 ml of tetrahydrofuran (thf) solution). The solution was stirred for 1 hour to assure complete reaction. The thf solvent was then removed via a vacuum to a cold trap held at −196� C. Pentane was added to precipitates the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me4HC5SiMe2Cl (15.34 g, 0.071 mol) was recovered as a pale yellow liquid.
Part 2. Me4HC5SiMe2Cl (10.0 g, 0.047 mol) was slowly added to a suspension of LiHN-t-Bu (3.68 g, 0.047 mol, �100 ml thf). The mixture was stirred overnight. The thf was then removed via a vacuum to a cold trap held at −196� C. Petroleum ether (�100 ml) was added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2Si(Me4HC5)(HN-t-Bu) (11.14 g, 0.044 mol) was isolated as a pale yellow liquid.
Part 3. Me2Si(Me4HC5)(HN-t-Bu) (11.14 g, 0.044 mol) was diluted with �100 ml Et20. MeLi (1.4 M, 64 ml, 0.090 mol) was slowly added. The mixture was allowed to stir for � hour after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me2Si(Me4C5)(N-t-Bu)]Li2, was washed with several small portions of ether, then vacuum dried.
Part 4. [Me2Si(Me4C5)(N-t-Bu)]Li2 (3.0 g, 0.011 mol) was suspended in �150 ml Et20. ZrCl4 (2.65 g, 0.011 mol) was slowly added and the resulting mixture was allowed to stir overnight. The ether was removed via a vacuum to a cold trap held at −196� C. Pentane was added to precipitated the LiCl. The mixture was filtered through Celite twice. The pentane was significantly reduced in volume and the pale yellow solid was filtered off and washed with solvent. Me2Si(Me4C5)(N-t-Bu)ZrCl2 (1.07 g, 0.0026 mole) was recovered. Additional Me2Si(Me4C5)(N-t-Bu)ZrCl2 was recovered from the filtrate by repeating the recrystallization procedure. Total yield, 1.94 g, 0.0047 mol).
2. MePhSi(C5Me4)(N-t-Bu)HfMe2 Part 1. MePhSiCl2 (14.9 g, 0.078 mol) was diluted with �250 ml of thf. Me4C5HLi (10.0 g, 0.078 mol) was slowly added as a solid. The reaction solution was allowed to stir overnight. The solvent was removed via a vacuum to a cold trap held at −196� C. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite, and the pentane was removed from the filtrate. MePhSi(Me4C5H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.
Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in �100 ml of thf. MePhSi(Me4C5H)Cl (15.0 g, 0.054 mol) was added drop wise. The yellow solution was allowed to stir overnight. The solvent was removed via vacuum. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite, and the filtrate was evaporated down. MePhSi(Me4C5H)(NH-t-Bu) (16.6 g, 0.053 mol) was recovered as an extremely viscous liquid.
Part 3. MePhSi(Me4C5H)(NH-t-Bu) (16.6 g, 0.053 mol) was diluted with -100 ml of ether. MeLi (76 ml, 0.106 mol, 1.4 M) was slowly added and the reaction mixture was allowed to stir for �3 hours. The ether was reduced in volume, and the lithium salt was filtered off and washed with pentane producing 20.0 g of a pale yellow solid formulated as Li2[MePhSi(Me4C5)(N-t-Bu)]��Et20.
Part 4. Li2[MePhSi(Me4C5)(N-t-Bu)]��Et20 (5.00 g, 0.0131 mol) was suspended in �100 ml of Et2O. HfCl4 (4.20 g, 0.0131 mol) was slowly added and the reaction mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite. The filtrate was evaporated to near dryness and filtered. The off white solid was washed with petroleum ether. MePhSi(Me4C5)(N-t-Bu)HfCl2 was recovered (3.54 g, 0.0058 mole).
POLYMERIZATIONS Example 1 A catalyst solution prepared from 19.7 mg of Me2Si(Me4C5)(N-t-Bu)ZrMe2 and 6 mg of [DMAH] [B(pfp)4] in 20 mls of toluene was added to a 1 liter stainless-steel autoclave containing 400 mls of hexane. The reactor temperature was maintained at 40� C. and stirred vigorously while ethylene was added at 90 psi. After 30 minutes the reaction was stopped giving 30 grams of HDPE after work-up. The GPC analysis showed a bimodal distribution with modes centered at 900,000 and 2,000.
Example 2 A catalyst solution prepared from 28.6 mg of Me2Si(Me4C5)(N-t-Bu)ZrMe2 and 9 mg of [DMAH] [B(pfp)]4 in 20 mls of toluene was added to a 1 liter stainless-steel autoclave containing 400 mls of hexane. The reactor temperature was set at 50� C. and was stirred vigorously while 100 mls of butene and 60 psi of ethylene were added. Following the addition of butene and ethylene, an instantanious increase in temperature to 90� C. was observed. After 30 minutes the reaction was stopped, yielding 130 grams of a waxy ethylene-butene copolymer. GPC analysis showed a bimodal distribution with modes centered at 27,000 and 2,000 in approximately equal ratios. IR spectroscopy showed the presence of butene in the copolymer.
Example 3 A catalyst solution prepared from 40 mg of MePhSi(C5Me4)(N-t-Bu)HfMe2 and 11 mg of [DMAH][]B(pfp)4] in 20 mls of toluene was added to a 1 liter autoclave containing 400 mls of hexane. The reactor temperature was set at 40� C., stirred vigorously and pressurized with ethylene (90 psi) for 15 minutes. The reactor temperature increased from 40 to 97� C. during the polymerization. The reactor was stopped and 98 grams of polyethylene was isolated having a Mw=47.7 K and a MWD=3.0.
Example 4 A catalyst solution prepared from 50 mg of Me2Si(C5Me4)(N-t-Bu)ZrMe2 and 68 mg of [DMAH][(C2B9H11)2Co] in 20 mls of toluene was added to a 1 liter autoclave containing 400 mls of hexane. The reactor temperature was set at 60� C., stirred vigorously and pressurized with ethylene (120 psi) for 60 minutes. The reactor was stopped and 0.44 grams of polyethylene was isolated having a Mw=538 K and a MWD=1.90.
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