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Patent US6423795 - Tetramethylcyclopentadienyl titanium compounds for ethylene-α-olefin ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsDescribed are certain tetramethylcyclopentadienyl titanium compounds, catalyst systems comprising such compounds and an activator, and to a process using such catalyst systems for the production of polyolefins, particularly ethylene-α-olefin copolymers having a high molecular weight and high level of...http://www.google.com/patents/US6423795?utm_source=gb-gplus-sharePatent US6423795 - Tetramethylcyclopentadienyl titanium compounds for ethylene-α-olefin-copolymer production catalystsAdvanced Patent SearchPublication numberUS6423795 B1Publication typeGrantApplication numberUS 08/467,430Publication dateJul 23, 2002Filing dateJun 6, 1995Priority dateJan 30, 1987Fee statusPaidAlso published asUS5621126Publication number08467430, 467430, US 6423795 B1, US 6423795B1, US-B1-6423795, US6423795 B1, US6423795B1InventorsJo Ann Marie Canich, Howard William Turner, Gregory George HlatkyOriginal AssigneeExxonmobil Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (20), Non-Patent Citations (5), Referenced by (4), Classifications (40), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetTetramethylcyclopentadienyl titanium compounds for ethylene-α-olefin-copolymer production catalystsUS 6423795 B1Abstract Described are certain tetramethylcyclopentadienyl titanium compounds, catalyst systems comprising such compounds and an activator, and to a process using such catalyst systems for the production of polyolefins, particularly ethylene-α-olefin copolymers having a high molecular weight and high level of α-olefin incorporation.
What is claimed is: 1. A method for producing an ethylene-α-olefin copolymer of greater than 20wt. % α-olefin content, comprising the steps of:
supplying ethylene and a liquid α-olefin to a reaction zone at a molar ratio of α-olefin to ethylene of less than 2:1 in an amount sufficient to maintain a pressure within the reaction zone of from about 0.019 to about 50,000 psia, introducing into contact with the ethylene and α-olefin in the reaction zone a catalyst system comprising: (A) a tetramethylcyclopentadienyl titanium component of the formula: wherein R1 and R2 are each independently a hydrocarbyl radical, each Q and Q′ is independently a hydride or alkyl radical, R′ is an aliphatic or alicyclic hydrocarbyl radical having from 3 to 20 carbon atoms and R′ is covalently bonded to the nitrogen atom through a 1� or 2� carbon atom, L is a neutral Lewis base where �w� denotes a number from 0 to 3; and
(B) an activator; said catalyst system being introduced in an amount sufficient to maintain a temperature within the reaction zone of from about −100 to about 300� C. 2. The method of claim 1 wherein the activator is a non-coordinating compatible anion and Q is selected from hydride and substituted and unsubstituted C1-C20 hydrocarbyl radicals.
3. The method of claim 1 wherein the activator is an alumoxane.
This is a divisional, of application Ser. No. 08/138,169 filed on Oct. 15, 1993, now U.S. Pat. No. 5,621,126, which is a CIP of Ser. No. 07/850,751 filed Mar. 13, 1992 now U.S. Pat. No. 5,264,409 which is a CIP of 07/581,841 filed Sep. 18, 1990 now U.S. Pat. No. 5,096,867 which is a CIP of Ser. No. 07/533,245 filed Jun. 4, 1990, now U.S. Pat. No. 5,055,438 which is a CIP of Ser. No. 07/406,945 filed Sep. 13, 1989 now abandoned also a CIP of Ser. No. 07/542,236 filed Jun. 22, 1990 and is a CIP of Ser. No. 07/938,198 filed Aug. 28, 1992 now abandoned which is a continuation of Ser. No. 07/133,480 filed Dec. 22, 1987, now abandoned which is a CIP of Ser. No. 07/008,800 filed Jan. 30, 1987 now abandoned and a CIP of Ser. No. 07/875,165 filed Apr. 28, 1992 now U.S. Pat. No. 5,278,119 which is a continuation of Ser. No. 07/133,052 filed Dec. 21, 1987, now abandoned which is a CIP of Ser. No. 07/011,471 filed Jan. 30, 1987 now abandoned.
FIELD OF THE INVENTION This invention relates to certain monocyclopentadienyl metal compounds, to a catalyst system comprising a monocyclopentadienyl metal compound and an activator, and to a process using such catalyst system for the production of polyolefins, particularly ethylene-α-olefin copolymers having a high molecular weight and high level of α-olefin incorporation.
BACKGROUND OF THE INVENTION As is well known, various processes and catalysts exist for homopolymerization or copolymerization of olefins. For many applications it is of primary importance for a polyolefin to have a high weight average molecular weight while having a relatively narrow molecular weight distribution. A high weight average molecular weight, when accompanied by a narrow molecular weight distribution, provides a polyolefin or an ethylene-α-olefin copolymer with high strength properties.
More recently a catalyst system has been developed wherein the transition metal compound has two or more cyclopentadienyl ring ligands�such transition metal compound being referred to as a metallocene�which catalyzes the production of olefin monomers to polyolefins. Accordingly, metallocene compounds of a Group IV B metal, particularly, titanocenes and zirconocenes, have been utilized as the transition metal component in such �metallocene� containing catalyst systems 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.
The zirconium metallocene species, as cocatalyzed or activated with an alumoxane, are commonly more active than their hafnium or titanium analogues for the polymerization of ethylene alone or together with an α-olefin comonomer. When employed in a non-supported form�i.e., as a homogeneous or soluble catalyst system�to obtain a satisfactory rate of productivity even with the most active zirconocene species typically requires the use of a quantity of alumoxane activator sufficient to provide an aluminum atom to transition metal atom ratio (A1:TM) of at least greater than 1000:1; often greater than 5000:1, and frequently on the order of 10,000:1. Such quantities of alumoxane impart to a polymer produced with such catalyst system an undesirable content of catalyst metal residue, i.e., an undesirable �ash� content (the nonvolatile metal content). In high pressure polymerization procedures using soluble catalyst systems wherein the reactor pressure exceeds about 500 bar only the zirconocene or hafnocene species may be used. Titanocene species are generally unstable at such high pressure unless deposited upon a catalyst support.
SUMMARY OF THE INVENTION The present invention is a catalyst system including a mono(cyclopentadienyl) metal compound and an activator component. The catalyst system is highly productive for polymerizing ethylene and α-olefins to produce a high molecular weight ethylene-α-olefin copolymer having a high content of α-olefin. More particularly, the present invention relates to certain mono(cyclopentadienyl) metal compounds which include an amido moiety having an aliphatic or alicyclic hydrocarbyl group covalently bonded thereto through a primary or secondary carbon atom.
DETAILED DESCRIPTION OF THE INVENTION This invention comprises the discovery of a subgenus of mono(cyclopentadienyl) metal compounds which, by reason of the presence therein of ligands of a particular nature, provide a catalyst of greatly improved performance characteristics compared to known members of the genus of mono(cyclopentadienyl) metal compounds. The mono(cyclopentadienyl) metal compounds of the present invention are represented by the formula: wherein: M is Zr, Hf or Ti;
(C5H4−xRx) is a cyclopentadienyl ring which is substituted with from zero to four substituent groups R, �x� is 0, 1, 2, 3, or 4 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 radical, an amido radical, a phosphido radical, and alkoxy radical or any other radical containing a Lewis acidic or basic functionality, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements, halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C5H4−xRx) is a cyclopentadienyl ring in which at least two adjacent R-goups are joined forming a C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
R′ is a radical selected from C1-C20 aliphatic and alicyclic hydrocarbyl radicals wherein one or more hydrogen atoms may be replaced by radicals selected from halogen, amido, phosphido, alkoxy or any other radical containing a Lewis acidic or basic functionality, with the proviso that R′ is covalently bonded to the nitrogen atom through a 1� or 2� carbon atom;
each Q is independently a halide, hydride, or substituted or unsubstituted C1-C20 hydrocarbyl, alkoxide, aryloxide, amide, phospide or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand, with the proviso that where any Q is a hydrocarbyl such Q is not a substituted or unsubstituted cyclopentadienyl radical;
�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 dimeric compounds are represented by the formula: A preferred class of compounds of the present invention are represented by the formula: wherein:
M represents Ti, Hf or Zr;
(C5H4−xRx) is as defined above with respect to Formula I;
each of R1 and R2 are independently selected from C1-C20 hydrocarbyl radicals;
each Q is independently selected from halide, hydride, substituted or unsubstituted C1-C20 hydrocarbyl radical, alkoxide, amide and phosphide radicals with the proviso that Q is not a substituted or unsubstituted cyclopentadienyl radical;
R′ is selected from C1-C20 aliphatic and alicyclic hydrocarbyl radicals with the proviso that R′ is covalently bonded to the nitrogen atom through a 1� or 2� carbon atom;
A more preferred class of compounds of the present invention are those compounds represented by Formula III wherein M is Ti; wherein R, R′, Q, and LW are as defined above; and R1 and R2 are selected from alkyl and aryl radicals having from 1 to 20 carbon atoms.
A most preferred class of compounds are represented by the above Formula III wherein R′ is selected from alicyclic radicals particularly those having from 6 to 12 carbon atoms.
diphenylsilyl(tetramethylcyclopentadienyl)-(cyclopropylamido)titanium dimethyl;
methylphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)titanium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(cyclodecylamido) hafnium dimethyl;
dimethylsilyl (tetramethylcyclopentadienyl)-(cyclooctylamido)zirconium dimethyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(cyclododecylamido)zirconium diphenyl;
diphenylsilyl(tetramethylcyclopentadienyl)-(n-octylamido)zirconium diphenyl;
Another preferred class of compounds of the present invention are those compounds represented by the formula: wherein R, R′, Q, M, and LW are as defined above; wherein T is selected from radicals of the formula (CR3R4) wherein R3 and R4 are independently selected from hydrogen and C1-C20 hydrocarbyl radicals; and wherein y is 1 or 2.
A more preferred class of compounds are those compounds represented by the above Formula IV wherein M is Ti. A most preferred class of compounds are those represented by the above Formula IV wherein M is Ti and wherein R3 and R4 are independently selected from hydrogen, C1-C6 alkyl radicals and C6-C12 aryl radicals.
methylene(tetramethylcyclopentadienyl)-(n-octadecylamido) titanium dimethyl;
1,1-dimethylethylene(tetramethylcyclopentadienyl)-(cyclopropylamido)titanium dimethyl:
1 2-dimethylethylenetetramethylcyclopentadienyl)-(cyclodecylamido)titanium dimethyl;
The above named specific compounds wherein each Q is methyl are prepared from the corresponding compound wherein each Q is chloro. Thus, specific compounds within Formula IV are those wherein each Q is chloro. Also, the corresponding compounds wherein each Q is phenyl, M is zirconium or hafnium in place of titanium and (CR3R4)y is methylphenylmethylene, tetramethylethylene or tetraethylethylene are also specific compounds within the above Formula IV.
Herein a 1� carbon atom is one which is a methyl radical or a carbon atom which is bonded to only one other carbon atom; a 2� carbon atom is one which is bonded to only two other carbon atoms, and a 3� carbon atom is bonded to three other carbon atoms. Preferably the R′ alicyclic or aliphatic hydrocarbyl group has three or more carbon atoms and is bonded to the nitrogen atom through a 2� carbon atom; most preferably the hydrocarbyl group is alicyclic.
Mono(cyclopentadienyl) metal compounds of the present invention have been discovered to produce a highly productive catalyst system which produces an ethylene-α-olefin copolymer of significantly greater molecular weight and α-olefin comonomer content as compared with other species of mono(cyclopentadienyl) metal compounds when utilized in an otherwise identical catalyst system under identical polymerization conditions. Further, within this subgenus of metal compounds it has been found that the nature and degree of substitution groups (R) of the cyclopentadienyl ring can be varied to produce a catalyst system having a �catalyst reactivity ratio (r1)� which may be varied from a high to a low value as may be most desired to best suit the catalyst system to a particular type of polymerization process. Particularly it has been found that as the number of substituents (R), which are preferably hydrocarbyl substituents increases, the reactivity ratio (r1) decreases, the lowest reactivity ratios being obtained by a titanium compound having a tetrahydrocarbyl substituted cyclopentadienyl group, preferably a tetramethylcyclopentadienyl group.
The most preferred class of cyclopentadienyl metal compounds are represented by the formula: wherein Q, L, R′, R, �x� and �w� are as previously defined and R1 and R2 are each independently selected from C1 to C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom; R1 and R2 may also be joined forming a C3 to C20 ring which incorporates the silicon bridge.
Among this class of compounds of Formula V, various substituent and ligand affects have been discovered which significantly affect the properties of a catalyst system. The nature and degree of substitutions (R) in the cyclopentadienyl ring was found to significantly influence the catalyst ability to incorporate α-olefin comonomers when producing an ethylene-α-olefin copolymer. For the greatest amount of comonomer incorporation, the cyclopentadienyl ring should be fully substituted (x=4) with hydrocarbyl groups (R), most preferably methyl groups. This affect is demonstrated by a comparison between Examples 83 to 85. Next, the nature of the R′ ligand of the amido group significantly influences the capability of a catalyst to incorporate α-olefin comonomer. Amido group R′ ligands which are aliphatic or alicyclic hydrocarbyl ligands bonded to the nitrogen atom through a 1� or 2� carbon atom provide for a greater degree of α-olefin comonomer incorporation than do R′ groups bonded through a 3� carbon atom or bearing aromatic carbon atoms. Further, wherein the R′ ligand is bonded to the nitrogen atom through a 2� carbon atom, the activity of the catalyst is greater when the R′ substituent is alicyclic than when R′ is bonded to the nitrogen through a 1� carbon atom of an aliphatic group of identical carbon number. With regard to an alicyclic hydrocarbyl R′ ligand it has been found that as the number of carbon atoms thereof increases the molecular weight of the ethylene-α-olefin copolymer increases while the amount of α-olefin comonomer incorporated remains about the same or increases. Further, as the carbon number of the alicyclic hydrocarbyl ligand increases the productivity of the catalyst system increases. This is demonstrated by Examples 71-76. Accordingly, the R′ ligand most preferred is cyclododecyl (C12H23).
The compounds most preferred for reasons of their high catalyst activity in combination with an ability to produce high molecular weight ethylene-α-olefin copolymers of high comonomer content is represented by the formula wherein R1 and R2 are each independently a C1 to C3 hydrocarbyl radical, each Q is independently a halide or alkyl radical, R′ is an aliphatic or an alicyclic hydrocarby radical of the formula (CnH2n+b) wherein �n� is a number from 3 to 20 and �b� is +1 in which case the ligand is aliphatic or −1 in which case the ligand is alicyclic. Of these compounds, the most preferred is that compound wherein R1 and R2 are methyl, each Q is methyl, n is 12, and the hydrocarbyl radical is alicyclic (i.e., b is −1). Most preferred is that compound wherein the (CnH2n−1) hydrocarbyl radical is a cyclododecyl group. Hereafter this compound is referred to for convenience as Me2Si(C5Me4)(NC12H23)TiQ2.
The alumoxane component is an oligomeric compound which may be represented by the general formula (R3�Al�O)m which is a cyclic compound, or may be R4(R5�Al�O�)m�AlR6 2 which is a linear compound. An alumoxane is generally a mixture of both the linear and cyclic compounds. In the general alumoxane formula R3, R4, R5 and R6 are, independently a C1-C5 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and �m� is an integer from 1 to about 50. Most preferably, R3, R4, R5 and R6 are each methyl and �m� is at least 4. When an alkyl aluminum halide is employed in the preparation of the alumoxane, one or more R3-6 groups may be halide.
Suitable alumoxanes utilized in the catalyst systems of this invention are those prepared by the hydrolysis of a trialkylaluminum; such as trimethylaluminum, triethylaluminum, tripropylaluminum; triisobutylaluminum, dimethylaluminumchloride, diisobutylaluminumchloride, diethylaluminumchloride, and the like. The most preferred alumoxane for use is methylalumoxane (MAO). Methylalumoxanes having an average degree of oligomerization of from about 4 to about 25 (�m�=4 to 25), with a range of 13 to 25, are the most preferred.
[(L′�H)+]d[(M′)m+Q′″1Q′″2 . . . Q′″n]d− wherein:
[L′�H] is a Bronsted acid;
Q′″l to Q′″n are, independently, hydride radicals, bridged or unbridged dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted hydrocarbyl radicals, halocarbyl and substituted halocarbyl radicals, and hydrocarbyl- and halocarbyl-substituted organometalloid radicals and any one, but not more than one, Of Q1 to Qn may be a halide radical;
[L′�H]+[BAr1Ar2X3X4]− wherein:
[L′�H]+ is a Bronsted acid;
In veiw of the above, when utilizing an activator comprising a non-coordinating compatible anion, the metal component should be one wherein each Q is selected from the group consisting of hydride and substituted and unsubstituted hydrocarbyl radicals. Preferred Q ligands are hydride, C1-C12 alkyl and C6-C12 aryl radicals. Most preferred are those Q ligands selected from methyl and phenyl radicals, particularly methyl radicals. The preferred metal components species for use with an activator comprising a non-coordinating compatible anion are those set forth above wherein each Q is methyl or phenyl.
The chemical reactions which occur upon combination of a monocyclopentadienyl metal compound with a non-coordinating compatible anion activator compound may be represented by reference to the general formulae set forth herein as follows: B′ represents a compatible ion corresponding to the general formulae set forth above. When the mono(cyclopentadienyl) metal compound and the non-coordinating compatible anion activator components used to prepare the improved catalysts of the present invention are combined in a suitable solvent or diluent, all or a part of the cation of the activator (the acidic proton) combines with one of the substituents on the metallocene compound. In the case where the metallocene component has a formula corresponding to that of the general formula above, a neutral compound is liberated, which neutral compound either remains in solution or is liberated as a gas. In this regard, it should be noted that if either Q in the metallocene component is a hydride, hydrogen gas may be liberated. Similarly, if either Q is a methyl radical, methane may be liberated as a gas. In the cases where the first component has a formula corresponding to those of general formulae of the reaction sequence shown directly above, one of the substituents on the is protonated but no substituent is liberated. In general, the rate of formation of the products in the foregoing reaction equations will vary depending upon the choice of the solvent, the acidity of the [L′�H]+ selected, the particular L′, the anion, the temperature at which the reaction is completed and the particular cyclopentadienyl derivative of the metal selected.
Another means of rendering the anion of the activator compound more resistant to degradation is afforded by fluoride substitution, especially perfluoro substitution, in the anion thereof. One class of suitable non-coordinating anions can be represented by the formula [B(C6F5)3Q′″]− where Q′″ is a monoanionic non-bridging radical as described above. The preferred anion of the activator compound of this invention, tetra(pentafluorophenyl)boron, hereafter referred to for convenience by the notation [B(C6F5)4]−, or [B(pfp)4]−, is virtually impervious to degradation and can be used with a much wider range of mono(cyclopentadienyl) metal cations, including those without substitution on the cyclopentadienyl rings, than anions comprising hydrocarbyl radicals. The tetra(pentafluoro)boron anion is illustrated below: Since this anion has little or no ability to coordinate to the mono(cyclopentadienyl) metal cation and is not degraded by the mono(cyclopentadienyl) metal cation, structures of the ion-pair catalysts using the [B(pfp)4]− anion depend on steric hindrance of substituents on the cyclopentadienyl rings of mono(cyclopentadienyl) metal compound the nature of the cation of the activator component, the Lewis base liberated from the protonolysis reaction, and the ratio at which the mono(cyclopentadienyl) metal and activator component are combined. Thus, preferred catalyst systems having a non-coordinating compatible ion activator are those compounds of the above Formulas I-V, and, specifically, those species set forth above, in combination with [B(pfp)4]−. If Lewis bases other than that liberated from the proton transfer process are present, they may complex to the metal to form modified catalysts of this invention.
The catalyst system may be conveniently prepared by placing the selected metal component and the selected activator component, in any order of addition, in an alkane or aromatic hydrocarbon solvent�preferably one which is also suitable for service as a polymerization diluent. Where the hydrocarbon solvent utilized is also suitable for use as a polymerization diluent, the catalyst system may be prepared in situ in the polymerization reactor. Alternatively, 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 phase 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 isobutane, 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, 1-butene, 1-hexene and the like.
The catalyst system ingredients�that is, the Group IV B metal component, the activator, 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�.
A typical polymerization process of the invention comprises the steps of contacting ethylene and a C3-C20 α-olefin alone, or with other unsaturated monomers including C3-C20 α-olefins, C4-C20 diolefins, and/or acetylenically unsaturated monomers with a catalyst comprising, in a suitable polymerization diluent, a mono(cyclopentadienyl) metal compound, as described above, and an activator. For example, a catalyst comprising a mono(cyclopentadienyl) metal compound as described above and either 1) a non-coordinating compatible anion activator or 2) an alumoxane activator. The alumoxane activator is utilized in an amount to provide a molar aluminum to titanium metal ratio of from about 1:1 to about 20,000:1 or more. The non-coordinating compatible anion activator is utilized in an amount to provide a molar ratio of monocyclopentadienyl metal compound to non-coordinating anion of 10:1 to about 1:1. The above reaction is conducted by reacting such monomers 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 copolymer 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 from about 1.5 to about 15.0.
The monomers for such process comprise ethylene in combination with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, most preferably 3 to 8 carbon atoms, for the production of an ethylene-α-olefin copolymer. It should be appreciated that the advantages as observed in an ethylene-α-olefin copolymer produced with a catalyst system of this invention would also be expected to he obtained in a copolymer of different α-olefins wherein ethylene is not used as a monomer as viewed in comparison to a copolymer of the same or different α-olefins produced under similar polymerization conditions with a catalyst system which does not use a monocyclopentadienyl Group IV B metal compound as defined herein. Accordingly, although this invention is described with reference to an ethylene-α-olefin copolymer and the advantages of the defined catalyst system for the production thereof, this invention is not to be understood to be limited to the production of an ethylene-α-olefin copolymer, but instead the catalyst system hereof is to be understood to be advantageous in the same respects to the production of a copolymer composed of two or more C3 or higher α-olefin monomers. Copolymers of higher α-olefin such as propylene, butene, styrene or higher α-olefins and diolefins can also be prepared. 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 psia to about 50,000 psia and the reaction temperature is maintained at from about −100� to about 300� C. Where the activator is an alumoxane, the aluminum to titanium metal molar ratio is preferably from about 1:1 to 20,000 to 1. A more preferable range would be 1:1 to 2000:1. The reaction time is preferably from about 10 seconds to about 1 hour.
Without limiting in any way the scope of the invention, one means for carrying out the process of the present invention for production of a copolymer is as follows: in a stirred-tank reactor liquid α-olefin monomer is introduced, such as 1-butene. The catalyst system is introduced via nozzles in either the vapor or liquid phase. Feed ethylene gas is introduced either into the vapor phase of the reactor, or sparged into the liquid phase as is well known in the art. The reactor contains a liquid phase composed substantially of liquid α-olefin comonomer, together wash dissolved ethylene gas, and a vapor phase containing vapors of all monomers. The reactor temperature and pressure may be controlled via reflux of vaporizing α-olefin monomer (autorefrigeration), as well as by cooling coils, jackets, etc. The polymerization rate is controlled by the concentration of catalyst. The ethylene content of the polymer product is determined by the ratio of ethylene to α-olefin comonomer in the reactor, which is controlled by manipulating the relative feed rates of these components to the reactor.
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 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 (=MWD) were less than 0.05 units. Mw/Mn was calculated from elution times. The numerical 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.
All procedures were performed under an inert atmosphere of helium or nitrogen. Solvent choices are often optional, for example, in most cases either pentane or 30-60 petroleum ether can be interchanged. The lithiated amides were prepared from the corresponding amines and either n-BuLi or MeLi. Published methods for preparing LiHC5Me4 include C. M. Fendrick et a. Organometallics, 3, 819 (1984) and F. H. K�hler and K. H. Doll, Z. Naturforich, 376, 144 (1982). Other lithiated substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and n-BuLi or MeLi, or by reaction of MeLi with the proper fulvene. TiCl4, ZrCl4 and HfCl4 were purchased from either Aldrich Chemical Company or Cerac. TiCl4 was typically used in its etherate form. The etherate, TiCl4.2Et2O, can be prepared by gingerly adding TiCl4 to diethylether. Amines, silanes, substituted and unsubstituted cyclopentadienyl compounds or precursors, and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems. Methylalumoxane was supplied by either Sherring or Ethyl Corp.
Further, since the full disclosure of U.S. application Ser. No. 07/581,841, now U.S. Pat. No. 5,096,867, has been incorporated herein, the Examples hereof are identified by designations which are consistent with the Example designations of the incorporated application. Examples of the incorporated application relating to the Zr or Hf metal classes of a mono(cyclopentadienyl) transition metal catalyst system are not here repeated (which are Examples A to L) for sake of brevity. Accordingly, not verbatim repeated herein (but incorporated) are Examples A to L, and certain other double letter designated Examples of the incorporated patent. Set forth verbatim herein as repeats of Examples of the incorporated application are Examples AT, FT, IT, JT 40-47, 53-58, 58, 67 and 70.
Example AT Compound AT: Part 1. MePhSiCl2 (14.9 g, 0.078 mol) was diluted with 250 ml of thf. Me4HC5Li (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(C5Me4H)Cl (15.0 g, 0.054 mol) was added dropwise. The yellow solution was allowed to stir overnight. The solvent was removed in vacuo. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite, and the filtrate was evaporated. MePhSi(C5Me4H)(NH-t-Bu) (16.6 g, 0.053 mol) was recovered as an extremely viscous liquid.
Part 3. MePhSi(C5Me4H)(NH-t-Bu) (17.2 g, 0.055 mol) was diluted with −20 ml of ether. n-BuLi (60 ml in hexane, 0.096 mol, 1.6 M) was slowly added and the reaction mixture was allowed to stir for −3 hours. The solvent was removed in vacuo to yield 15.5 g (0.48 mol) of a pale tan solid formulated as Li2[MePhSi(C5Me4)(N-t-Bu)].
Part 4. Li2[MePhSi(C5Me4)(N-t-Bu)] (8.75 g, 0.027 mol) was suspended in −125 ml of cold ether (−30� C.). TiCl4.2Et2O (9.1 g, 0.027 mol) was slowly added. The reaction was allowed to stir for several hours prior to removing the ether via vacuum. A mixture of toluene and dichloromethane was then added to solubilize the product. The mixture was filtered through Celite to remove the LiCl. The solvent was largely removed via vacuum and petroleum ether was added. The mixture was cooled to maximize product precipitation. The crude product was filtered off and redissolved in toluene. The toluene insolubles were filtered off. The toluene was then reduced in volume and petroleum ether was added. The mixture was cooled to maximize precipitation prior to filtering off 3.34 g (7.76 mmol) of the yellow solid MePhSi(C5Me4)(N-t-Bu)TiCl2.
Example FT Compound FT: Part 1. (C5Me4H)SiMe2Cl was prepared as described in Example BT for the preparation of compound BT, Part 1.
Part 2. (C5Me4H)SiMe2Cl (5.19 g, 0.029 mol) was slowly added to a solution of LiHNC6H11 (2.52 g, 0.024 mol) in −125 ml of thf. The solution was allowed to stir for several hours. The thf was removed via vacuum and petroleum ether was added to precipitate the LiCl which was filtered off. The solvent was removed from the filtrate via vacuum yielding 6.3 g (0.023 mol) of the yellow liquid, Me2Si(C5Me4H)(HNC6H11).
Part 3. Me2Si(C5Me4H)(HNC6H11) (6.3 g, 0.023 mol) was diluted with −100 ml of ether. MeLi (33 ml, 1.4 M in ether, 0.046 mol) was slowly added and the mixture was allowed to stir for 0.5 hours prior to filtering off the white solid. The solid was washed with ether and vacuum dried. Li2[Me2Si(C5Me4)(NC6H11)] was isolated in a 5.4 g (0.019 mol) yield.
Part 4. Li2[Me2Si(C5Me4)(NC6H11)] (2.57 g, 8.90 mmol) was suspended in −50 ml of cold ether. TiCl4.2Et2O (3.0 g, 8.9 mmol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and dichloromethane was added. The mixture was filtered through Celite to remove the LiCl byproduct. The solvent was removed from the filtrate and a small portion of toluene was added followed by petroleum ether. The mixture was chilled in order to maximize precipitation. A brown solid was filtered off which was initially dissolved in hot toluene, filtered through Celite, and reduced in volume. Petroleum ether was then added. After refrigeration, an olive green solid was filtered off. This solid was recrystallized twice from dichloromethane and petroleum ether to give a final yield of 0.94 g (2.4 mmol) of the pale olive green solid, Me2Si(C5Me4)(NC6H11)TiCl.
Example IT Compound IT: Part 1. (C5Me4H)SiMe2Cl was prepared as described in Example BT for the preparation of Compound BT, part 1.
Part 2. (C5Me4H)SiMe2Cl (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 was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2Si(C5Me4H)(NH-t-Bu) (11.14 g, 0.044 mol) was isolated as a pale yellow liquid.
Part 3. Me2Si(C5Me4H)(NH-t-Bu) (11.14 g, 0.044 mol) was diluted with −100 ml of ether. 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(C5Me4)(N-t-Bu)]Li2, was washed with several small portions of ether, then vacuum dried.
Part 4. [Me2Si(C5Me4)(N-t-Bu)Li2 (6.6 g, 0.025 mol) was suspended in cold ether. TiCl4.2Et2O (8.4 g, 0.025 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. Methylene chloride was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was significantly reduced in volume and petroleum ether was added to precipitate out the product. This mixture was refrigerated prior to filtration in order to maximize precipitation. Me2Si(C5Me4)(N-t-Bu)TiCl2 was isolated (2.1 g, 5.7 mmol).
Example JT Compound JT: Part 1. (C5Me4H)SiMe2Cl was prepared as described in Example BT for the preparation of Compound Bt, Part 1.
Part 2. (C5Me4H)SiMe2Cl (8.0 g, 0.037 mol) was slowly added to a suspension of LiHNC12H23 (Cl2H23=cyclododecyl, 7.0 g, 0.037 mol, −80 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 and toluene was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2Si(C5Me4H)(NHC12H23) (11.8 g, 0.033 mol) was isolated as a pale yellow liquid.
Part 3. Me2Si(C5Me4H)(NHC12H23) (11.9 g, 0.033 mol) was diluted with −150 ml of ether. MeLi (1.4 M, 47 ml, 0.066 mol) was slowly added. The mixture was allowed to stir for 2 hours after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me2Si(C5Me4)(NC12H23)]Li2, was washed with several small portions of ether, then vacuum dried to yield 11.1 g (0.030 mol) of product.
Part 4. [Me2Si(C5Me4)(NC12H23)]Li2 (3.0 g, 0.008 mol) was suspended in cold ether. TiCl4.2Et2O (2.7 g, 0.008 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. Methylene chloride was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was significantly reduced in volume and petroleum ether was added to precipitate out the product. This mixture was refrigerated prior to filtration in order to maximize precipitation. The solid collected was recrystallized from methylene chloride and Me2Si(C5Me4)(NC12H23)TiCl2 was isolated (1.0 g, 2.1 mmol).
Example KT Compound KT: Part 1. (C5Me4H)SiMe2Cl was prepared as described in Example A for the preparation of compound A, Part 1.
To this solution, MeLi (1.4 M, 34 ml, 0.0476 mol) was slowly added. Upon completion of the reaction, a small amount of TiCl4.2Et2O was added to scavenge the excess MeLi. The solution was then cooled to −30� C. and an additional 7.75 g (0.030 mol) of TiCl4.2Et2O was added. The mixture was allowed to stir overnight. The solvent was removed and pentane was added. The resulting mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and chilled to induce crystallization of the product. Filtration yielded 4.2 g (0.0087 mol) Me2Si(C5Me4)(NC12H25)TiCl2.
Example LT Compound LT: Part 1. (C5Me4H)SiMe2Cl was prepared as described in Example A for the preparation of compound A, Part 1.
Part 2. (C5Me4H)SiMe2Cl (12.0 g, 0.056 mol) was diluted with 300 ml of thf. LiHNC8H15(C8H15=cyclooctyl, 742 g, 0.056 mol) was slowly added and the mixture was allowed to stir overnight. The reaction product, Me2Si(C5Me4H)(HNC8H15) was not isolated. The thf was removed and 300 ml of diethyl ether was added. MeLi (1.12M, 105 ml, 0.118 mol) was slowly added to form the dilithiated salt, Li2[Me2Si(C5Me4)(NC8H15)]. This mixture was cooled to −30� C., and TiCl4.2Et2O (19.14 g, 0.057 mol) was slowly added. The resulting mixture was allowed to stir overnight. The ether was removed in vacuo, and pentane was added to solubilize the product. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and chilled to −40� C. to induce crystallization of the product. Filtration yielded 7.9 g (0.019 mol) of Me2Si(C5Me4)(NC8H15)TiCl2.
Example MT Compound MT: Part 1. (C5Me4H)SiMe4Cl (6.0 g, 0.028 mol) was diluted with 150 ml of thf. LiHNC8H17 (C8H17=n-octyl, 3.7 g, 0.030 mol) was slowly added. The mixture was allowed to stir overnight. The reaction product, Me2Si(C5Me4H(HNC8H17) was not isolated prior to adding MeLi (2.1 M, 35 ml, 0.074 mol) to give Li2[Me2Si(C5Me4)(NC8H17)]. The solvent was removed via vacuum and replaced with diethyl ether, then cooled to −30� C. TiCl4.2Et2O (8.46 g, 0.025 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed in vacuo and methylene chloride was used to solubilize the product. The solvent mixture was filtered through Celite to remove the LiCl. The filtrate was evaporated down to dryness and pentane was added. The pentane soluble fraction was cooled to −40� C. to induce crystallization of the product. After filtration, Me2Si(C5Me4)(NC8H17)TiCl2 was isolated (1.8 g, 0.0042 mol).
Example NT Compound NT: Part 1. (C5Me4H)SiMe2Cl was prepared as described in Example A for the preparation of compound A, Part 1.
Part 2. (C5Me4H)SiMe2Cl (6.0 g, 0.028 mol) was diluted in 150 ml of thf. LiHNC6H13 (C6H13=n-hexyl, 2.99 g, 0.028 mol) was slowly added. The mixture was allowed to stir overnight. The thf was removed via vacuum and replaced with diethyl ether. The reaction product Me2Si(C5Me4H)(HNC6H13) was not isolated prior to adding MeLi (1.4 M, 45 Ml, 0.063 mol) to give Li2(Me2Si(C5Me4)(NC6H13)]. The resulting mixture was then cooled to −30� C. TiCl4.2Et2O (8.6 g, 0.025 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed in vacuo and pentane was used to solubilize the product. The solvent mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and cooled to −40� C. to induce crystallization of the product. While crystalline material appeared in the flask at −40� C., upon slight warming, it dissolved back into solution and therefore could not be isolated by filtration. Me2Si(C5Me4)(NC6H13)TiCl2 was isolated in an oil form by removing the solvent from the above solution. (4.0 g, 0.010 mol).
Example OT Compound OT: Part 1. MePhSi(C5Me4H)Cl was prepared as described in Example AT for the preparation of compound AT, Part 1.
Part 2. MePhSi(C5Me4H)Cl (6.0 g, 0.022 mol) was diluted with ether. LiHN-s-Bu (1.7 g, 0.022 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed and a mixture of toluene and petroleum ether was added. This mixture was filtered through Celite to remove the LiCl. The solvent was removed via vacuum leaving behind the viscous liquid, MePhSi(C5Me4H)(HN-s-Bu). To this liquid which was diluted with ether, 28 ml (0.039 mol 1.4 M in ether) MeLi was slowly added. After stirring overnight, a small portion of TiCl4.2Et2O (total of 5.86 g, 0.017 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum, dichloromethane was added and the mixture was filtered through Celite. The filtrate was evaporated down producing a brown solid. Petroleum ether was added and the mixture was filtered. The brown solid remaining on the filter stick was discarded and the filtrate was reduced in volume and refrigerated to maximize precipitation. After filtration and washing with cold aliquots of petroleum ether, a dark mustard yellow solid was isolated and identified as MePhSi(C5Me4)(N-s-Bu)TiCl2 (2.1 g, 4.9 mmol).
Example PT Compound PT: Part 1. MePhSi(C5Me4H)Cl was prepared as described in Example AT for the preparation of compound AT, Part 1.
Part 2. MePhSi(C5Me4H)Cl (6.0 g, 0.022 mol) was diluted with ether. LiHN-n-Bu (1.7 g, 0.022 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and petroleum ether was added. This was filtered through Celite to remove the LiCl. The solvent was removed from the filtrate leaving behind a viscous yellow liquid which was diluted with ether. To this, 28 ml of MeLi (1.4 M in ether, 0.038 mol) was added and the mixture was allowed to stir overnight. A small portion of TiCl4.2Et2O (total of 5.7 g, 0.017 mol) was slowly added. In spite of the slow addition, the highly exothermic reaction bumped, thus some product loss occurred at this point in the reaction. The remaining mixture was stirred overnight. The solvent was then removed via vacuum. Dichloromethane was added and the mixture was filtered through Celite to remove the LiCl. The solvent was removed and petroleum ether was added. The mixture was refrigerated to maximize precipitation. Filtration produced a yellow-brown solid which was recrystallized from petroleum ether. The final filtration produced 2.0 g (4.6 mmol) of MePhSi(Me4C5)(N-n-Bu)TiCl2.
Example OT Compound OT: Part 1. (C5Me4H)SiMe2Cl was prepared as described in Example A for the preparation of compound A, Part 1.
Part 2. (C5Me4H)SiMe2Cl (9.0 g, 0.042 mol) was diluted in ether. LiHn-s-Bu (3.31 g, 0.042 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether was added. This mixture was filtered through Celite to remove the LiCl. The solvent was removed from the filtrate leaving behind the pale yellow liquid, Me2Si(C5Me4H)(HN-s-Bu) (10.0 g, 0.040 mol.
Part 4. Li2[Me2Si(C5Me4)(N-s-Bu)] (7.0 g, 0.027 mol) was suspended in cold ether. TiCl4.2Et2O (8.98 g, 0.027 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and dichloromethane was added. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and petroleum ether was added. This mixture was refrigerated to maximize precipitation prior to filtering off the olive green solid. The solid was recrystallized from dichloromethane and petroleum ether yielding 2.4 g (6.5 mol) of the yellow solid, Me2Si(C5Me4)(N-s-Bu)TiCl2.
Example RT Compound RT: Part 1. (C5Me4H)SiMe2Cl was prepared as described in Example A for the preparation of compound A, Part 1.
Part 2. (C5Me4H)SiMe2Cl (8.0 g, 0.037 mol) was diluted with ether. LiHN-n-Bu (2.95 g, 0.037 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether was added. The mixture was filtered through Celite to remove the LiCl. The solvent was removed from the filtrate leaving behind the yellow liquid, Me2Si(C5Me4H)(HN-n-Bu)(8.6 g, 0.034 mol).
Part 3. Me2Si(C5Me4H)(HN-n-Bu) (8.6 g, 0.034 mol) was diluted with ether. MeLi (50 ml, 1.4 M in ether, 0.070 mol) was slowly added and the mixture was allowed to stir for two hours. The solvent was removed leaving behind 10.2 g (0.035 mol) of the yellow solid, Li2[Me2Si(C5Me4)(N-n-Bu)].1/3Et2O.
Part 4. Li2[Me2Si(C5Me4)(N-n-Bu)].1/3Et2O (6.0 g, 0.021 mol) was suspended in cold ether. TiCl4.2Et2O (7.04 g, 0.0212 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed and dichloromethane was added. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and petroleum ether was added. The mixture was refrigerated to maximize precipitation prior to filtering off a mixture of dark powder and yellow crystals. The material was redissolved in a mixture of dichloromethane and toluene. A small portion of petroleum ether was added and the brown precipitate was filtered off and discarded. The filtrate was reduced in volume, additional petroleum ether was added and the mixture was placed back in the refrigerator. Later, 3.65 g of the maize yellow solid, Me2Si(C5Me4)(N-n-Bu)TiCl2 was filtered off.
Example ST Compound ST: Part 1. Me2SiCl2 (210 ml, 1.25 mol) was diluted with a mixture of ether and thf. LiMeC5H4 (25 g, 0.29 mol) was slowly added, and the resulting mixture was allowed to stir for a few hours, after which time the solvent was removed in vacuo. Pentane was added to precipitate the LiCl, and the mixture was filtered through Celite. The pentane was removed from the filtrate leaving behind a pale yellow liquid, Me2Si(MeC5H4)Cl.
Part 3. Me2Si(MeC5H4)(HNC12H23) (18.4 g, 0.058 mol) was diluted in ether. MeLi (1.4 M in ether, 82 ml, 0.115 mol) was slowly added. The reaction was allowed to stir for several hours before reducing the mixture in volume and then filtering off the white solid, Li2[Me2Si(MeC5H3)(NC12H23)] (14.3 g, 0.043 mol).
Part 4. Li2[Me2Si(MeC5H3)(NC12H23)] (7.7 g, 0.023 mol) was suspended in cold ether. TiCl4.2Et2O (7.8 g, 0.023 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum. Dichloromethane was added and the mixture was filtered through Celite. The dichloromethane was reduced in volume and petroleum ether was added to maximize precipitation. This mixture was then refrigerated for a short period of time prior to filtering off a yellow/green solid identified as Me2Si(MeC5H3)(NC12H23)TiCl2 (5.87 g, 0.013 mol).
Example TT Compound TT: Part 1. Me2SiCl2 (7.5 ml, 0.062 mol) was diluted with −30 ml of thf. A t-BuH4C5Li solution (7.29 g, 0.057 mol −100 ml of thf) was slowly added, and the resulting mixture was allowed to stir overnight. The thf was removed in vacuo. Pentane was added to precipitate the LiCl, and the mixture was filtered through Celite. The pentane was removed from the filtrate leaving behind a pale yellow liquid, Me2Si(t-BuC5H4)Cl (10.4 g, 0.048 mol).
Part 3. Me2Si(t-BuC5H4)(HNC12H23) (12.7 g, 0.035 mol) was diluted with ether. To this, MeLi (1.4 M in ether, 50 ml, 0.070 mol) was slowly added. This was allowed to stir for two hours prior to removing the solvent via vacuum. The product, Li2[Me2Si(t-BuC5H3)(NC12H23)] (11.1 g, 0.030 mol) was isolated.
The polymerization run was performed in a 1-liter autoclave reactor equipped with a paddle stirrer, an external water jacket for temperature control, a regulated supply of dry nitrogen, ethylene, propylene, 1-butene and hexane, and a septum inlet for introduction of other solvents or comonomers, transition metal compound and alumoxane solutions. The reactor was dried and degassed thoroughly prior to use. A typical run consisted of injecting 400 ml of toluene, 5 ml of 1.0 M MAO, 0.206 mg compound AT (0.2 ml of a 10.3 mg in 10 ml of toluene solution) into the reactor. The reactor was then heated to 80� C. and the ethylene (60 psi) was introduced into the system. The polymerization reaction was limited to 30 minutes. The reaction was ceased by rapidly cooling and venting the system. The solvent was evaporated off of the polymer by a stream of nitrogen. Polyethylene was recovered (11.8 g, MW=279,700, MWD=2.676).
Using the same reactor design and general procedure as described in Example 40, 400 ml of toluene, 5.0 ml cf 1.0 M MAO, and 0.2 ml of a preactivated compound AT solution (10.3 mg of compound AT dissolved in 9.5 ml of toluene and 0.5 ml of 1.0 M MAO) were added to the reactor. The reactor was heated to 80� C., the ethylene was introduced (60 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 14.5 g of polyethylene was recovered (MW=406,100, MWD=2.486).
Using the same reactor design and general procedure described in Example 40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0 M MAO, and 1.03 mg of compound AT (1.0 ml of a 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C, the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 29.2 g of an ethylene-1-hexene copolymer was recovered (MW 129,800, MWD=2.557, 53.0 SCB/1000C by 13C NMR).
Using the same reactor design and general procedure described in Example 40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0 M MAO, and 1.03 mg of compound AT (1.0 ml of 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 50� C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 15.0 g of an ethylene-1-hexene copolymer was recovered (MW=310,000, MWD=2,579, 47.2 SCB/1000C by 13C NMR).
For this Example a stirred 1 L steel autoclave reaction vessel which was equipped to perform continuous Ziegler polymerization reactions at pressures to 2500 bar and temperatures up to 300� C. was used. The reaction system was supplied with a thermocouple and pressure transducer to measure temperature and pressure continuously, and with means to supply continuously purified compressed ethylene and 1-butene (or propylene). Equipment for continuously introducing a measured flow of catalysts solution, and equipment for rapidly venting and quenching the reaction, and of collecting the polymer product were also a part of the reaction system. The polymerization was performed with a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent. The temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 0.888 g of solid compound AT with 0.67 L of a 30 wt % methylalumoxane solution in 4.3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.56 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 RPM. The yield of polymer products was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 50,200, a molecular weight distribution of 2.36 and 60.1 SCB/1000C as measured by 13C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to propylene of 2.6 without the addition of a solvent, the temperature of a cleaned reactor containing ethylene and propylene was equilibrated at the desired reaction temperature of 140� C. The catalyst solution was prepared by mixing 0.779 g of solid compound AT with 0.5 L of a 30 wt % methylalumoxane solution in 24.5 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.9 L/hr which resulted in a temperature of 140� C. in the reactor. During this run, ethylene and propylene were pressured into the autoclave at a total pressure of 2200 bar. The reactor contents were stirred at 1000 RPM. The yield of polymer product was 2.3 kg/hr of an ethylene-propylene copolymer which had a weight average molecular weight of 102,700, a molecular weight distribution of 2.208 and density of 0.863 g/cc.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent. The temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 0.859 g of solid FT with 30 wt % methylalumoxane solution and toluene such that the catalyst concentration was 0.162 g/L with an Al/M molar ratio of 1200. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 1.15 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300. The reactor contents were stirred at 1000 RPM. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 61,400, a molecular weight distribution of 2.607 and 104.8 SCB/1000C by 13C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 170� C. The catalyst solution was prepared by mixing 0.925 g of solid compound AT with 2 L of a 10 wt % methylalumoxane solution in 8 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.28 L/hr which resulted in a temperature of 170� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1306 bar. The reactor contents were stirred at 1000 RPM. The yield of polymer product was 3.7 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 69,500, a molecular weight distribution of 2.049 and 35.7 SCB/1000C by 13C NRM.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.94 g of solid compound IT with 30 wt % methylalumoxane solution and toluene such that the catalyst concentration was 0.388 g/L and the Al/M molar ratio was 600. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.42 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 RPM. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 50,000, 1 molecular weight distribution of 2.467 and 69 SCB/1000C as measured by 1H NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.78 g of solid Compound JT with 30 wt % methylalumoxane solution and toluene such that the catalyst concentration was 0.318 g/L and the Al/M molar ratio was 1400. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.55 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 RPM. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 72,600, a molecular weight distribution of 2.385 and 110 SCB/1000C as measured by 1H NMR.
The catalyst solution was prepared by mixing a specified amount of solid transition metal component with a 30 weight percent methylalumoxane solution and this catalyst solution was then further diluted in toluene under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate which resulted in the desired reactor temperature of 180� C., which was the polymerization temperature of all examples. The reactor contents were stirred at 1000 RPM and a reactor mass flow rate of 40 kg/g was used for all examples. The reactor pressure was maintained at 1300 bar and no hydrogen was supplied to the reactor. Exact run conditions including catalyst preparation [transition metal component (TMC) and amount (g), methylalumoxane (MAO) volume used (L), total volume of catalyst solution (L) and concentration (g TMC/L) and (g MAO/L)], catalyst feed rate (L/hr), polymer production rate (kg polymer/hr), molar Al/M ratio, productivity (kg polymer/g catalyst) and polymer characteristics including weight average MW (Daltons), molecular weight distribution (MW/MN), melt index g/10 minute at 190� C.), weight percent comonomer (determined by 1H NMR or 13C NMR), and catalyst reactivity ratios (r1) are collected in Table 1.
Example AS An ionic catalyst was prepared by dissolving 50 ml of dimethylsilyl(cyclododecylamido)-tetramethylcyclopentadienyltitanium dimethyl and 25 mg N,N-dimethylanilinium tetrakis(pentafluorophenyl)boron in 10 ml toluene. Dry, oxygen-free hexane (400 ml) was added to a 1 liter stainless steel autoclave which had been previously flushed with nitrogen. Under nitrogen, a hexane solution (2 ml) containing 0.25% triisoprenylaluminum was transferred into the autoclave by means of a double-ended needle, followed by 4 ml of the catalyst solution. The ratio of titanium containing catalyst to boron containing activator was 3.7. The solution in the autoclave was heated to 80� C. and 4.42 atmospheres of ethylene (0.228 moles) were introduced. Polymerization was carried out for 0.1 hours, after which time the autoclave was vented and opened. The yield of polyethylene was 2.1 grams. This corresponds to productivity of 61 kg polymer/mole activator atmosphere hour, or 269 kg polymer/mole activator hour.
Example AT An ionic catalyst was prepared and utilized substantially as described in Example AS except that dimethlsilyl(N-t-butylamido)tetramethylcyclopentadienyltitanium dimethyl was substituted for dimethylsilyl(cyclododecylamido)tetramethylcyclopentadienyltitanium dimethyl.
From the above examples, particularly as collected in Table 1, it appears that for a catalyst system wherein the Group IV B transition metal component is a titanium species of the following structure: the nature of the R′ group dramatically influence the catalytic properties of the system. For production of ethylene-α-olefin copolymers of greatest comonomer content, at a selected ethylene to α-olefin monomer ratio, R′ is preferably a non-aromatic substituent, such as an alkyl or cycloalkyl substituent preferably bearing a primary or secondary carbon atom attached to the nitrogen atom.
11.3 42.0
13.2 41.9
19 24.0
10 42.8
17.62 13CNMR
13.8 17.38 13CNMR
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS5026798Sep 13, 1990Jun 25, 1991Exxon Chemical Patents Inc.Coordination catalystUS5055438Jun 4, 1990Oct 8, 1991Exxon Chemical Patents, Inc.Olefin polymerization catalystsUS5057475Sep 13, 1990Oct 15, 1991Exxon Chemical Patents Inc.Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerizationUS5064802 *Jul 3, 1990Nov 12, 1991The Dow Chemical CompanyCyclopentadienyl, polymerization catalystsUS5066741Jul 30, 1990Nov 19, 1991The Dow Chemical CompanyProcess for preparation of syndiotactic vinyl aromatic polymersUS5096867Sep 13, 1990Mar 17, 1992Exxon Chemical Patents Inc.Polymer products of high molecular weight and narrow molecular weight distribution using small amounts of an alumoxane with the titanium complexUS5132380Sep 12, 1991Jul 21, 1992The Dow Chemical CompanyMetallocene catalysts for olefin polymerizationUS5189192Jan 16, 1991Feb 23, 1993The Dow Chemical CompanyCoordination catalystsUS5227440Aug 28, 1991Jul 13, 1993Exxon Chemical Patents Inc.Mono-Cp heteroatom containing Group IVB transition metal complexes with MAO: supported catalysts for olefin polymerizationUS5264405Mar 13, 1992Nov 23, 1993Exxon Chemical Patents Inc.Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalystsUS5272236 *Oct 15, 1991Dec 21, 1993The Dow Chemical CompanyElastic substantially linear olefin polymersUS5278272Sep 2, 1992Jan 11, 1994The Dow Chemical CompanyElastic substantialy linear olefin polymersEP0277004A1 *Jan 27, 1988Aug 3, 1988Exxon Chemical Patents Inc.Catalysts, method of preparing these catalysts and method of using said catalystsEP0416815A2Aug 30, 1990Mar 13, 1991The Dow Chemical CompanyConstrained geometry addition polymerization catalysts, processes for their preparation, precursors therefor, methods of use, and novel polymers formed therewithEP0468651A1Jul 1, 1991Jan 29, 1992The Dow Chemical CompanyAddition polymerization catalyst with oxidative activationEP0514828A1May 19, 1992Nov 25, 1992The Dow Chemical CompanyPreparation of addition polymerization catalystsEP0520732A1Jun 22, 1992Dec 30, 1992The Dow Chemical CompanyHomogeneous olefin polymerization catalyst by ligand abstraction with lewis acidsWO1993008199A1Oct 13, 1992Apr 29, 1993Dow Chemical CoPreparation of metal coordination complexWO1993008221A2Oct 15, 1992Apr 29, 1993Dow Chemical CoElastic substantially linear olefin polymersWO1993013140A1Dec 21, 1992Jul 8, 1993Exxon Chemical Patents IncA modified monocyclopentadienyl transition metal/alumoxane catalyst system for polymerization of olefins* Cited by examinerNon-Patent CitationsReference1K�kenh�hner, "Organotitan (IV) Agentien: Komplexe Chiraler Chelatliganden und Enantioselektire c-c-Verkn�pfungen" (University of Marburg, Germany 1986).2K�kenh�hner, "Untersuchungen zur Darsteliung Chiraler Organotian (IV)-Verbindungen f�r Enantioselektire Synthesen" (1983) (unpublished Dipolmarbeit, University of Marburg, Germany).3M. 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Soc. 113, pp 3623-3625, 1991.** Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS6806326Nov 6, 2001Oct 19, 2004The Dow Chemical CompanyConstrained geometry addition polymerization catalystsUS6825369 *Mar 10, 1994Nov 30, 2004The Dow Chemical CompanyMetal complex compoundsUS7163907 *Jun 22, 1990Jan 16, 2007Exxonmobil Chemical Patents Inc.comprising Group IV-B transition metal compounds and an ion-exchange activator compound; for the production of polyolefins, particularly polyethylene, polypropylene, and ethylene- alpha -olefin copolymersUS7247686Oct 17, 2002Jul 24, 2007Basell Polyolefine GmbhSolid cocatalyst component for olefin polymerization and catalyst system thereof* Cited by examinerClassifications U.S. Classification526/160, 526/348.3, 526/348.4, 526/943, 526/348.6, 526/127, 526/348.5, 526/348.2, 526/161International ClassificationC08F10/06, C08F4/659, C08F210/06, C08F110/02, C08F10/00, C08F110/06, C08F210/18, C07F7/10, C07F17/00, C08F4/6592, C08F210/16, C08F4/64Cooperative ClassificationY10S526/943, C08F4/6592, C08F10/06, C07F7/10, C08F210/06, C08F4/65912, C08F4/65908, C08F110/02, C08F4/65922, C08F210/16, C07F17/00, C08F110/06, C08F10/00, C08F210/18European ClassificationC08F10/00, C08F10/06, C07F7/10, C07F17/00, C08F210/16Legal EventsDateCodeEventDescriptionDec 30, 2013FPAYFee paymentYear of fee payment: 12Dec 22, 2009FPAYFee paymentYear of fee payment: 8Dec 28, 2005FPAYFee paymentYear of fee payment: 4Jul 9, 2002ASAssignmentOwner name: EXXONMOBIL CHEMICAL PATENTS INC., TEXASFree format text: CHANGE OF NAME;ASSIGNOR:EXXON CHEMICAL PATENTS INC.;REEL/FRAME:013063/0532Effective date: 20010125Owner name: EXXONMOBIL CHEMICAL PATENTS INC. 13501 KATY FREEWAFree format text: CHANGE OF NAME;ASSIGNOR:EXXON CHEMICAL PATENTS INC. /AR;REEL/FRAME:013063/0532RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google