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Patent USRE40234 - Process for producing crystalline poly-α-olefins with a monocyclopentadienyl ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsThe invention is a catalytic process using a Group IV B transition metal component and an alumoxane component to polymerize α-olefins to produce high crystallinity and high molecular weight poly-α-olefins....http://www.google.com/patents/USRE40234?utm_source=gb-gplus-sharePatent USRE40234 - Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst systemAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUSRE40234 E1Publication typeGrantApplication numberUS 07/973,107Publication dateApr 8, 2008Filing dateNov 6, 1992Priority dateSep 13, 1989Also published asCA2090872A1, CA2090872C, DE69132836D1, DE69132836T2, EP0548277A1, EP0548277B1, US5026798, WO1992005204A1Publication number07973107, 973107, US RE40234 E1, US RE40234E1, US-E1-RE40234, USRE40234 E1, USRE40234E1InventorsJo Ann M. CanichOriginal AssigneeExxonmobil Chemical Patents, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (10), Non-Patent Citations (10), Referenced by (2), Classifications (45) External Links: USPTO, USPTO Assignment, EspacenetProcess for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US RE40234 E1Abstract
1. A process for producing crystalline poly-α-olefins comprising the steps of
(i) contacting an α-olefin monomer at a temperature and pressure sufficient to polymerize such monomer with a catalyst system comprising; comprising:
(A) an alumoxane, and (B) a group Group IV-B transition metal component of the formula wherein M is Zr, Hf or Ti in its highest formal oxidation state; R is a substituent group with “x” denoting the degree of substitution (x=0, 1, 2, 3 or 4) 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 radical, an amido radical, a phosphido radical, an 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, and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or a radical other radicals containing a Lewis acidic or basic functionality, or at least two adjacent R-groups are joined forming C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl 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 each R′ is, independently R′ is a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals where one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, and an alkoxy radical or a other radical containing a Lewis acidic or basic functionality, and “z” is the coordination number of the element J; each Q is, independently, any univalent anionic ligand or two Q's are a divalent anionic chelating ligand; ligand, provided that Q is not a substituted or unsubstituted cyclopentadienyl ring;
T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where “w” denotes a number from 0 to 3; (ii) recovering a crystalline poly-α-olefin. 2. The process of claim 1, wherein the Group IV-B transition metal component is of the formula: wherein R1 and R2 are, independently, a C1 to C20 hydrocarbyl radicals, or substituted C1 to C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom; R1 and R2 may also be joined forming a C3 to C20 ring.
4. The process of claim 3 wherein R is a C1 to C20 hydrocarbyl radical, “x” is 1 and R′ is a C6 to C20 cyclohydrocarbyl radical or an aromatic radical.
5. The process of claim 1 wherein the Group IV-B transition metal component is of the formula: wherein R1 and R2 are independently a C1 to C20 hydrocarbyl radicals, or substituted C1 to C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom; R1 and R2 may also be joined forming a C3 to C20 ring. 6. The process of claim 5 where wherein J is nitrogen.
7. The process of claim 6 wherein R′ is an alkyl radical or cyclic cycloalkyl radical.
8. The process of claim 1 wherein the Group IV-B transition metal component is of the formula formula:
“x” is 0, 1 or 2;
R1 and R2 are independently a C1 to C20 hydrocarbyl radicals, or substituted C1 to C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom; R1 and R2 may also be joined forming a C3 to C20 ring. 9. The process of claim 8 wherein J is nitrogen.
10. The process of claim 9 wherein R′ is a cycloalkyl radical.
13. The process of claim 1 wherein T is a covalent bridging group containing silicon, J is nitrogen and when R is an alkyl radical, R′ is a cyclohydrocarbyl or aromatic radical, and or when “x” is 2 or 4 and the R substituents form a polycyclic ring system, R′ is an alkyl or cyclohydrocarbyl radical.
This invention relates to a process for polymerizing α-olefins which utilize utilizes certain monocyclopentadienyl metal compounds of a Group IV B transition metal of the Periodic Table of Elements in an alumoxane activated catalyst system to produce crystalline poly-α-olefins, particularly polypropylene and α-olefin copolymers of propylene.
Traditional Ziegler-Natta catalysts 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.
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 herein as a “metallocene “metallocene”—which catalyzes the production of olefin monomers to polyolefins. Accordingly, 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 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 the production of polyolefins.
The zirconocenes, as cocatalyzed or activated with an alumoxane, are commonly more active than their hafnium or titanium analogous 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 (Al: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 zirconium or hafnium species of metallocenes may be used. Titanium species of metallocenes are generally unstable at such high pressures unless deposited upon a catalyst support. A wide variety of Group IV B transition metal compounds have been named as possible candidates for an alumoxane cocatalyzed catalyst system. Although bis(cyclopentadienyl) Group IV B transition metal compounds have been the most preferred and heavily investigated for use in alumoxane activated catalyst systems for polyolefin production, suggestions have appeared that mono and tris(cyclopentadienyl) transition metal compounds may also be useful. See, for example U.S. Pat. Nos. 4,522,982; 4,530,914 and 4,701,431. Such mono(cyclopentadienyl) transition metal compounds as have heretofore been suggested as candidates for an alumoxane activated catalyst system are mono(cyclopentadienyl) transition metal trihalides and trialkyls.
More recently, International Publication No. WO 87/03887 describes the use of a composition comprising a transition metal coordinated to at least one cyclopentadienyl and at least one heteroatom ligand as a transition metal component fo ruse in an alumoxane activated catalyst system for α-olefin polymerization. The composition is broadly defined as a transition metal, preferably of Group IV B of the Periodic Table, which is coordinated with at least one cyclopentaidienyl ligand and one to three heteroatom ligands, the balance of the transition metal coordination requirement being satisfied with cyclopentadienyl or hydrocarbyl ligands. Catalyst systems described by this reference are illustrated solely with reference to transition metal compounds which are metallocenes, i.e., bis(cyclopentadienyl) Group IV B transition metal compounds.
The degree and type of tacticity of a polyolefin molecule is a are critical determinant determinants of the physical properties which a resin composed of such polymer molecules will exhibit. Other critical determinants of the properties which a resin will exhibit are the type and relative concentration of monomers and comonomers, the weight average molecular weight (Mw) of the polymer molecules comprising the resin bulk, the molecular weight distribution (MWD) and the composition distribution of the resin.
Atactic poly-α-olefins are those wherein the hydrocarbyl groups pendent to the polymer molecule backbone assume no regular order in space with reference to the backbone. This random, or atactic, structure is represented by a polymer backbone of alternating methylene and methine carbons, with randomly oriented branches substituting the methine carbons. The methine carbons randomly have R and S configurations, creating adjacent pairs either of like configuration (a “meso” or “m” dyad) or of unlike configuration (a “racemic” or “r” dyad). The atactic form of a polymer contains approximately equal fractions of meso and racemic dyads.
Isotactic poly-α-olefins are those wherein the pendent hydrocarbyl groups are ordered in space to the same side or plane of the polymer backbone chain. Using isotactic polypropylene as an example, the isotactic structure is typically described as having the pendent methyl groups attached to the ternary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the carbon backbone chain of the polymer, e.g., the methyl groups are all above or below the plane as shown below. The degree of isotactic regularity may be measured by NMR techniques. Bovey's NMR nomenclature for an isotactic pentad is . . . mmmm . . . with each “m” representing a “meso” dyad or successive methyl groups on the same side in of the plane.
In the normal isotactic structure of a poly-α-olefin, all of the monomer units have the same stereochemical configuration, with the exception of random errors which appear along the polymer. Such random errors almost always appear as isolated inversions of configuration which are corrected in the very next α-olefin monomer insertion to restore the original R or S configuration of the propagating polymer chain. Single insertions of inverted configuration give rise to rr triads, which distinguish this isotactic structure in its NMR from the isotactic stereoblock form. As is known in the art, any deviation or inversion in the regularity of the structure of the chains lowers the degree of isotacticity and hence the crystallinity of which the polymer is capable. There are two other types of “errors” which have been observed in isotactic polymers prepared using metallocene-alumoxane catalyst systems which act to lower the melting point and/or Tg of the material. These errors, as shown below arise when a monomer is added to the growing polymer chain in a 1, 3 or 2,1 fashion. Long before anyone had discovered a catalyst system which produced the isotactic stereoblock form of a poly-α-olefin, the possible existence of a polymer of such micro-structure had been recognized and mechanisms for its formation had been proposed based on conventional Ziegler-Natta mechanisms in Langer, A. W., Lect. Bienn. Polym. Symp. 7th (1974); Ann. N.Y. Acad. Sci. 295, 110-126 (1977). The first example of this form of polypropylene and a catalyst which produces it in a pure form were reported in U.S. Pat. No. 4,522,982. The formation of stereoblock isotactic polymer differs from the formation of the normal isotactic structure in the way that the propagation site reacts to a stereochemical error in the chain. As mentioned above, the normal isotactic chain will return to the original configuration following an error because the stereochemical regulator, the catalytic active metal species and its surrounding ligands, continue to dictate the same stereochemical preference during monomer insertion. In stereoblock propagation, the catalytic active metal site itself changes from one which dictates a monomer insertion of R configuration to one which dictates an S configuration for monomer insertion. The isotactic stereo-block form is shown below. This occurs either because the metal and its ligands change to the opposite stereochemical configuration or because the configuration of the last added monomer, rather than the metal chirality, controls the configuration of the next added monomer. In Ziegler-Natta catalysts, including the above referenced system, the exact structure and dynamic properties of the active site are not well understood, and it is virtually impossible to distinguish between the “site chirality exchange” and “chain end control” mechanisms for the formation of isotactic stereoblock poly-α-olefins.
Unlike normal isotactic polymers, the lengths of individual blocks of the same configuration in the stereo-block structure vary widely due to changing reaction conditions. Since only the erroneous parts of the chains affect the crystallinity of the resin product, in general, normal isotactic polymers and isotactic stereoblock polymers of long block length (greater than 50 isotactic placements) have similar properties.
Syndiotactic poly-α-olefins are those wherein the hydrocarbyl groups pendent to the polymer molecular backbone alternate sequentially in order from one side or plane to the opposite side or plane relative to the polymer backbone, as shown below. In NMR nomenclature, this pentad is described as . . . rrr . . . in which each r represents a “racemic” dyad, i.e., successive methyl groups on alternative sides of the plane. The percentage of r dyads in the chain determines the degree of syndiotacticity of the polymer.
Syndiotactic propagation has been studied for over 25 years; however, only a few good syndiospecific catalysts have been discovered, all of which are extremely sensitive to monomer bulkiness. As a result, well-characterized syndiotactic polymers are limited only to polypropylenes. . The molecular chain backbone of a syndiotactic polymer can be considered to be a copolymer of olefins with alternating stereochemical configurations. Highly syndiotactic polymers are generally highly crystalline and will frequently have high melting points similar to their isotactic polymorphs.
Like isotactic poly-α-olefins, syndiotactic poly-α-olefins are capable of exhibiting a high degree of crystallinity, hence are suitable for high strength applications provided their Mw exceeds about 100,000. Syndiotactic poly-β-olefins poly-α-olefins are in part characterized by their exhibition of a melting point temperature.
For any of the above described materials the final resin properties and its their suitability for particular applications depend depends on the type of tacticity, the melting point (stereoregularity), the average molecular weight, the molecular weight distribution, the type and level of monomer and comonomer, the sequence distribution, and the presence or absence of head or end group functionality. Accordingly, the catalyst system by which such a stereoregular poly-α-olefin resin is to be produced should, desirably, be versatile in terms of Mw, MWD, tacticity type and level, and comonomer choice. Further, the catalyst system should be capable of producing these polymers with or without head and/or end group functionality, such as olefinic unsaturation. Still further, such catalyst system must be capable, as a commercially practical constraint, of producing such resins at an acceptable production rate. Most preferably, the catalyst system should be one which, at its productivity rate, provides a resin product which does not require a subsequent treatment to remove catalyst residue to a level which is acceptable for the resin in the end use application desired. Finally, an important feature of a commercial catalyst system is its adaptability to a variety of processes and conditions.
Catalysts that produce isotactic polyolefins are also disclosed in U.S. Pat. No. 4,794,096. This patent discloses a chiral, stereorigid metallocene catalyst which is activated by an alumoxane cocatalyst which is reported to polymerize olefins to isotactic polyolefin forms. Alumoxane cocatalyzed metallocene structures which have been reported to polymerize stereoregularly are the ethylene bridged bis-indenyl and bis-tetrahydroindenyl titanium and zirconium (IV) catalyst. Such catalyst systems were synthesized and studied in Wild et al., J. Organomet. Chem. 232, 233-47 (1982), and were later reported in Ewen and Kaminsky et al., mentioned above, to polymerize β-olefins α-olefins stereoregularly. Further reported in West German Off DE 3443087A1 (1986), but without giving experimental verification, is that the bridge length of such stereorigid metallocenes can vary from a C1 to C4 hydrocarbon and the metallocene rings can be simple or bi-cyclic but must be asymmetric.
Metallocene-alumoxane catalyst generally require a high content of alumoxane cocatalyst to be sufficiently productive for commercial use. Accordingly, metallocene-alumoxane produced isotactic poly-α-olefin resins generally have a higher than desired catalyst residue content. Hafnocene systems, which yield polymers of higher average Mw than the zirconium analogs, analogues, have very low activities even at high alumoxane concentrations.
More recently, a metallocene based catalyst system has been disclosed which is stated to be capable of production of syndiotactic polypropylene of high stereo-regularity. U.S. Pat. No. 4,892,851 describes catalyst systems consisting of a bridged metallocene having at least two differently substituted cyclopentadienyl ring ligands which, when cocatalyzed with an alumoxane, is stated to be capable of production of syndiotactic polypropylene. Again, in commercial production to obtain a sufficient productivity level with such catalyst system, the content of alumoxane is undesirably high and consequently the catalyst residue in the resin so produced is undesirably high.
In view of the difficulty and practical limitations in the synthesis of bridged metallocene complexes necessary for the production of an alumoxane activated metallocene catalyst system capable of producing crystalline, poly-α-olefins, it would be desirable to develop new catalytic processes which produce highly crystalline forms of poly-α-olefins of high molecular weight and relatively narrow molecular weight distributions.
The “Group IV B transition metal component” of the catalyst system is represented by the formula: wherein:
M is Zr, Hf or Ti in its highest formal oxidation state (+4, d0 complex); (C2H4-xRx)(C 5 H 4-x R x) 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, an 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; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, aklylboridoalkylborido radicals or any other radical containing a Lewis acidic or basic functionality; or (C5H4-xRx) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
(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, 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 wherein one or more hydrogen atoms are replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing a Lewis acidic or basic functionality, and “z” is the coordination number of the element J; each Q may be independently any univalent anionic ligand such as a halide, hydride, or substituted or unsubstituted C1-C20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where any Q is a hydrocarbyl such Q is different from (C5H4-xRx), or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand; 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, tetra-ethylammonium chloride, 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 meaning as M and Q′ has the same meaning as Q. Such dimeric compounds are represented by the formula: The alumoxane component of the catalyst may be represented by the formulas: (R3—Al—O)m; R4(R5—Al—O)m −AlR 6 R4(R 5 —Al—O)m —AlR 6 2 or mixtures thereof, wherein R3-R6 are, independently, a C1-C5 alkyl group or halide and “m” is an integer ranging from 1 to about 50 and preferably is from about 13 to about 25.
Catalyst systems of the invention may be prepared by placing the “Group IV B transition metal component” and the alumoxane 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 α-olefin monomer.
Those species of the Group IV B transition metal component wherein the metal is titanium have been found to impart beneficial properties to a catalyst system which are unexpected in view of what is known about the properties of bis(cyclopentaidienyl) titanium compounds which are cocatalyzed by alumoxanes. Whereas titanocenes in their soluble form are generally unstable in the presence of aluminum alkyls, the monocyclopentadienyl titanium metal components of this invention, particularly those wherein the heteroatom is nitrogen, generally exhibit greater stability in the presence of aluminum alkyls and higher catalyst activity rates.
A typical polymerization process of the invention such as for the polymerization or copolymerization of propylene comprises the steps of contacting propylene or other C4 -C 20 α-olefins alone, or with other unsaturated monomers including C 3 -C 20 α-olefins, C 4 -C 20 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, a Group IV B transition metal component illustrated above; and a methylalumoxane in an amount to provide a molar aluminum to transition metal ratio of from about 1:1 to about 20,000:1 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 poly-α-olefin having a weight average molecular weight of from about 1,000 or less to about 2,000,000 or more and a molecular weight distribution of from about 1.5 1 to about 15.0.
As discussed further hereafter, by proper selection of the type and pattern R substituents for the cyclopentadienyl ligand in relationship to the type of R′ substituent of the heteroatom ligand the transition metal component for the catalyst system may be tailored to function in the catalyst system to produce highly crystalline poly-α-olefins to the total or substantial avoidance of the production of atactic poly-α-olefin molecules which are amorphous.
The Group IV B transition metal component of the catalyst system is represented by the general formula: wherein M is Zr, Hf or Ti in its highest formal oxidation state (+4, d0 complex);
(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; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, aklylborido radicals or any other radical containing a Lewis acidic or basic functionality; or (C5H4-xRx) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
(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, 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 radical, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing a Lewis acidic or basic functionality, and “z” is the coordination number of the element J;
each Q is, independently, any univalent anionic ligand such as a halide, hydride, or substituted or unsubstituted C1-C20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where any Q is a hydrocarbyl such Q is different from (C5H4-xRx), or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand;
and 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 meaning as M and Q′ has the same meaning as Q. Such compounds are represented by the formula: 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”.
Suitable, but not limiting, Group IV B transition metal compounds which may be utilized in the catalyst system of this invention include those wherein the T group bridge is a dialkyl, diaryl or alkylaryl silane, silyl, or methylene or ethylene. Exemplary 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.
Exemplary hydrocarbyl radicals for 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 halogen atoms for Q include chlorine, bromine, fluorine and iodine, with chlorine being preferred. Exemplary alkoxides and aryloxides for Q are methoxide, phenoxide and substituted phenoxides such as 4-methylphenoxide. Exemplary amides of Q are dimethylamide, diethylamide, methylethylamide, di-t-butylamide, diisoproylamide diisopropylamide and the like. Exemplary aryl amides are diphenylamide and any other substituted phenyl amides. Exemplary phosphides of Q are diphenylphosphide, dicyclohexylphosphide, diethylphosphide, dimethylphosphide 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”.
Suitable hydrocarbyl and substituted hydrocarbyl radicals, which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, will contain from 1 to about 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals, amido-substituted hydrocarbon radicals, phosphido-substituted hydrocarbon radicals, alkoxy-substituted hydrocarbon radicals, and cyclopentadienyl rings containing one or more fused saturated or unsaturated rings. Suitable organometallic radicals, which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl and the like. Other suitable radicals that may be substituted for one or more hydrogen atom in the cyclopentadienyl ring include halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals and the like. Examples of cyclopentadienyl ring groups (C5H4-xRx) which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in Column column 2 of Table 1 under the heading (C5H4-xRx). Suitable R′ radicals of the heteroatom J ligand are independently a hydrocarbyl radical selected from the group consisting of 1 to about 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and the like; substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical and a an alkylborido radical, or a radical containing a Lewis acidic or basic functionality, and the like. Examples of heteroatom ligand groups (JR′z-2) which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in column 3 of Table 1 under the heading (JR′z-2).
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: dimethylsilylfluorenyl-t-butylamido zirconium dichloride, dimethylsilylfluorenyl-t-butylamido hafnium dichloride, dimethylsilylfluorenylcycohexylamide zirconium dihalide, and dimethylsilylfluorenylcyclohexylamido hafnium dichloride.
As noted, titanium species of the Group IV B transition metal compound have generally been found to yield catalyst systems which in comparison to their zirconium or hafnium analogues, are of higher activity. Illustrative, but not limiting of the titanium species which may exhibit such superior properties are; are: dimethylsilylfluorenyl-t-butylamido titanium dichloride, dimethylsilylindenylcyclohexylamide titanium dichloride, dimethylsilyl-t-butylcyclopentadienylcyclododecylamido titanium dichloride, dimethylsilylmethylcyclopentadienylcyclododecylamido titanium dichloride, dimethylsilylmethylcyclopentadienyl-2,6-diisopropylphenylamido titanium dichloride, dimethylsilylmethylcyclopentadienylcyclohexylamido titanium dichloride, and dimethylsilylmethylcyclopentadienyl-2,5-di-t-butylphenylamido titanium dichloride.
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 dimeric compounds is are determined by the steric bulk of the ligands about the metal center. For example, the t-butyl group in Me2(Si(Me4C5)(N-t-Bu)ZrCl2 has greater steric requirements than the phenyl group in Me2Si(Me4C5)(NPh)ZrCl2•Et2O thereby not permitting ether coordination in the former compound. Similarly, due to the decreased steric bulk of the trimethylsilylcyclopentadienyl group in [Me2Si(Me3SiC5H3)(N-t-Bu)ZrCl2]2 versus that of the tetramethylcyclopentadienyl group in Me2Si(Me4C5)(N-t-Bu)ZrCl2, Me2 Si(Me 4 C 5)(N-t-Bu)ZrCl 2 , the former compound is dimeric and the latter is not.
To illustrate members of the Group IV B transition metal component, select any combination of the species in Table 1. An example of a bridged species would be dimethylsilyclopentadienyl-t-butylamidodichloro dimethylsilylcyclopentadienyl-t-butylamidodichloro zirconium.
(C5H4-2Rx)
(JR′z-2)
(t-butylamide
diethylsilyl
phenylamido
di-n-propylsilyl
1,2-dimethylcyclopentadienyl
p-n-butylphenylamido
diisopropylsilyl
1,3-dimethylcyclopentadienyl
cyclohexylamido
di-n-butylsilyl
perflurophenylamido
di-t-butylsilyl
1,2-diethylcyclopentadienyl
n-butylamido
di-o-hexylsilyl
tetramethylcyclopentadienyl
methylamido
methylphenylsilyl
ethylcyclopentadienyl
ethylamido
ethylmethylsilyl
n-butylcyclopentadienyl
n-propylamido
cyclohexylmethylcyclopentadienyl
isopropylamido
di(p-t-butylphenethylsilyl)
n-octylcyclopentadienyl
benzylamido
βphenylpropylcyclopentadienyl
t-butylphosphido
cyclopentamethylenesilyl
ethylphosphido
cyclotetramethylenesilyl
propylcyclopentadienyl
phenylphosphido
cyclotrimethylenesilyl
t-butylcyclopentadienyl
cyclohexylphosphido
dimethylgermanyl
benzylcyclopentadienyl
diethylgermanyl
diphenylmethylcyclopentadienyl
trimethylgermylcyclopentadienyl
eosyl
t-butyltamido
trimethylstannylcyclopentadienyl
triethylplumbylcyclopentadienyl
trifluromethylcyclopentadienyl
trimethylsilylcyclopentadienyl
pentamethylcyclcopenta-
dienyl (when y = 0) methylene
octahydrofluorenyl
diethylmethylene
N,N-dimethylamidocyclopentadienyl
dimethylamido
dimethylphosphidocyclopentadienyl
diethylamido
methoxycyclopentadienyl
methylethylamido
diethylethylene
dimethylboridocyclopentadienyl
di-t-butylamido
dipropylethylene
(N,N-dimethylamidomethyl)cyclopentadienyl
diphenylamido
tetrafluorocyclopentadienyl
diphenylphosphido
dimethylpropylene
dicyclohexylphosphido
diethylpropylene
dimethylphosphido
1,1-dimethyl-3,3-
methylidene (both Q)
ethylidene (both Q)
1,1,4,4-tetramethyl-
propylidene (both Q)
The class of transition metal components most preferred for use in the process for production of crystalline poly-β-olefins poly-α-olefins is that wherein the covalent bridging group T contains silicon and the heteroatom J of the heteroatom ligand is nitrogen. Accordingly, the preferred class of transition metal components are of the formula: wherein Q, L, R′, R, “x” and “w” are as previously defined and R1 and R2 are each independently a C1 to C20 hydrocarbyl radicals, substituted C1 to C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom; R1 and R2 may also be joined forming a C3 to C20 ring which incorporates the silicon bridge.
The alumoxane component of the catalyst system 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 R3 , R 4 , R 5 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 which may be 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.
The catalyst systems employed in the method of the invention comprise a complex formed upon admixture of the Group IV B transition metal component with an alumoxane component. The catalyst system may be prepared by addition of the requisite Group IV B transition metal and alumoxane components to an inert solvent in which olefin polymerization can be carried out by a solution slurry, gas or bulk phase polymerization procedure.
The catalyst system may be conveniently prepared by placing the selected Group IV B transition metal component and the selected alumoxane component, in any order to addition, in an alkane or aromatic hydrocarbon solvent—preferably one which is also suitable for service as a polymerization diluent. When 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. 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 transition metal, the alumoxane, 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 −10� 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.
At all times, the individual catalyst system components, as well as the catalyst system once formed, are protected from oxygen and moisture. Therefore, the reactions to prepare the catalyst system are performed in an oxygen and moisture free atmosphere and, where the catalyst system is recovered separately separately, it is recovered in an oxygen and moisture free atmosphere. Preferably, therefore, the reactions are performed in the presence of an inert dry gas such as, for example, helium or nitrogen.
The monomer for such process comprises an α-olefin having 3 to 20 carbon atoms. Propylene is a preferred monomer. Homopolymers of higher α-olefin such as butene, styrene and copolymers thereof with ethylene and/or C4 or higher α-olefins, diolefins, cyclic olefins and internal olefins can also be prepared. Conditions most preferred for the homo- or copolymerization of the α-olefin are those wherein an α-olefin is submitted to the reaction zone at pressures of from about 0.09 0.019 psia to about 50,000 psia and the reaction temperature is maintained at from about −100� to about 300� C. The aluminum to transition metal molar ratio is preferably from about 1:1 to 18,000 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 polymer is as follows: in a stirred-tank reactor liquid α-olefin monomer is introduced, such as propylene. The catalyst system is introduced via nozzles in either the vapor or liquid phase. The reactor contains a liquid phase composed substantially of the liquid α-olefin monomer together with a vapor phase containing vapors of the monomer. 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 preferred polymerization diluents for practice of the process of the invention are aromatic diluents, such as toluene, or alkanes, such as hexanes.
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 (=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.
Calculations involved in the characterization of polymers by 13CNMR 13 C NMR follow the work of F. A. Bovey in “Polymer Conformation and Configuration” Academic Press, New York, 1969.
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 al. Organometallics, 3, 819 (1984) and F. H. K�hler and K. H. Doll, Z. Naturforsch, 376, 144 (1982). Lithiated substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and D-BuLi 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 and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems. Methylalumoxane was supplied by either Schering or Ethyl Corp.
Transition Metal—Components
Compound A: 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 2. Me2Si(t-BuC5H4)Cl (8.0 g, 0.037 mol) was diluted with thf. THF. To this, LiHNChd 12H23 LiHNC12 H 23 (7.0 g, 0.037 mol) was slowly added. The mixture was allowed to stir overnight. The solvent was removed via vacuum and toluene was added to precipitate the LiCl. The toluene was removed from the filtrate leaving behind a pale yellow liquid, Me2Si(t-BuC5H4)(HNC12H23)(12.7 g, 0.035 mol).
Part 3. Me2Si(t-BuC5H4)(HNC12H23)(12.7 g, 0.035 mol) was diluted with ether. To this, MeLi (1.4M 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.
Part 4. Li2[Me2Si(t-BuC5H3)(NC12H23)] (10.9 g, 0.029 mol) was suspended in cold ether. TiCl4•2Et2O (9.9 g, 0.029 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 solvent was removed and pentane was added. The product is completely soluble in pentane. This solution was passed through a column containing a top layer of silica and a bottom layer of Celite. The filtrate was then evaporated down to an olive green colored solid identified as Me2Si(t-BuC5H3)(NC12H23)TiCl2 (5.27 g, 0.011 mol).
Compound B: 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 2. Me2Si(MeC5H4)Cl (10.0 g, 0.058 mol) was diluted with a mixture of ether and THF. To this, LiHNC12H23 (11.0 g, 0.058 mol) Was was slowly added. The mixture was allowed to stir overnight. The solvent was removed via vacuum and toluene and pentane were added to precipitate the LiCl. The solvent was removed from the filtrate leaving behind a pale yellow liquid, Me2Si(MeC5H4)(HNC12H23)(18.4 g, 0.058 mol).
Part 3. Me2Si(MeC5H4)(HNC12H23) (18.4 g, 0.058 mol) was diluted in ether. MeLi (1.4M in ether, 82 ml, 0.115 mol) was slowly added. The reaction was stirred for several hours before reducing the volume and then filtering off the white solid, Li2[Me2Si(MeC5H3)(NC12H23)] (14.2 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 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 Me2(Si(MeC5H3)(NC12H23)TiCl2 Me2 Si(MeC 5 H 3)(NC 12 H 23)TiCl 2 (5.87 g, 0.013 mol).
Compound C: Part 1. Me2SiCl2 (150 ml, 1.24 mol) was diluted with ˜200 ml of ether. Li(C13H9)•Et2O (lithiated fluorene etherate, 28.2 g, 0.11 mol) was slowly added. The reaction was allowed to stir for −1 ˜1 hr prior to removing the solvent via vacuum. Toluene was added and the mixture was filtered through Celite to remove the LiCl. The solvent was removed from the filtrate, leaving behind the off-white solid, Me2Si(C13H9)Cl (25.4 g, 0.096 mol).
Part 2. Me2Si(C13H9)Cl (8.0 g, 0.031 mol) was suspended in ether and THF in a ratio of 5:1. LiHNC6H11 (3.25 g, 0.031 mol) was slowly added. The reaction mixture was allowed to stir overnight. After removal of the solvent via vacuum, toluene was added and the mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume to give a viscous orange liquid. To this liquid which was diluted in ether, 43 ml of 1.4M MeLi (0.060 mol) was added slowly. The mixture was allowed to stir overnight. The solvent was removed via vacuum to produce 13.0 g (0.031 mol) of Li2[Me2Si(C13H8)(NC6H11)]•1.25 Et2O.
Part 3. Li2[Me2Si(C13H8)(NC6H11)]•1.25Et2O (6.5 g, 0.15 0.015 mol) was dissolved in cold ether. TiCl4•2Et2O (5.16 g, 0.017 mol) was slowly added. The mixture was allowed to stir overnight. The solvent was removed via vacuum and methylene chloride was added. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and petroleum ether was added. This was refrigerated to maximize precipitation prior to filtering off the solid. Since the solid collected was not completely soluble in toluene, it was mixed with toluene and filtered to remove the toluene insolubles. The filtrate was reduced in volume and petroleum ether was added to induce precipitation. The mixture was refrigerated prior to filtration. The red-brown solid Me2Si(C13H8)(NC6H11)TiCl2 was isolated (2.3 g, 5.2 mmol).
Compound D: Part 1. Me2Si(C13H9)Cl was prepared as described in Example C for the preparation of compound C, Part 1.
Part 2. Me2Si(C13H9)Cl (8.0 g, 0.031 mol) was diluted in ether. LiHN-t-Bu (2.4 g, 0.030 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed in vacuo and methylene chloride was added to precipitate out the LiCl which was filtered off. The solvent was removed from the filtrate leaving behind an oily yellow liquid identified as Me2Si(C13H9)(NH-t-Bu) (8.8 g, 0.028 mol).
Part 3. Me2Si(C13H9)(NH-t-Bu) (8.8 g, 0.028 mol) was diluted in ether. MeLi (1.4M, 41 ml, 0.057 mol) was slowly added and the reaction was allowed to stir for about two hours. The solvent was removed via vacuum leaving behind an orange solid identified as Li2[Me2Si(C13H8)(N-t-Bu)]•Et2O.
Part 4. Li2[Me2Si(C13H8)(N-t-Bu)]•Et2O (3.0 g, 0.008 mol) was dissolved in ether. ZrCl4 (1.84 g, 0.008 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and methylene chloride was added to precipitate the LiCl which was filtered off. The solvent was reduced in volume and petroleum ether was added to precipitate the product. The mixture was refrigerated to maximize precipitation prior to being filtered. Me2Si(C13H8)(N-t-Bu)(N-t-Bu)ZrCl2 was isolated as a yellow solid (1.9 g, 0.005 mol.) mol). Example E
Compound E: Part 1. Li2[Me2Si(C13H8)(NC6H1-1)•1.25 Et2O was prepared as described in Example C, Part 3 for the preparation of Compound C.
Part 2. Li2[Me2Si(C13H8)(NC6H11)•1.25Et2O (3.25 g, 7.6 mmol) was dissolved in ether. HfCl4 (1.78, 5.6 mmol) was slowly added. The orange mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and methylene chloride was added. The mixture was filtered through Celite to remove LiCl. The filtrate was reduced in volume and petroleum ether was added. This was refrigerated to maximize precipitation prior to filtering off the orange solid. After filtration of the mixture, the product Me2Si(C13H8)(NC6H11)HfCl2 (1.9 g, 3.3 mmol) was isolated.
Compound F: Part 1. Li2[Me2Si(C13H8)(N-t-Bu)]•Et2O was prepared as described in Example D, Part 3 for the preparation of Compound D.
Part 2. Li2[Me2Si(C13H8)(N-t-Bu)]•Et2O (2.8 g, 7.3 mmol was dissolved in ether. HfCl4 (2.35 g, 7.3 mmol) was slowly added and the reaction mixture was allowed to stir over night. The solvent was removed via vacuum and toluene was added. The mixture was filtered through Celite to remove LiCl. The filtrate was reduced in volume and petroleum ether was added. This was refrigerated to maximize precipitation prior to filtering off the pale orange solid. After filtration of the mixture, the product Me2Si(C13H8)(N-t-Bu)HfCl2 (1.9 g, 3.5 mmol) was isolated.
Compound G: Part 1. LiC9H7 (40 g, 0.33 mol, lithiated indene=Li(Hind)) was slowly added to Me2SiCl2 (60 ml, 0.49 mol) in ether and THF. The reaction was allowed to stir for 1.5 hours prior to removing the solvent via vacuum. Petroleum ether was then added, and the LiCl was filtered off. The solvent was removed from the filtrate via vacuum, leaving behind the pale yellow liquid, (Hind)Me2SiCl (55.7 g, 0.27 mol).
partPart 2. (Hind)Me2SiCl (17.8 g, 0.085 mol) was diluted with ether. LiHNC6H11 (9.0 g, 0.086 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether was added. The LiCl was filtered off and the solvent was removed via vacuum to give a viscous yellow liquid. To this liquid which was diluted in ether, 118 ml of 1.4 M MeLi (0.17 mol) was added and the mixture was allowed to stir for two hours. The solvent was removed via vacuum yielding the pale yellow solid, Li2[Me2Si(ind)(NC6H11)]•�Et2O (27.3 g, 0.085 mol).
Part 3. Li2[Me2Si(ind)(NC6H11)]•�Et2O (10.0 g, 0.031 mol) was suspended in ether. A small amount of TiCl4•2Et2O was added and the mixture was stirred for approximately five minutes. The mixture was then cooled to −30� C. before adding the remaining TiCl4•2Et2O (total: 10.5 g, 0.031 mol). The mixture was allowed to stir over night. The solvent was removed via vacuum and methylene chloride was added. The mixture was filtered through Celite and the brown filtrate was reduced in volume. Petroleum ether was added and the mixture was refrigerated to maximize precipitation. A brown solid was filtered off which was mixed in hot toluene and filtered through Celite to remove the toluene insolubles. Petroleum ether was added to the filtrate and the mixture was again refrigerated prior to filtering off the solid. This solid was recrystallized twice; once from ether and petroleum ether and once from toluene and petroleum ether. The last recrystallization isolated the pale brown solid, Me2Si(ind)(NC6H11)TiCl2 (1.7 g, 4.4 mmol).
Compound H: Part 1. Me2Si(MeC5H4)Cl was prepared as described in Example B, Part 1 for the preparation of Compound B.
Part 2. Me2Si(MeC5H4)Cl (11.5 g, 0.067 mol) was diluted with ether. LiHN-2,6-i-PrC6H3 LiHN- 2,6 -i-Pr 2 C 6 H 3 (12.2 g, 0.067 mol) was slowly added. The mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and dichloromethane was added to precipitate the LiCl. The mixture was filtered and the solvent was removed from the filtrate leaving behind the viscous yellow liquid, Me2Si(MeC5H4)(HN-2,6-i-PrC6H3). Me2 Si(MeC 5 H 4)(HN- 2,6 -i-Pr 2 C 6 H 3).Assuming a ˜95% yield, 90 ml of MeLi (1.4 M in ether, 0.126 mol) was slowly added to a solution of Me2Si(MeC5H4)(HN-2,6-i-PrC6H3) in Me2 Si(MeC 5 H 4)(HN- 2,6 -i-Pr 2 C 6 H 3) in ether. This was allowed to stir overnight. The solvent was reduced in volume and the mixture was filtered and the solid collected was washed with aliquots of ether, then vacuum dried. The product, Li2[Me2Si(MeC5H3)(N-2,6-i-PrC6H3)], Li2 [Me 2 Si(MeC 5 H 3)(N- 2,6 -i-Pr 2 C 6 H 3)], was isolated (13.0 g, 0.036 mol).
Part 3. Li 2[Me2Si(MeC5H3)(N-2,6-i-PrC6H3)] Li2 [Me 2 Si(MeC 5 H 3)(N- 2,6 -i-Pr 2 C 6 H 3)](7.0 g, 0.019 mol) was diluted in cold ether. TiCl4•2Et2O (6.6 g, 0.019 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 an orange solid which was recrystallized from dichloromethane and identified as Me2Si(MeC5H3)(N-2,6-i-PrC6H3)TiCl2 Me2(Si(MeC 5 H 3)(N- 2,6 -i-Pr 2 C 6 H 3)TiCl 2 (1.75 g, 4.1 mmol).
Compound I: Part 1. Me2Si(MeC5H4)Cl was prepared as described in Example B, Part 1 for the preparation of compound B.
partPart 2. Me2Si(MeC5H4)Cl (10.0 g, 0.058 mol) was diluted with ether. LiHNC6H11 (6.1 g, 0.058 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and toluene was added to precipitate the LiCl. vacuum The toluene was removed from the filtrate leaving behind a pale yellow liquid, Me2Si(MeC5H4)(HNC6H11). The yield was assumed to be ˜95%. Based on this, two equivalents of MeLi (1.4 M in ether, 0.11 mol, 80 ml) was slowly added to an ether solution of Me2Si(MeC5H4)(HNC6H11). This was stirred for a few hours before removing the solvent and isolating the product, Li2[Me2Si(MeC5H3)(NC6H11)] (12.3 g, 0.050 mol).
Part 3. Li2[Me2Si(MeC5H3)(NC6H11)] (7.25 g, 0.029 mol) was suspended in cold ether. TiCl4.2Et2O TiCl4 •2Et 2 O (9.9 g, 0.029 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 maize colored solid which was recrystallized from dichloromethane and identified as Me2Si(MeC5H3)(NC6H11)TiCl2 (3.25 g, 9.2 mmol).
Compound J: Part 1. Me2Si(MeC5H4)Cl was prepared as described in Example B, Part 1 for the preparation of Compound B.
Part 2. Me2Si(MeC5H4)Cl (10.0 g, 0.059 mol) was diluted with ether. LiHN-2,5-t-Bu2C6H3 (12.2 g, 0.58 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and toluene was added to precipitate the LiCl. The toluene was removed from the filtrate leaving behind a pale yellow liquid, Me2Si(MeC5H4)(HN-2,5-t-Bu2C6H3). The yield was assumed to be ˜95%. Based on this, two equivalents of MeLi (1.4 M in ether, 0.11 mol, 80 ml) was slowly added to an ether solution of Me2Si(MeC5H4)(HN-2,5-t-Bu2C6H3). This was stirred for a few hours before removing the solvent and isolating the product, Li2[Me2Si(MeC5H3)(N-2,5-t-Bu2C6H3)] (7.4 g, 0.021 mol).
Part 3. Li2[Me2Si(MeC5H3)(N-2,5-t-Bu2C6H3)] (6.3 g, 0.018 mol) was suspended in cold ether. TiCl4•2Et2O (6.0 g, 0.18 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 solid which was recrystallized from dichloromethane giving an orange solid identified as Me2Si(MeC5H3)(N-2,5-t-Bu2C6H3)TiCl2 (2.4 g, 5.2 mmol).
Polymerization—Compound A
Using the same reactor design and general procedure already described in copending application U.S. Ser. No. 533,245 already described 533,245, 400 ml of toluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 1.58 mg of compound A (1.0 ml of 15.8 mg of compound a in 10 ml of toluene) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for 30 minutes followed by rapidly cooling and venting the system. The polymer was precipitated out and filtered off giving 0.7 g of crystalline polypropylene (MW=169,500, MWD=1.605, m=0.725, r=0.275, 115 chain defects/1000 monomer units).
Polymerization—Compound B
Polymerization—Compound C
Using the same reactor design and general procedure already described, 100 ml of toluene, 100 ml of propylene, 5 ml of 1.0M MAO, and 2.46 mg of compound C (2 ml of 12.3 mg of compound C in 10 ml of toluene) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for 1 hour, followed by rapidly cooling and venting the system. The polymer was precipitated out and filtered off giving 2.2 g of crystalline polypropylene (MW=29,000, MWD=2.673, m=0.356, r=0.641, 110.5 chain defects/1000 monomer units, mp=143� C.) and a trace amount of amorphous polypropylene which was isolated from the filtrate.
Polymerization—Compound D
Using the same reactor design and general procedure already described, 100 ml of toluene, 200 ml of propylene, 5 ml of 1.0M MAO, and 6.4 mg of compound D (5 ml of 12.4 mg of compound D in 10 ml of toluene) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for one hour, followed by rapidly cooling and venting the system. The polymer was precipitated out and filtered off giving 1.4 g of crystalline polypropylene (MW=76,900, MWD=1.553, m=0.982, r=0.18, 9.1 defects/1000 monomer units, mp=145� C.) and trace amount of amorphous polypropylene which was isolated from the filtrate.
Polymerization—Compound E
Polymerization—Compound F
Using the same reactor design and general procedure already described, 100 ml of hexane, 500 ml of propylene, 10.0 ml of 1.0M MAO, and 3.4 mg of compound F (2.0 ml of 17.0 mg of compound F in 10 ml of toluene) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for 2.5 hours followed by rapidly cooling and venting the system. The polymer was precipitated out and filtered off giving 3.1 g of crystalline polypropylene (MW=70,600, MWD=1.726, m=0.858, r=0.143, 45.2 chain defects/1000 monomer units, mp=144� C.).
Polymerization—Compound G
Using the same reactor design and general procedure already described, 200 ml of toluene, 200 ml of propylene, 5.0 ml of 1.0M MAO, and 5.5 mg of compound G (5.0 ml of 11.0 mg of compound G in 10 ml of toluene) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for 1.0 hour followed by rapidly cooling and venting the system. The polymer was precipitated out and filtered off giving 2.4 g of crystalline polypropylene (MW=71,300, MWD=1.812, m=0.866, r=0.134, 52 chain defects/1000 monomer units, mp=147� C.) and trace amount of amorphous polymer.
Polymerization—Compound H
Using the same reactor design and general procedure already described, 100 ml of toluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 0.86 mg of compound H (1.0 ml of 8.6 mg of compound H in 10 ml of toluene) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for one hour followed by rapidly cooling and venting the system. The polymer was precipitated out and filtered off giving 2.8 g of crystalline polypropylene (MW=170,300, MWD=2.275, m=0.884, r=0.116, 46.5 chain defects/1000 monomer units, mp=151� C.).
Polymerization—Compound I
Using the same reactor design and general procedure already described, 100 ml of toluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 0.70 mg of compound I (1.0 ml of 7.0 mg of compound I in 10 ml of toluene) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for one hour followed by rapidly cooling and venting the system. The polymer was precipitated out and filtered off giving 2.3 g of crystalline polypropylene (MW=145,500, MWD=3.551, m=0.860, r=0.140, 57.1 chain defects/1000 monomer units, mp=151�0 151� C.).
Polymerization—Compound J
Using the same reactor design and general procedure already described, 100 ml of toluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 1.0 mg of compound J 1.0 ( 1.0 ml of 10.0 mg of compound J in 10 ml of toluene) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for one hour followed by rapidly cooling and venting the system. The polymer was precipitated out and filtered off giving 1.4 g of crystalline polypropylene (MW=211,400, MWD=2.734, m=0.750, r=0.250, 97.3 chain defects/1000 monomer units, mp=144� C.).
Component (TMC)
mmole�
3.30 � 10−3 2.5
naa 0.725
2.11 � 10−3 2.5
naa 0.547
5.61 � 10−3 5.0
1.41 � 10−3 5.0
6.26 � 10−3 10.0 1600
1.42 � 10−3 5.0
2.00 � 10−3 2.5
1400 170,300
1.99 � 10−3 2.5
1156 145,500
10 J
2.18 � 10−3 2.5
aData not available. By appropriate selection of (1) Group IVB IV-B transition metal component for use in the catalyst system; (2) the type and amount of alumoxane used; (3) the polymerization diluent type and volume; and (4) reaction temperature, one may tailor the product polymer to the weight average molecular weight value desired while still maintaining the molecular weight distribution at a value below about 4.0.
The stereochemical control of the polymer formed is highly dependent on the exact structure of the transition metal component. Those transition metal components containing zirconium or hafnium (M=Zr or Hf) appear to have greater stereoregularity (fewer chain defects) than these those containing titanium (M=Ti). By appropriate selection of the transition metal component of the catalyst system a wide variety of crystalline poly-α-olefins with differing stereochemical structure are possible.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3258455Jun 6, 1960Jun 28, 1966Montedison SpaPolypropylene having syndiotactic structureUS3305538Nov 20, 1962Feb 21, 1967Montedison SpaPolymerization processUS4522982Jun 6, 1983Jun 11, 1985Exxon Research & Engineering Co.Isotactic-stereoblock polymers of alpha-olefins and process for producing the sameUS4530914Jun 6, 1983Jul 23, 1985Exxon Research & Engineering Co.Process and catalyst for producing polyethylene having a broad molecular weight distributionUS4701432Jun 9, 1986Oct 20, 1987Exxon Chemical Patents Inc.Supported polymerization catalystUS4769510Nov 25, 1985Sep 6, 1988Hoechst AktiengesellschaftProcess for the preparation of polyolefinsUS4794096Sep 11, 1987Dec 27, 1988Fina Technology, Inc.Hafnium metallocene catalyst for the polymerization of olefinsUS4892851Jul 15, 1988Jan 9, 1990Fina Technology, Inc.Process and catalyst for producing syndiotactic polyolefinsEP0406912A2Sep 24, 1987Jan 9, 1991Mitsui Petrochemical Industries, Ltd.Process for polymerizing olefinsWO1987003887A1Dec 25, 1986Jul 2, 1987Mitsui Petrochemical Industries, Ltd.Process for polymerization of alpha-olefinsNon-Patent CitationsReference1A. W. Langer, Jr., "Base Effects on Selected Ziegler-Type Catalysts"; Annals of The New York Academy of Sciences, vol. 295, 110-126; The Place of Transition Metals in Organic Synthesis Conference in November 11-12, 1976.2C. M. Fendrick, et al., "Manipulation of Organoactinide Coordinative Unsaturation and Stereochemistry. Properties of Chelating Bis(polymethylcyclopentiadienyl) Hydrocarbyls and Hydrides"; Organometallics, 3, 819-821; Feb. 1984; Department of Chemistry, Northwestern University, Evanston, Illinois 60201.3F. H. Kohler and K. H. Doll, "NMR Spectroscopy on Paramagnetic Complexes, XXVII[1] Paramagnetic 1, 1', 2, 2', 3, 3', 4, 4'-Octamethylmetallocenes"; 144-150: Z. Naturforsch 37b (1982); Anorganisch-chemisches Institut der Technischen Universitat Munchen, Lichtenbergstrasse 4, D-8046 Garching.4F. R. W. P. Wild, et al., "Synthesis and Molecular Structures of Chiral ansa-Titanocene Derivatives with Bridged Tetrahydroindenyl Ligands"; Journal of Organometallic Chemistry, 232 (1982) 233-247, Printed in The Netherlands; Elsevier Sequoia S. A., Lausanne.5J. A. Ewen, "Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene/Methylalumoxane Catalysts"; 6355-6364, J. Am. Chem. Soc. 1984 106.6J. G. Rooney and G. Ver Strate, "On Line Determination by Light Scattering of Mechanical Degradation in the GPC Process"; 207-235, Liquid Chromatography of Polymers and Related Materials III; Marcel Dekker, Inc., New York and Basel.7Kukenhohner, "Untersuchungen zur Darstellung Chiraler Organotitan (IV)-Verbindungen fur Enantioselektire Synthesen" (1983) (unpublished Diplomarbeit, University of Marburg, Germany).8KukenHohner, Organotitan (IV) Agentien: Komplexe Chiraler Chelatliganden und Enantioselektire c-c- Verkuupfungen (University of Marburg, Germany 1986).9M. Reetz, Organotitanium Reagents in Organic Synthesis, pp. 117 and 121 (Springer-Verlay 1986.10W. Kaminsky, et al., "Polymerization of Propene and Butene with a Chiral Zirconocene and Methylalumoxane as Cocatalyst"; Chem. Int. Ed. Engl. 24 (1985) No. 6, 507-508.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS8664461Mar 19, 2012Mar 4, 2014Exxonmobil Chemical Patents Inc.Catalysts for producing polyalpha-olefins and processes related theretoWO2013141911A1Dec 14, 2012Sep 26, 2013Exxonmobil Chemical Patents Inc.New catalysts for producing polyalpha-olefinsClassifications U.S. Classification526/127, 526/150, 526/160, 526/943, 502/117, 526/161, 502/103, 526/172, 526/132International ClassificationC08F10/06, C08F210/06, C08F4/60, B01J31/18, C08F210/18, C07F7/00, C07F7/10, C08F210/16, C08F110/02, C07F17/00, C08F110/06, C08F4/64, C08F4/6592, C08F4/00, C08F4/659, C08F10/00, C08F4/642Cooperative ClassificationY10S526/943, C08F210/18, C08F10/00, C08F210/06, C07F7/10, C08F4/65908, C07F17/00, C08F110/02, C08F4/65916, C08F10/06, C08F4/6592, C08F4/65912, C08F110/06, C08F210/16European ClassificationC07F17/00, C08F210/16, C07F7/10, C08F10/06, C08F10/00RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services