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US6265338B1 - Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin copolymer production catalysts - Google Patents
Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin copolymer production catalysts Download PDF
US6265338B1
US6265338B1 US08562076 US56207695A US6265338B1 US 6265338 B1 US6265338 B1 US 6265338B1 US 08562076 US08562076 US 08562076 US 56207695 A US56207695 A US 56207695A US 6265338 B1 US6265338 B1 US 6265338B1
US08562076
The invention is a catalyst system including a monocyclopentadienyl titanium compound, where the monocyclopentadienyl group is bonded to a silylene-imido moiety which is further bonded to the titanium atom, and an alumoxane component which 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.
This application is a Continuation-in-Part of U.S. patent application Ser. No. 581,841 filed Sep. 13, 1990, now U.S. Pat. No. 5,096,867 which in turn is a Continuation-in-Part of U.S. patent application Ser. No. 533,245 filed Jun. 4, 1990, now U.S. Pat. No. 5,055,438 which in turn is a Continuation-in-Part of U.S. patent application Ser. No. 406,945 filed Sep. 13, 1989, now abandoned; all are incorporated by reference.
This invention relates to the discovery of various catalyst ligand structure affects which are reflected in the activity of the catalyst system and in the physical and chemical properties possessed by a polymer produced with a monocyclopentadienyl titanium metal catalyst system. Accordingly, various species within the general class of monocyclopentadienyl titanium catalyst as disclosed by commonly-owned U.S. patent application Ser. No. 581,841, now U.S. Pat. No. 5,096,867 have been discovered to be vastly superior in terms of the ability of such species to produce ethylene-α-olefin copolymers of high molecular weight with high levels of α-olefin comonomer incorporation and at high levels of catalyst productivity.
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 system for the production of polyolefins and ethylene-α-olefin copolymers. When such metallocenes are cocatalyzed with an aluminum alkyl—as is the case with a traditional type Ziegler-Natta catalyst system—the catalytic activity of such metallocene catalyst system is generally too low to be of any commercial interest.
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 zirconium species of metallocene 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.
Commonly owned copending U.S. application Ser. No. 581,841, now U.S. Pat. No. 5,096,867 disclosed the discovery of a class of monocyclopentadienyl Group IV B transition metal compounds which, when activated with an alumoxane, may be employed as a catalyst system in solution, slurry or bulk phase polymerization procedure to produce a polyolefin of high weight average molecular weight and relatively narrow molecular weight distribution.
The “Group IV B transition metal component” of the catalyst system disclosed in application Ser. No. 581,841, now U.S. Pat. No. 5,096,867 is represented by the formula:
(C2H5−y−zRx) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, “x” is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen 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 (C5H5−y−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−l−y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur, and each R′ is, independently a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms 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;
“y” is 0 or 1 when w is greater than 0; y is 1 when w is 0; when “y” is 1, T is a covalent bridging group containing a Group IV A or V A element such as, but not limited to, a dialkyl, alkylaryl or diaryl silicon or germanium radical, alkyl or aryl phosphine or amine radical, or a hydrocarbyl radical such as methylene, ethylene and the like;
L is a neutral Lewis base such as diethylether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylainine, and the like; and “w” is a number from 0 to 3. L can also be a second transition metal compound of the same type such that the two metal centers M and M′ are bridged by Q and Q′, wherein M′ has the same meaning as M and Q′ has the same meaning as Q. Such dimeric compounds are represented by the formula:
As further disclosed in U.S. application Ser. No. 581,841, now U.S. Pat. No. 5,096,867 that class 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(cyclopentadienyl) 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, particularly those wherein the heteroatom is nitrogen, generally exhibit greater stability in the presence of aluminum alkyls, higher catalyst activity rates and higher α-olefin comonomer incorporation.
This invention comprises the discovery of a subgenus of monocyclopentadienyl titanium compounds which, by reason of the presence therein of ligands of a particular nature, provide a catalyst of greatly improved performance characteristics compared to other members of the genus of monocyclopentadienyl titanium compounds as described in copending U.S. application Ser. No. 81,844, now U.S. Pat. No. 5,096,867. The subgenus of monocyclopentadienyl titanium catalyst most preferred is that wherein the heteroatom ligand is an amido group, the nitrogen atom of which is bridged through a bridging group (T) to the cyclopentadienyl ring and wherein the nitrogen atom is covalently bonded through a 1° or 2° carbon atom to an alicyclic or aliphatic hydrocarbyl group. Herein a 1° carbon atom is one which is methyl 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 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. Monocyclopentadienyl titanium compounds within this subgenus 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 monocyclopentadienyl titanium compounds when utilized in an otherwise identical catalyst system under identical polymerization conditions. Further, within this subgenus of titanium 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 disclosure of U.S. application Ser. No. 581,641, now U.S. Pat. No. 5,096,867, is hereby incorporated by reference.
As disclosed in U.S. application Ser. No. 581,841, now U.S. Pat. No. 5,096,867, wherein it is desired to produce an α-olefin, copolymer which incorporates a high content of α-olefin, the class of Group IV B transition metal compound preferred is one of titanium. The most preferred class of titanium metal compounds are represented by the formula:
Among this class of titanium compounds 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 atoms, 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 affects of the bridging group ligands R1 and R2 has been found to be of less significance. The nature of the R1 and R2 ligands exerts a small effect upon the activity of a catalyst. For greatest catalyst activity the R1 and R2 ligands are preferably alkyl, most preferably methyl. The Q anionic ligands of the transition metal have not been observed to exert any particular influence on the catalyst or polymer properties, as demonstrated by comparison of Examples 71 and 86. Accordingly, as a convenience in the production of the transitional metal component the Q ligands are preferably chlorine or methyl.
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 chlorine or 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 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 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.
The catalyst system may be conveniently prepared by placing the selected titanium metal component and the selected alumoxane 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.
In a preferred embodiment of the process of this invention the catalyst system is utilized in the liquid phase (slurry, solutions, suspension or bulk phase or combinations thereof), high pressure fluid phase or gas phase polymerization of an olefin monomer. These processes may be employed singularly or in series. The liquid phase process comprises the steps of contacting an ethylene and a α-olefin monomer with the catalyst system in a suitable polymerization diluent and reacting the monomers in the presence of the catalyst system for a time and at a temperature sufficient to produce an ethylene-α-olefin copolymer of high molecular weight.
The monomers for such process comprise ethylene in combinations with an α-olefin having 3 to 20 carbon atoms for the production of an ethylene-α-olefin copolymer. It should be appreciated that the advantages as observed in a ethylene-α-olefin copolymer produced with a catalyst system of this invention would also be expected tog be 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 titanium 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. The aluminum to titanium metal molar ratio is preferably from about 1:1 to 18,000 to 1. A more preferably range would be 1:1 to 2000:1. The reaction time is preferably from about 10 seconds to about 1 hour.
The α-olefin to ethylene molar ratio often bears importantly upon the production capacity of a reactor of any design—i.e., whether for solution or gas phase production, etc.—for production of an ethylene based copolymer (i.e.—a copolymer the molar ratio of which is 50% or greater ethylene). The more ethylene input to a reactor in a given unit of time, the greater will be the amount of ethylene based copolymer product obtained in that same unit of time. Yet, polymers are designed for a variety of end services and this design constraint dictates the molar percentage of incorporated α-olefin which must be obtained in the targeted copolymer product. The “catalyst reactive ratio (r1)” of a catalyst system defines the property of the system of assimilating an ethylene monomer into a polymer molecule chain in preference to a particular α-olefin comonomer. The larger the r1 number, the greater the preference of the catalyst system for incorporating an ethylene monomer rather than a α-olefin monomer. Thus, to achieve a targeted α-olefin monomer incorporation (C60) in the product polymer, the higher the r1 value of a catalyst system, the larger must be the Cα/C2 molar ratio of monomers used in the reactor, and as the Cα/C2 ratio increases the lower is the production capacity of the reactor.
Further, since it is the ratio of Cα/C2 in the medium wherein polymerization occurs which is critical (i.e., liquid phase, gas phase, or super critical fluid phase, etc.) the low r1 values for the catalyst systems of this invention permit the catalyst systems to be used in a wider variety of polymerization procedures than was heretofore believed to be practically possible. Particularly within this range of possibilities is that of the gas phase polymerization of an ethylene α-olefin copolymer of a greater than heretofore believed possible level of α-olefin incorporation.
As before noted, a catalyst system wherein the Group IV B transition metal component is titanium has the ability to incorporate high contents of α-olefin comonomers. Accordingly, the selection of the titanium metal component to have the cyclopentadienyl group to be tetramethyl substituted and to have an amido group bridged through its nitrogen atom to the cyclopentadienyl ring wherein the nitrogen of the amido group is bonded through a 1° or 2° carbon atom to an aliphatic or alicyclic hydrocarbyl group, most preferably an alicyclic hydrocarbyl group is another parameter which may be utilized as a control over the α-olefin content of the ethylene-α-olefin copolymer within a reasonable ratio of ethylene to α-olefin comonomer. For reasons already explained, in the production of an ethylene-α-olefin copolymer a molar ratio of α-olefin to ethylene of 2.0 or less is preferred, and a ratio of 1.6 or less is more preferred.
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.
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. Köhler 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. 58,1,8414 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 monocyclopentadienyl 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 out 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 ˜φml 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, 1.6M) 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 2. (C5Me4H)SiMe2Cl (5.19 g, 0.024 mol) was slowly added to a solution of LiHNC4H11 (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, 1.4M 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)(NC4H11)] 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) (NC4H11)TiCl.
EXAMPLE IT Compound IT
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 (1.4M, 64 ml, 0.090 mol) was slowly added. The mixture was allowed to stir for ½ 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
Part 2. (C5Me4H)SiMe2Cl (8.0 g, 0.037 mol) was slowly added to a suspension of LiHNC12H23 (C12H23=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 ½ 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
To this solution, MeLi (1.4M, 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 4.29 (0.0087 mol) Me2Si(C5Me4)(NC12H25)TiCl2.
EXAMPLE LT Compound LT
Part 2. (C5Me4H)SiMe2Cl (12.0 g, 0.056 mol) was diluted with 300 ml of thf. LiHNC8H15(C8H15=cyclooctyl, 7.42 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 2. (C5Me4H)SiMe2Cl (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 (2.1M, 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 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 (1.4M, 45 Ml, 0.063 mol) to give Li2[Me2Si(C5Me4)(NC6H13)]. The resulting mixture was then cooled to −30° C. TiCl4.2Et2 (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 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 1.4M 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 2. MePhSi(C5Me4H)Cl (6.0 G, 0.022 mol) was diluted with either. 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 (1.4M 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 2.09 (4.6 mmol) of MePhSi(Me4C5)(N-n-Bu)TiCl2.
Part 1. (C5Me4H)SiMe2Cl as 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 3. Me2Si(C5Me4H)(HN-s-Bu) (10.0 g, 0.040 mol) was diluted with ether. MeLi (58 ml, 1.4M in ether, 0.081 mol) was added and the mixture was allowed to stir overnight. The solvent was reduced in volume and the white solid wa filtered off and washed with small portions of ether. Li2[Me2Si(C5Me4)(N-s-Bu)] (10.1 g, 0.038 mol) was isolated after vacuum drying.
EXAMPLE RT Compound RT
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 remote 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. Me Si(C5Me4H (HN-n-Bu) (8.6 g, 0.034 mol) was diluted with ether. MeLi (50 ml, 1.4M 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)].⅓Et2O.
Part 4. Li2[Me2Si(C5Me4)(N-n-Bu)].⅓Et2O (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(MeC5H4Cl.
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 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 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. TiCl4.2Et2 (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 add 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)(HCN12H23) (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).
Me2Si(C5Me4)(NC12H23)TiMe2 was prepared by adding a stoichiometric amount of MeLi (1.4M in ether) to Me2Si(C5Me4)(NC12H23)TiCl2 (Compound JT from Example JT) suspended in ether. The white solid recrystallized from toluene and petroleum ether was isolated in a 57% yield.
EXAMPLE 40 Polymerization—Compound AT
The polymerization run was performed in a 1-liter autoclave reactor equipped with a paddle stirrer, an external water jacked 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 1.0M 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).
EXAMPLE 41 Polymerization—Compound AT
EXAMPLE 42 Polymerization—Compound AT
Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of 1-hexene, 7.0 ml of 1.0M 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 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, 48.6 g of an ethylene-1-hexene copolymer was recovered (MW=98,500, MWD=1.745, 117 SCB/1000 C by 13C NMR).
EXAMPLE 43 Polymerization—Compound AT
Using the same reactor design and general procedure described in Example 40, 375 ml of toluene, 25 ml of 1-hexene, 7.021 of 1.0M 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/1000 C by 13C NMR).
EXAMPLE 44 Polymerization—Compound AT
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 1.0M 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/1000 C by 13C NMR).
EXAMPLE 45 Polymerization—Compound AT
Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of propylene, 7.0 ml of 1.0M MAO, and 2.06 mg of compound AT (2.0 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, 46.0 g of an ethylene-propylene copolymer was recovered (MW=110,200, MWD=5.489, 20 wt % ethylene by IR).
EXAMPLE 46 Polymerization—Compound AT
Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1.0M 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, 35.1 g of an ethylene-1-butene copolymer was recovered (MW=94,400, MWD=2.405, 165 SCB/1000 C by 13C NMR).
EXAMPLE 47 Polymerization—Compound AT
Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of 1-octene, 7.0 ml of 1.0M MAO, and 1.04 mg of compound AT (1.0 ml of a 10.4 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, 30.6 g of an ethylene-1-octene copolymer was recovered (MW=73,100, MWD=2.552, 77.7 SCB/1000 C by 13C NMR).
EXAMPLE 53 Polymerization—Compound AT
EXAMPLE 54 Polymerization—Compound AT
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 1-butene to ethylene 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-1butene copolymer which had a weight average molecular weight of 50,200, a molecular weight distribution of 2.36 and 60.1 SCB/1000 C as measured by 13C NMR.
EXAMPLE 55 Polymerization—Compound AT
Using the same reactor design as described in Example 54, and using a molar ratio of propylene to ethylene 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 a density of 0.863 g/cc.
EXAMPLE 56 Polymerization—Compound FT
Using the same reactor design as described in Example 54, and using a molar ratio of 1-butene to ethylene 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/1000 C by 13C NMR.
EXAMPLE 58 Polymerization—Compound AT
Using the same reactor design as described in Example 54, and using a molar ratio of 1-butene to ethylene 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 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.7 kg/hr of an ethylene-1butene copolymer which had a weight average molecular weight of 69,500, a molecular weight distribution of 2.049 and 35.7 SCB/1000 C by 13C NMR.
EXAMPLE 67 Polymerization—Compound IT
Using the same reactor design as described in Example 54, and using a molar ratio of 1-butene to ethylene 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 50,800, a molecular weight distribution of 2.467 and 69 SCB/1000 C as measured by 1H NMR.
EXAMPLE 70 Polymerization—Compound JT
Using the same reactor design as described in Example 54, and using a molar ratio of 1-butene to ethylene 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 thus 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/1000 C 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 the 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 for all examples. The reactor contents were stirred at 1000 rpm and a reactor mass flow rate of 40 kg/hr 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 minutes at 190° C.), weight percent comonomer (determined by 1H NMR or 13C NMR), and catalyst reactivity ratios (r1) are collected in Table 1.
Total Feed Production TMC Catalyst
Ex. TMC MAO Vol TMC MAO Rate Rate Productivity Productivity
# (g) (L) (L) (g/L) (g/L) (L/hr) (kg/hr) Al/M (kg/g) (kg/g)
JT 71 0.540 0.4 10 0.0540 10.4 1.75 5.1 1595 54 0.28
KT 72 2.259 1.8 6 0.3765 78.3 0.51 3.9 1723 20 0.10
LT 73 1.480 1.2 8 0.1850 39.2 0.46 4.0 1541 48 0.22
MT 74 1.366 1.0 6 0.2277 43.5 0.58 4.0 1398 31 0.16
FT 75 0.859 0.6 5.3 0.1620 29.5 1.14 4.2 1239 23 0.12
WT 76 1.441 1.2 8 0.1801 39.2 1.51 4.4 1485 16 0.07
AT 77 0.888 0.7 5 0.1776 35.0 0.56 4.35 1461 44 0.22
OT 78 1.934 1.3 6 0.3223 54.4 0.62 4.3 1252 22 0.13
PT 79 1.900 1.3 6 0.3167 54.4 0.96 3.75 1274 12 0.07
IT 80 0.878 0.8 10 0.0878 19.6 0.84 4.3 1416 59 0.26
QT 81 0.953 0.9 10 0.0953 23.5 1.32 4.9 1565 39 0.16
RT 82 0.885 0.9 10 0.0885 23.5 1.68 4.65 1685 31 0.12
JT 83 1.494 0.5 10 0.1494 13.1 1.02 3.9 721 26 0.29
ST 84 3.053 1.0 12 0.2540 21.8 0.51 2.9 643 22 0.26
TT 85 3.043 1.0 18 0.1690 14.5 1.11 2.6 708 14 0.16
UT 86 1.566 1.0 5 0.3132 52.2 0.35 5.0 1258 46 0.27
Ex. Wt %
# MW MWD MI C4 Method r1
JT 71 63,600 2.363 11.3 42.0 1HNMR 4.4
KT 72 84,100 4.775 3.3 40.8 1HNMR 4.7
LT 73 72,700 3.610 7.9 42.0 1HNMR 4.4
MT 74 78,300 4.601 5.0 40.8 1HNMR 4.7
FT 75 61,400 2.607 13.2 41.9 13CNMR 4.4
WT 76 85,400 3.971 3.6 44.0 1HNMR 4.1
AT 77 50,200 2.360 19 24.0 13CNMR 10
OT 78 64,600 2.494 8.1 43.6 13CNMR 4.1
PT 79 71,200 2.259 3.8 41.1 13CNMR 4.6
IT 80 63,600 2.751 6.6 32.4 1HNMR 6.7
QT 81 64,500 2.342 10 42.8 1HNMR 4.3
RT 82 71,100 2.262 8.8 40.0 1HNMR 4.8
JT 83 78,200 2.617 5.2 30.8 1HNMR 4.6
ST 84 60,500 2.183 8.5 17.62 13CNMR 15.0
TT 85 53,900 2.308 13.8 17.38 13CNMR 15.2
UT 86 70,200 2.441 4.6 46.4 13CNMR 3.7
the nature of the R′ group dramatically influence the catalyst 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.
(A) a transition metal component of the formula
wherein R1 and R2 are each independently a hydrocarbyl radical, each Q and Q′ is independently a halide or a C1-C20 hydrocarbyl radical, provided neither Q nor Q′ is a substituted or unsubstituted cyclopentadienyl ring, R′ is an aliphatic or alicyclic hydrocarbyl radical of the formula (CnH2n+b) wherein “n” is a number from 3 to 20 and “b” is +1 for aliphatic and −1 for alicyclic ligands, 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 each R is, independently a C1-4 hydrocarbyl radical or hydrogen, x is 0, 1, 2, 3 or 4, and two adjacent R groups may join to form a C4-10 ring; and
2. The catalyst of claim 1, wherein R1 and R2 are each independently a C1 to C6 hydrocarbyl radical.
3. The catalyst of claim 2, wherein R′ is an alicyclic hydrocarbyl radical.
4. The catalyst of claim 3, wherein R′ is cyclododecyl.
5. The catalyst of claim 4, wherein R1 and R2 are methyl.
6. The catalyst of claim 5, wherein each Q and Q′ is chloride or methyl.
7. A catalyst comprising:
wherein R1 and R2 are each independently a hydrocarbyl radical, each Q and Q′ is independently a halide or a C1-C20 hydrocarbyl radical, provided neither Q nor Q′ is a substituted or unsubstituted cyclopentadienyl ring, R′ is an aliphatic or alicyclic hydrocarbyl radical of the formula (CnH2n+b) wherein “n” is a number from 3 to 20 and “b” is +1 for aliphatic and −1 for alicyclic ligands, 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
8. The catalyst of claim 7, wherein R′ is cyclododecyl.
9. The catalyst of claim 8, wherein R1 and R2 are methyl.
10. The catalyst of claim 9, wherein each Q and Q′ is chloride or methyl.
US08562076 1989-09-13 1995-11-22 Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin copolymer production catalysts Expired - Lifetime US6265338B1 (en)
US08562076 US6265338B1 (en) 1989-09-13 1995-11-22 Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin copolymer production catalysts
US6265338B1 true US6265338B1 (en) 2001-07-24
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US08562076 Expired - Lifetime US6265338B1 (en) 1989-09-13 1995-11-22 Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin copolymer production catalysts
US (1) US6265338B1 (en)
US5489659A (en) * 1993-02-19 1996-02-06 Mitsubishi Chemical Corporation Catalyst component for use in the polymerization of α-olefins and process for producing α-olefin polymers using the same