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Patent USRE37788 - Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsDescribed are certain mono(cyclopentadienyl) Group IV B metal compounds, catalyst systems comprising such mono(cyclopentadienyl) metal compounds and an activator, and to a process using such catalyst systems for the production of polyolefins, particularly ethylene-α-olefin copolymers having a high molecular...http://www.google.com/patents/USRE37788?utm_source=gb-gplus-sharePatent USRE37788 - Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalystsAdvanced Patent SearchPublication numberUSRE37788 E1Publication typeGrantApplication numberUS 09/141,176Publication dateJul 9, 2002Filing dateAug 27, 1998Priority dateJan 30, 1987Publication number09141176, 141176, US RE37788 E1, US RE37788E1, US-E1-RE37788, USRE37788 E1, USRE37788E1InventorsJo Ann M. CanichOriginal AssigneeExxon Chemical Patents, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (19), Non-Patent Citations (14), Referenced by (7), Classifications (41), Legal Events (1) External Links: USPTO, USPTO Assignment, EspacenetMonocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalystsUS RE37788 E1Abstract Described are certain mono(cyclopentadienyl) Group IV B metal compounds, catalyst systems comprising such mono(cyclopentadienyl) metal compounds and an activator, and to a process using such catalyst systems for the production of polyolefins, particularly ethylene-α-olefin copolymers having a high molecular weight and high level of α-olefin incorporation.
M is Zr, Hf or Ti; (C5H4-xRx) is a cyclopentadienyl ring which is substituted with from zero to four substituent groups R, �x� is 0, 1, 2, 3, or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, and alkoxy radical, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group IV A of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C5H4-xRx) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; R′ is a radical selected from C1C3-C20 aliphatic and alicyclic hydrocarbyl radicals wherein one or more hydrogen atoms may be replaced by radicals selected from halogen, amido, phosphido, alkoxy or any other radical containing a Lewis acidic or basic functionality, with the proviso that R′ is convalently bonded to the nitrogen atom through a 1� or 2� carbon atom; each Q may be independently an univalent anionic ligand, or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand with the proviso that where any Q is a hydrocarbyl such Q is not a substituted or unsubstituted cyclopentadienyl radical; T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base; and �w� is a number from 0 to 3. 2. A compound of the formula: wherein:
M represents Ti, Hf or Zr; (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, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group IV A of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C5H4-xRx) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; each of R1 and R2 are independently selected from C1-C20 hydrocarboyl radicals; each Q is independently selected from halide, hydride, substituted or unsubstituted C1-C20 hydrocarbyl radical, alkoxide, aryloxide, amide and phosphide radicals with the proviso that Q is not a substituted or unsubstituted cyclopentadienyl radical; R′ is selected from C1C3 -C20 aliphatic and alicyclic hydrocarbyl radicals with the proviso that R′ is covalently bonded to the nitrogen atom through a 1� or 2� carbon atom; L is a neutral Lewis base; and �w� is a number from 0 to 3. 3. The compound of claim 2 wherein M is Ti.
6. A compound of the formula: M is Zr, Hr or Ti in its highest formal oxidation state (+4, do 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, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group IV of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals; alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C5H4-xRx) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; R′ is a radical selected from C1C3-C20 aliphatic and alicyclic hydrocarbyl radicals wherein one or more hydrogen atoms may be replaced by radicals selected from halogen, amido phosphido, alkoxy or any other radical containing a Lewis acidic or basic functionality, with the proviso that R′ is covalently bonded to the nitrogen atom through a 1� or 2� carbon atom; each Q may be independently an univalent anionic ligand selected from a halide, hydride, or substituted or unsubstituted C1-C20 hydrocarbyl, alkoxide, aryloxide, amide, phosphide, or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand with the proviso that where any Q is a hydrocarbyl such Q is not a substituted or unsubstituted cyclopentadienyl radical,; �w� is a number from 0 to 3; T is selected from radicals of the formula (CR3R4) wherein R3 and R4 are independently selected from hydrogen and C1-C20 hydrocarbyl radicals; and y is 1 or 2. 7. The compound of claim 6 wherein M is Ti.
M is Ti and R3 and R4 are selected from hydrogen, C1-C6 alkyl radicals and C6-C12 aryl radicals. 9. A compound 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, R′ is an aliphatic or alicyclic hydrocarbyl radical having from 1 3to 20 carbon atoms and R′ is covalently bonded to the nitrogen atom through a 1� or 2� carbon atom, L is a neutral Lewis base where �w� denotes a number from 0 to 3 and each R is, independently a C1-C4 hydrocarbyl radical or hydrogen, x is 0, 1, 2, 3 or 4, or two adjacent R groups may join to form a C4-C10 ring.
10. The compound of claim 9, having the formula: wherein R1 and R2 are each independently a hydrocarbyl radical, each Q and Q′ is independently a halide or alkyl radical, R′ is an aliphatic or alicyclic hydrocarbyl radical of from 1 3to 20 carbon atoms and R′ is covalently bonded to the nitrogen atom through a 1� or 2� carbon atom, and L is a neutral Lewis base where �w� denotes a number from 0 to 3.
More recently a catalyst system has been developed wherein the transition metal compound has two or more cyclopentadienyl ring ligands�such transition metal compound being referred to as a metallocene�which catalyzes the production of olefin monomers to polyolefins. Accordingly, metallocene compounds of a Group IV B metal, particularly, titanocenes and zirconocenes, have been utilized as the transition metal component in such �metallocene� containing catalyst systems for the production of polyolefins and ethylene-α-olefin copolymers. When such metallocenes are cocatalyzed with an aluminum alkyl�as is the case with a traditional type Ziegler Natta catalyst system�the catalytic activity of such metallocene catalyst system is generally too low to be of any commercial interest.
The zirconium metallocene species, as cocatalyzed or activated with an alumoxane, are commonly more active than their hafnium or titanium analogues for the polymerization of ethylene alone or together with an α-olefin comonomer. When employed in a non-supported form�i.e., as a homogeneous or soluble catalyst system�to obtain a satisfactory rate of productivity even with the most active zirconocene species typically requires the use of a quantity of alumoxane activator sufficient to provide an aluminum atom to transition metal atom ratio (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 zirconocene or hafnocene species may be used. Titanocene species are generally unstable at such high pressure unless deposited upon a catalyst support.
(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 g, is, independently, a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, and alkoxy radical or any other radical containing a Lewis acidic or basic functionality, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements, halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C5H4-xRx) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
Mono(cyclopentadienyl) metal compounds of the present invention have been discovered to produce a highly productive catalyst system which produces an ethylene-α-olefin copolymer of significantly greater molecular weight and α-olefin comonomer content as compared with other species of mono(cyclopentadienyl) metal compounds when utilized in an otherwise identical catalyst system under identical polymerization conditions. Further, within this subgenus of metal compounds it has been found that the nature and degree of substitution groups (R) of the cyclopentadienyl ring can be varied to produce a catalyst system having a �catalyst reactivity ratio (r1)� which may be varied from a high to low value as may be most desired to best suit the catalyst system to a particular type of polymerization process. Particularly it has been found that as the number of substituents (R), which are preferably hydrocarbyl substituents increases, the reactivity ratio (r1) decreases, the lowest reactivity ratios being obtained by a titanium compound having a tetrahydrocarbyl substituted cyclopentadienyl group, preferably a tetramethylcyclopentadienyl group.
The most preferred class of cyclopentadienyl metal compounds are represented by the formula: wherein Q, L, R′, R, �x� and �w� are as previously defined and R1 and R2 are each independently selected from C1 to C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom; R1 and R2 may also be joined forming a C3 and C20 ring which incorporates the silicon bridge.
The compounds most preferred for reasons of their high catalyst activity in combination with an ability to produce high molecular weight ethylene-α-olefin copolymers of high comonomer content is represented by the formula wherein R1 and R2 are each independently a C1 to C3 hydrocarbyl radical, each Q is independently a halide or alkyl radical, R′ is an aliphatic or an alicyclic hydrocarbyl radical of the formula (CnH2+b) wherein �n� is a number from 3 to 20 and �b� is +1 in which case the ligand is aliphatic or −1 in which case the ligand is alicyclic. Of these compounds, the most preferred is that compound wherein R1 and R2 are methyl, each Q is methyl, n is 12, and the hydrocarbyl radical is alicyclic (i.e., b is −1). Most preferred is that compound wherein the CnH2n−1 hydrocarbyl radical is a cyclododecyl group. Hereafter this compound is referred to for convenience as Me2Si(C5Me4) (NC12H23)TiQ2.
The alumoxane component is an oligomeric compound which may be represented by the general formula (R3�Al�O)m which is a cyclic compound, or may be R4(R5�Al�O�)m�AlR6 2 which is a linear compound. An alumoxane is generally a mixture of both the linear and cyclic compounds. In the general alumoxane formula R3, R4, R5 and R6 are, independently a C1-5 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.
Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in �100 ml of thf. MePhSi(C5Me4H)Cl (15.0 g, 0.054 mol) was added dropwise. The yellow solution was allowed to stir overnight. The solvent was removed in vacuo. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite, and the filtrate was evaporated. MePhSi(C5Me4H)(NH-t-Bu) (16.6 g, 0.053 mol) (was recovered as an extremely viscous liquid.
Part 3. MePhSi)(C5Me4H) (NH-t-Bu) (17.2 g, 0.055 mol) was diluted with �20 ml of ether. n-BuLi (60 ml in hexane, 0.096 mol, 1.6 M) was slowly added and the reaction mixture was allowed to stir for �3 hours. The solvent was removed in vacuo to yield 15.5 g (0.48 mol) of a pale tan solid formulated as Li2[MePhSi(C5Me4) (N-t-Bu)].
Part 4. Li2[MePhSi(C5Me4)(N-t-Bu)] (8.75 g, 0.027 mol) was suspended in �125 ml of cold ether (−30� C.). TiCl4.2Et2O (9.1 g, 0.027 mol) was slowly added. The reaction was allowed to stir for several hours prior to removing the ether via vacuum. A mixture of toluene and dichloromethane was then added to solubilize the product. The mixture was filtered through Celite to remove the LiCl. The solvent was largely removed via vacuum and petroleum ether was added. The mixture was cooled to maximize product precipitation. The crude product was filtered off and redissolved in toluene. The toluene insolubles were filtered off. The toluene was then reduced in volume and petroleum ether was added. The mixture was cooled to maximize precipitation prior to filtering off 3.34 g (7.76 mmol) of the yellow solid MePhSi(C5Me4)(N-t-Bu)TiCl2.
Part 2. (C5Me4H)SiMe2Cl (5.19 g, 0.029 mol) was slowly added to a solution of LiHNC6H11 (2.52 g, 0.024 mol) in �125 ml of thf. The solution was allowed to stir for several hours. The thf was removed via vacuum and petroleum ether was added to precipitate the LiCl which was filtered off. The solvent was removed from the filtrate via vacuum yielding 6.3 g (0.023 mol) of the yellow liquid, Me2Si(C5Me4H) (HNC6H11).
Part 4. Li2[Me2Si(C5Me4)(NC6H11)] (2.57 g, 8.90 mmol) was suspended in �50 ml of cold ether. TiCl4.2Et2O (3.0 g, 8.9 mmol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and dichloromethane was added. The mixture was filtered through Celite to remove the LiCl byproduct. The solvent was removed from the filtrate and a small portion of toluene was added followed by petroleum ether. The mixture was chilled in order to maximize precipitation. A brown solid was filtered off which was initially dissolved in hot toluene, filtered through Celite, and reduced in volume. Petroleum ether was then added. After refrigeration, an olive green solid was filtered off. This solid was recrystallized twice from dichloromethane and petroleum ether to give a final yield of 0.94 g (2.4 mmol) of the pale olive green solid, Me2Si(C5Me4) (NC6H11)TiCl. Me2 Si(C 5 Me 4) (NC 6 H 11)TiCl 2 . 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 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)(NHC2H23) (11.8 g, 0.033 mol) was isolated as a pale yellow liquid.
Part 3. Me2Si(C5Me4H)(NHC12H23) (11.9 g, 0.033 mol) was diluted with �150 ml of ether. MeLi (1.4 M, 47 ml, 0,066 mol) was slowly added. The mixture was allowed to stir for 2 hours after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me2Si(C5Me4)(NC12H23)]Li2, was washed with several small portions of ether, then vacuum dried to yield 11.1 g (0,030 mol) of product.
Part 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).
EXAMPLES 71-86 Each of the compounds of Examples KT through TT were used to prepare an ethylene-1-butene copolymer. The polymerization reactions were carried out in the same reactor design as described in Example 54. With the sole exception of Example 83, all All polymerizations were carried out using a molar ratio of 1-butene to ethylene of 1.6 without the addition of a solvent. In Example 83 a 1-butene to ethylene ratio of 2.0 was used. The temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C.
EXAMPLE AT An ionic catalyst was prepared and utilized substantially as described in Example AS except that dimethylsilyl(N-t-butylamido)tetramethylcyclopentadienyltitanium dimethyl was substituted for dimethylsilyl(cyclododecylamido) tetramethylcyclopentadienyltitanium dimethyl.
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Identical oppositions have been filed in Interference Nos. 102,954 (Paper No. 495), 102,955 (Paper No. 488), 103,067 (Paper No. 358) and 103,819 (Paper No. 116).2 *Chemical Abstracts, vol. 117, No. 12, Abstract No. 112121, 1992.*3 *Chemical Abstracts, vol. 123, No. 16, Abstract No. 199423, 1995.*4Decision of APJ Downey on Stevens et al. Motion No. 57 (Paper No. 535).5Decision of APJ Downey on Stevens Oral Request for Reconsideration of her Decision in Paper No. 535 (Paper No. 363 [sic-536]).6Decision of APJ Downey on Stevens Oral Request for Reconsideration of her Decision in Paper No. 535 (Paper No. 363 [sic�536]).7 *K�kenhohner, "Organotitan (IV) Agentien: Komplexe Chiraler Chelatliganden und Enantioselektire c-c-Verknuptungen" (University of Marburg, Germany), 1986.8 *K�kenhohner, "Untersuchugen zur Darstellung Chiraler Organotitan(IV)-Vebindungen fur Enantioselektire Synthesen",(unbublished Diplomarbeit, University of Marburg, Germany), 1983.*9 *M. Reetz, Organotitanium Reagents in Organic Synthesis, pp. 117 and 121 (Springer-Verlay), 1986.*10Stevens et al. Motion No. 57 to Restore Jurisdiction to the ex parte Examiner in Interference No. 102,953 (Paper No. 526) and appended 37 C.F. R. � 1.607 Request For Interference with Pat. No. 5,621,126. Identical motions have been filed in Interference Nos. 102,954 (Paper No. 490), 102,955 (Paper No. 483), 103,067 (Paper No. 353) and 103,819 (Paper No. 103).11Stevens et al.'s 37 C.F.R. � 1.607 Request For Interference with Pat. No. 5,621,126 and reissue application Ser. No. 09/141,176.12Stevens et al.'s C.F.R. � 1.607 Request For Interference with Pat. No. 5,631,391 and 5,621,126, and reissue application Ser. Nos. 09/141,478 and 09/141,176.13Stevens Repy No. 57 (Paper No. 534). Identical replies have been filed in Interference Nos. 102,954 (Paper No. 498), 102,955 (Paper No. 491), 103,067 (Paper No. 361) and 103,819 (Paper No. 126).14 *US 5,168,111, 12/1992, Canich (withdrawn)** Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS7041841 *Nov 9, 1992May 9, 2006Exxonmobil Chemical Patents Inc.Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst systemUS7569646 *Jul 11, 1991Aug 4, 2009Exxonmobil Chemical Patents Inc.Group IVB transition metal compoundsUS8309501Apr 16, 2010Nov 13, 2012Exxonmobil Chemical Patents Inc.Ethylene-based copolymers, lubricating oil compositions containing the same, and methods for making themUS8378042Sep 29, 2009Feb 19, 2013Exxonmobil Chemical Patents Inc.Finishing process for amorphous polymersUS8389452Apr 16, 2010Mar 5, 2013Exxonmobil Chemical Patents Inc.Polymeric compositions useful as rheology modifiers and methods for making such compositionsUS8618033Jan 12, 2011Dec 31, 2013Exxonmobil Chemical Patents Inc.Ethylene copolymers, methods for their production, and useWO2011094057A1Jan 11, 2011Aug 4, 2011Exxonmobil Chemical Patents Inc.Copolymers, compositions thereof, and methods for making them* Cited by examinerClassifications U.S. Classification556/9, 556/12, 556/56, 556/54, 526/943, 556/52, 502/152, 502/117, 526/160, 502/103, 556/11International ClassificationC08F210/16, C08F210/18, C08F110/02, C07F17/00, C08F110/06, C08F10/06, C08F4/659, C08F4/64, C08F4/6592, C08F10/00, C07F7/10, C08F210/06Cooperative ClassificationC08F4/65922, C08F4/65912, C08F210/18, C08F210/06, C08F110/06, C08F10/00, C08F4/6592, C07F17/00, C08F4/65908, C08F210/16, C07F7/10, C08F110/02, C08F10/06European ClassificationC08F10/06, C08F10/00, C07F17/00, C07F7/10, C08F210/16Legal EventsDateCodeEventDescriptionDec 30, 2008CCCertificate of correctionRotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google