text:
|Numéro de publication
|Type de publication
|Numéro de demande
|Date de publication
|25 mai 1999
|Date de dépôt
|26 mars 1998
|Date de priorité
|20 oct. 1995
|État de paiement des frais
|Autre référence de publication
|Numéro de publication
|Howard William Turner, Charles Stanley Speed, Bernard Jean Folie, Donna Jean Crowther, George Alan Vaughan, Richard Allen Fisher, John Flexer Walzer, Jr.
|Cessionnaire d'origine
|Exxon Chemical Patents Inc.
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|BiBTeX, EndNote, RefMan
|Citations de brevets (20), Citations hors brevets (4), Référencé par (75), Classifications (27), Événements juridiques (4)
|Liens externes: USPTO, Cession USPTO, Espacenet
This application is a continuing application of U.S. Ser. No. 08/769,191, filed Dec, 18, 1996, now U.S. Pat. No. 5,767,208, issued Jun. 16, 1998 which is a continuation-in-part of U.S. Ser. No. 08/545,973, filed Oct. 20, 1995, now abandoned, and is a conversion of a Provisional Application Number 60/008,893 filed Dec. 19, 1995.
This invention relates to catalyst system selection and high temperature process conditions for polymerization of monomers containing ethylenic or acetylenic unsaturation wherein the catalyst system is single-sited and comprises a transition metal cation and a stabilizing, compatible non-coordinating anion.
Ionic catalyst systems for olefin polymerization based on transition metal compounds such as metallocene compounds are recent but now well-known. Such metallocene compounds are based on transition metals capable of supporting at least one pi-bound aromatic ligand, typically a cyclopentadienyl or substituted cyclopentadienyl ligand and at least one additional ligand which can be abstracted so as to form a catalytically active cation structure. Co-catalyst anions are needed to stabilize these cations, which are highly reactive, but those anions must be capable of doing so without either closely coordinating with the cation that its reactivity, and thus polymerization activity, is diminished, or transferring an anionic fragment to the cation so as to alter its polymerization capability. Single coordination complexes and multi-nuclear coordination complexes based on the Group IIIA or 13 elements, such as boron or aluminum, have shown particular suitability as effective co-catalyst anion sources. See, the disclosures in EP-A-0 277 003, EP-A-0 277 004 and their equivalents, U.S. Pat. Nos. 5,198,401 and 5,278,119, particularly Examples 27 and 32. Example 32 of '119 discloses the use of bis(trimethylsilylcyclopentadienyl) hafnium dimethyl as the metallocene compound. Example 27 of '401 lists dimethylsilylbis (indenyl) zirconium dimethyl in column 9, line 16.
Homogeneous processes such as high pressure, high temperature polymerization processes, such as those at 500 bar and above, have shown particular suitability with such catalyst systems since these systems exhibit greater stability than those using alumoxanes co-catalysts at 160° C. and above. This allows for the greater productivity that occurs with greater reactivities at high temperature, the high pressure maintaining an essentially single phase reaction medium while permitting the higher temperatures. See U.S. Pat. No. 5,408,017 and equivalent WO-A-93/05732. A generic, broad description of suitable metallocene compounds is given as is a generic description of suitable anion precursors. The examples include the metallocene compounds dimethylsilylbis (4,5,6,7 tetrahydro-indenyl) zirconium dimethyl and dimethylsilylbis (4,5,6,7 tetrahydro-indenyl) hafnium dimethyl. The former showed significantly higher catalyst productivity (expressed as kg-PE/g-activator) in Table 2, ranging from 100 to 160, while that of the hafnium compound exhibited only 60. A similar olefin polymerization process that can be operated at high temperature and pressure is disclosed in WO 95/07941. The principal problem addressed is build up of polar material in recycle streams of the reactor, the solution is the use of bulky scavengers, e.g., those having at least one tertiary carbon atom, such as triisobutyl alumoxane. Me2 Si(Ind)2 Hf Me2 is shown in Comparative Example 3 and Example 4, and said to be active longer and illustrative of high conversions.
The selection of substituents on the pi-bound, cyclopentadienyl ligands in the metallocene compounds has been identified as a means of increasing performance in olefin polymerization processes. For example, see U.S. Pat. No. 5,304,614 where specifically substituted indenyl ligands and their methods of preparation are described. Very high molecular weight polyethylene at high activity is said to be possible by use of the described metallocene compounds based on any of the group IVB, Vb or VIb metals. Zirconium and hafnium are said to be preferred and the preferred substituent structure is characterized by 1) alkylene or silylene groups bridging two cyclopentadienyl ligands bound to the metal atoms and 2) 4,7-substituted benzo groups fused on the respective sides opposite the H- or C2 to C4 2-substituent on those same cyclopentadienyl groups. Examples 14-18 are of homopolymer polyethylene using specifically substituted bis(indenyl)zirconocenes with an alumoxane co-catalyst at a temperature of 70° C. and ethylene pressure of 5 bar. Productivity ranged from 35 to 56 g PE for 1 hour of polymerization reaction. The highest production was reported for Me2 Si (3,4,7-Me3 Ind)3 Zr Cl2.
In EP-A1-0 612 768, bridged and unbridged hafnium metallocene compounds stabilized by non-coordinating anions after activated with alkyl-aluminum co-catalysts are said to demonstrate high catalyst activity over the zirconium analogues when utilized in processes at temperatures at or exceeding 120° C. The medium pressure solution processes are preferably to be conducted at pressures of 500 to 3500 kg/cm2. All listed hafnocenes are dichloride-substituted embodiments and each of the working examples of the invention is alkylene bridged, with cyclopentadienyl, indenyl or fluorenyl pi-bound ligands.
Catalyst systems based on monocyclopentadienyl titanium compounds activated with alumoxane suitable for the preparation of ethylene-α-olefin copolymers of high molecular weight and high a-olefin content are described in U.S. Pat. No. 5,264,405. This patent teaches that the cyclopentadienyl group should be fully substituted with methyl groups and bridged to an amido group having an aliphatic or alicyclic hydrocarbyl ligand bonded through a 1° or 2° carbon. Copolymerization of ethylene with propylene in Example 45 with a bridged monocyclopentadienyl Group 4 metal catalyst compound at 80° C. produced a copolymer with 20 wt. % ethylene having an Mn of about 20,080. In each Example 55 with the same catalyst as with Example 45, at a reaction temperature of 140° C., an ethylene-propylene copolymer having a density of 0.863, indicative of an amorphous ethylene copolymer, exhibited an Mn of about 46,500.
Due to the sensitivities of ionic catalyst systems to polar impurities, solution polymerization processes utilizing scavenging compounds, for example alkyl aluminum compounds or alkyl alumoxanes, have been described. See, for example, U.S. Pat. Nos. 5,153,157 and 5,241,025, describing Group-IIIA metal scavenger compounds and processes. WO-A-94/07927 addresses a similar process as adapted for monocyclopentadienyl catalyst systems, it describes advantages of bulky scavengers when the monocyclopentadienyl catalyst compounds do not contain bulky substituents to impede interaction with the scavenging compounds. Triisoprenyl aluminum is exemplified and triisobutyl aluminum is listed along with tri-n-octyl and tri-n-hexyl aluminum as suitable bulky scavengers.
In view of the breadth of the disclosures concerning the use of metallocenes for olefin polymerization, and the general industrial need to employ the most effective catalysts and processes so as to have increased productivities while maintaining both comonomer incorporation and high molecular weight polymer preparation capability, additional investigative efforts were required. In particular general knowledge based on observations in the field gave rise to the traditional understanding that under temperatures exceeding about 80° C. increased comonomer incorporation using metallocene catalysts resulted in lower molecular weight polymer.
Invention Disclosure
It has been discovered in resulting investigations that even when subjected to the demanding conditions of high temperature in solution and high pressure processes, high molecular weight ethylene copolymers (M.I.≦10, preferably, M.I.≦1) can be polymerized in the presence of stable, single-sited discrete ionic catalyst systems, for example, those having cations derived from the transition metal compound group consisting of 1) bridged, unsubstituted- or substituted-indenyl, or fluorenyl group containing, hafnium compounds; 2) bridged hetero-atom containing, substituted or unsubstituted monocyclopentadienyl titanium compounds; 3) unbridged, bulky Group 15 containing, bulky monocyclopentadienyl titanium compounds; 4) Group 4 or 5 compounds containing bulky chelating diamide ancillary ligands; and 5) Group 8 metal diimine compounds wherein the metal is in a +2 oxidation state, such as Pd(II) and Ni(II). Accordingly the invention is in part a process for copolymerizing ethylene and at least one higher olefin, that is C3 to C20, preferably C4 to C8, alpha-olefin, diolefin, or C4 to C20 cyclic olefin, comprising the step of contacting said monomers with one or more of the stable, single-sited ionic catalysts with a cation above and a stabilizing, compatible non-coordinating anion in a polymerization reaction with a reaction medium temperature of 90° C. or above, and optionally at a pressure exceeding 50 bar, preferably exceeding 75 bar for solution processes and 500 bar for high pressure supercritical phase processes. The invention is also in part a modified process comprising the additional step of introducing into either the reaction medium, recycle stream or the monomer feedstocks prior to the polymerization reaction, a scavenger for polar impurities, most preferably a trialkyl aluminum each alkyl being a long-chain, linear-alkyl.
Detailed Description and Best Mode of the Invention
The bridged hafnium compounds of the invention include those having one or more carbon, silicon, or germanium atoms bridging two cyclopentadienyl (Cp) ligands of the hafnium metal centers, said ligands optionally containing one or more hydrocarbon substituents. When the Cp ligand is an indenyl or fluorenyl group, substitutions can be made either on the 5 or 6 member ring carbon atoms. Substituents typically include one or more C1 to C30 hydrocarbon groups selected from linear, branched, cyclic, aliphatic, aromatic or combined groups, whether in a fused-ring or pendant configuration. For the purposes of this application the term "hydrocarbon" is meant to include those compounds or groups that have essentially hydrocarbon characteristics but optionally contain not more than about 10 mol. % non-carbon, polar atoms, such as oxygen, sulfur, nitrogen and phosphorous. Similarly the use of hetero-atom containing cyclopentadienyl rings, where a non-carbon atom replaces one of the ring carbons, is considered for this specification to be within the terms "cyclopentadienyl", "indenyl", and "fluorenyl".
Specific bridged hafnium catalysts include those derived from: (1) indenyl-based complexes such as the rac- or meso-isomer of dimethylsilyl bis (indenyl)hafnium dimethyl, dimethylsilyl bis(4,5,6,7-tetrahydro-indenyl) hafnium dimethyl, dimethylsilyl bis(2-methyl-indenyl) hafnium dimethyl, dimethylsilyl bis(2-propyl-indenyl) hafnium dimethyl, dimethylsilyl bis(4-methyl, 2-phenyl-indenyl) hafnium dimethyl; (2) cyclopentadienyl complexes such as dimethylsilyl (cyclopentadienyl)(tetramethyl cyclopentadienyl) hafnium dibenzyl, dimethylsilyl bis(cyclopentadienyl) hafnium dimethyl; and (3) fluorenyl-based complexes such as dibutylsilyl (fluorenyl) (cyclopentadienyl) hafnium dimethyl and dimethylsilyl (indenyl) (fluorenyl) hafnium dihydride, or i-propyl (cyclopentadienyl) (fluorenyl) hafnium dimethyl.
In particular, for the bridged bis indenyl hafnium compounds, it has been found that increasing the degree of substitution on the indenyl ligands is effective for increased comonomer incorporation, an effect surprising in view of the general knowledge in the art. Thus when the indenyl substituents include at least two sigma bound hydrocarbon radicals replacing hydrogen atoms on the ring atoms, the performance exceeds that where either of zero substituents or just one substituent are present. For example dimethylsilyl bis(2-methyl, 4-phenyl-indenyl) hafnium dimethyl has been found to provide one or both of higher comonomer incorporation and higher molecular weight as compared to dimethylsilyl bis(2-methyl-indenyl) hafnium dimethyl, which is better in one or both of these features than dimethylsilyl bis(indenyl) hafnium dimethyl. Thus preferably the ligation on the indenyl radicals in the bulky hafnium compounds will generally comprise two or more C1 to C30 hydrocarbon substituents as defined above.
The silicon bridged hetero-atom containing, substituted or unsubstituted monocyclopentadienyl titanium compounds of the invention are any of those described in the art, see for example those described in U.S. Pat. No. 5,264,405, WO 92/00333 and U.S. Pat. No. 5,408,017. The substituted cyclopentadienyl ligand is one having hydrocarbon substituents as defined for the cyclopentadienyl, indenyl and fluorenyl ligands of the bridged hafnium compounds above. Each document in incorporated by reference for purposes of U.S. patent practice.
The unbridged, bulky Group 15 containing, bulky monocyclopentadienyl titanium compounds of the invention are unbridged titanium compounds having ancillary ligands including a substituted, bulky cyclopentadienyl ligand, a substituted, bulky Group 15 heteroatom ligand, and two uninegative, activation reactive ligands at least one of which that can be abstracted for activation of the remaining metal compound to a catalytically active state and one of which is either similarly abstractable or has a σ-bond to the transition metal into which an olefin or diolefin can insert for coordination polymerization. Typically, for any of the catalysts of this invention, uninegative, activation reactive ligands are selected from the group comprising hydride, lower alkyl, e.g., C1 to C4, or silyl. The bulky cyclopentadienyl ligand is one having substituents as defined for the cyclopentadienyl, indenyl or fluorenyl ligands of the bridged hafnium compounds above, particularly lower alkyl-substituted ligands, such as tetramethyl and pentamethyl cyclopentadienyl ligands. The bulky Group 15 heteroatom ligand is typically a hydrocarbon substituted Group 15 element, preferably nitrogen, wherein the hydrocarbon substituents are covalently bound to the heteroatom through a secondary or tertiary carbon or silicon atom. See also, copending application U.S. Ser. No. 08/545,973, filed Oct. 20, 1995 (Atty. Docket No. 95B059) which is incorporated by reference for purposes of U.S. patent practice.
Ionic catalysts derived from Group IVB metal precursors where the ancillary ligand system does not contain a cyclopentadienyl ligand may also be employed in this invention. In general, these systems will be prepared from an ionic activator or Lewis Acid activator and a Group IVB metal containing precursor of the following general formula: ##STR1## wherein:
A is an optional bridging substituent,
L1 and L2 are the same or different non-Cp ancillary ligands,
M is a Group IVB metal, and
R1 and R2 are the same or different σ-bonded groups such as hydride or hydrocarbyl.
An example of a suitable non-Cp ancillary ligand system is described in "Conformationally Rigid Diamide Complexes: Synthesis and Structure of Tantalum(III) Alkyne Derivatives", D. H. McConville, el al, Organometallics 1995, 14, 3154-3156. Among the Group 4 metals, the Group 4 metals are preferred especially those of titanium. The Group 4 metal compounds will additionally comprise at least two uninegative, activation reactive ligands at least one of which that can be abstracted for activation of the remaining metal compound to a catalytically active state and one of which is either similarly abstractable or has a σ-bond to the transition metal into which an olefin or diolefin can insert for coordination polymerization. The Group 4 metal compounds having the described ligands can be prepared as illustrated in the Organometallics article except that the Group 5 metal halide is replaced with a Group 4 tetrahalide
The Ni2+ and Pd2+ complexes of the invention are diimine complexes that can be prepared by methods equivalent to those used for the compounds described in "New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and α-Olefins", M. Brookhart, el al, J. Am. Chem. Soc., 1995, 117, 6414-6415. These can be either the dialkyl ether adducts as described, or alkylated reaction products of the described dihalide complexes that can be activated to a cationic state by the anion precursors according to the invention.
In general effective scavenging compounds for ionic polymerization catalysts include those aluminum alkyl compounds listed in U.S. Pat. Nos. 5,153,157 and 5,241,025. The term "scavenger" is used in its art-recognized sense of being sufficiently Lewis acidic to coordinate with polar contaminates and impurities adventiously occurring in the polymerization feedstreams or reaction medium. In particular, for processes utilizing recycle streams of unconverted monomer for reprocessing, the necessity to use polar compounds as catalyst deactivators, or "killers", such as water or lower alcohols, effectively necessitates the use of scavengers, as does the natural occurrence of polar impurities in monomer feedstreams. It has been discovered, however, that the use of excess scavenger has a deleterious effect on catalyst performance, and that the proper choice of scavenger is important to minimize the effects. Addition of excess scavenger causes lower productivity, molecular weight and comonomer incorporation. This effect can be easily seen by comparing Examples 1.2, 1.6, 1.7, and 1.8 in Table 1 of the examples section, when the addition of 6 equivalents of triethylaluminum (TEAL) caused an increase in productivity but as more TEAL was added productivity decreased as did the molecular weight and comonomer content of the product. Replacing TEAL with triisobutyl aluminum (TIBA) (Examples 1.9-1.12) improved the catalyst performance under excess scavenger conditions but did not completely remedy the situation.
Experiments under high temperature conditions showed similar trends. In order to further improve the performance of the ionic catalyst system, a systematic study of more substituted scavengers was carried out. Based on the observation that TIBA performed better than TEAL, it was expected that more highly substituted aluminum alkyl compounds, such as Al(CH2 CMe3)2 Me, where Me is methyl, would be superior to TIBA because of the increase steric bulk around the Al atom. Comparative tests under high temperature conditions showed that Al(CH2 CMe3)2 Me was inferior to TIBA and caused sudden loss of productivity at very low levels of scavenger. Further studies showed that the preferred scavenger is a long chain, linear tri-alkyl aluminum compound, and that longer chains are preferred over shorter chains.
Non-limiting examples of effective long chain, linear tri-alkyl ligand-containing scavengers include those comprised in the group defined by the formula M'R'R"R'", where M' is Al, and each of the R groups independently is a C4 or higher linear, branched or cyclic alkyl group, preferably C6 or higher, most preferably C8 or higher. The long chain, linear alkyl aluminums where each alkyl substituent was of a length of C8 or higher, preferably C9 and higher were observed to exhibit optimal performance, that defined as having the least deleterious effect when used at a level in excess of the optimum level as described in the following paragraph. Specifically included are: tri-n-octyl aluminum, tri-n-decyl aluminum, tri-n-dodecyl aluminum, tri-n-hexadecyl aluminum, and the higher carbon number equivalents, e.g., (C20)3 Al, including those with mixed ligation, and mixed scavenger compounds as well. The hydrolyzed derivatives of these alkyl-ligand containing organoaluminum compounds will additionally be suitable. Additionally, it will be apparent that those scavenging compounds comprising both long-chain, linear and bulky ligands or mixed linear ligands, each ligand as described above, will also be suitable, but perhaps less desirable due to more involved or expensive syntheses.
The long chain, linear-alkyl ligand-containing scavengers of the foregoing paragraph will be useful in any insertion polymerization process for olefinically or acetylenically unsaturated monomers with any of the ionic catalyst systems known in the art or those in development, where such make use of non-coordinating anions and the resulting catalyst sensitivities require elimination of polar impurities. Suitable catalyst systems appear in the catalyst references listed in the Background in this application, additional catalysts include those Group 5 and 6 transition metal catalyst systems of WO 94/01471 based on U.S. Ser. No. 08/086,772 filed Jul. 1, 1993, the disclosures of which are incorporated by reference for purposes of U.S. patent practice. Examples of suitable process conditions include those of gas phase, solution, slurry or bulk polymerization processes for any polymers or copolymers of two or monomers selected from the group consisting of ethylene, propylene, C4 -C20 α-olefins, strained ring cyclic olefins, macromers of up to 100 or more mer units having olefinic unsaturation in the 1-position, or acetylenically unsaturated monomers. Such processes utilize -50° C. to 300° C. temperature and 0 to 3000 bar pressure. Polymers and copolymers having molecular weights equivalent to an M.I. of 100 and below can be prepared in these processes.
The scavengers, whichever are selected, should be utilized in a manner consistent with the sought productivity, polymer molecular weight, and polymer comonomer content. In particular, only that amount sufficient to neutralize the effects of the adventitious catalyst poisons should be utilized, the better purified the comonomer feedstreams into the reactor and as well the other feedstreams or added reactants and recycle, the less scavenger will be required. The amount is preferably as little as possible and can be adjusted empirically by observing the rates of reaction, adiabatic temperature rise, and other indicators of reaction efficiencies observable in the polymerization process, each being maximized holding all variables other than the addition of scavenger constant. Excess scavenger has been observed to cause a reduction in productivity, molecular weight and comonomer incorporation.
Means of preparing the ionic catalyst systems comprising cations of the described transition metal compounds and suitable non-coordinating anions are conventionally known, see for example U.S. Pat. No. 5,198,401 and WO 92/00333. Typically the methods comprise obtaining from commercial sources or synthesizing the selected transition metal compounds comprising an abstractable ligand, e.g., hydride, alkyl or silyl group, and contacting them with an ionizing non-coordinating anion source or precursor in an aromatic solvent. The anion source acts to ionize the transition metal compounds by abstracting the univalent hydride, alkyl or silyl ligand that complements its total valency. The abstraction leaves the transition metal compounds in a +1 cationic state, which is counterbalanced by the stable, compatible and bulky, non-coordinating anion. See the filler description in U.S. Pat. No. 5,198,401, referred to above. Conditions of adiabatic polymerization processes such as practiced at high pressure, result in temperatures exceeding 160° C. and above. These higher operating temperatures lead to increasing instability that is reflected in more difficult higher olefin comonomer incorporation and reduced molecular weight polymer. However, the single site catalysts of this invention under those same conditions evidence higher stability, greater comonomer incorporation and higher retained molecular weight as evidenced in the tabulated observations below.
The non-coordinating anion sources of the invention includes any of those conventionally known to be useful for olefin polymerization with metallocenes, including those known to be useful with the single cyclopentadienyl containing Group 4 transition metals. A representative listing of suitable anions is in U.S. Pat. No. 5,198,401, EP-A-0 426 637, EP-A-0 427 697, EP-A-0 520 732, EP-A-0 573 403, WO 95/24268 and U.S. Pat. No. 5,387,568. Those may be introduced into the catalyst preparation step as either ionic compounds having a cation which abstracts a non-cyclopentadienyl ligand of the transition metal compounds or as neutral compounds which upon abstraction of the non-cyclopentadienyl ligand, leave as a by-product the non-coordinating anion portion. Additionally, it is known that the use of alkylating compounds along with an anion source enables the use of transition metal compounds having ligands too strongly bound to the transition metal center to be abstracted by the anion source, e.g., transition metal dihalides. Typical alkylating sources may be any of the strongly Lewis acidic organoaluminum compounds such as the lower carbon number alkyl aluminums and alkylalumoxanes. See EP-A-0 500 944, EP-A-0 570 982 and EP-A1-0 612 768 for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anion precursor compounds. Each of the above documents is incorporated by reference for purposes of U.S. patent practice. Most preferably transition metal compounds not having halide ligands on the metal center are used for the ionic catalyst systems of this invention since in situ alkylation processes may result in competing reactions and interactions that tend to interfere with the overall polymerization efficiency under conditions of high temperature in accordance with this invention.
A class of preferred anion precursor compounds are hydrated salts comprising a Group 1 or 2 cation and a non-coordinating anion as described above. The hydrated salts can be prepared by reaction of the metal cation-non-coordinating anion salt with water, for example, by hydrolysis of the commercially available or readily synthesized LiB(pfp)4 which yields Li·H2 O! B(pfp)4 !, where (pfp) is penta- or perfluorophenyl. The by-product of ionization of the abstractable ligand-containing transition metal compounds with this precursor is LiOH which is non-volatile and thus is not recycled in the separation phase wherein the polymer is removed from monomer and any diluent prior to recycle. Tests have shown that this low-cost precursor operates to form ionic catalysts having properties essentially equivalent to those formed with the preferred precursor compounds represented by Ph3 C! B(pfp)4 ! and PhMe2 NH! B(pfp)4 !, Ph representing phenyl and Me representing methyl. As with the long chain, linear-alkyl ligand-containing scavengers noted above, this non-volatile by-product anion precursor will be suitable for use with any of the ionic catalyst systems known in the art or those in development, where such make use of non-coordinating anions. Catalytically suitable transition metal compounds capable of cationization include those Group 4 to 6 and 8 compounds addressed above. Again, examples of such include gas phase, solution, slurry and bulk polymerization processes for any polymers or copolymers of two or monomers selected from the group consisting of ethylene, propylene, C4 -C20 α-olefins, strained ring cyclic olefins, macromers of up to 100 or more mer units having olefinic unsaturation in the 1-position, or acetylenically unsaturated monomers. Such processes utilize -50° C. to 300° C. temperature and 0 to 3000 bar pressure.
Known alkylalumoxanes are additionally suitable as catalyst activators for the invention single-site transition metal compounds comprising halide ligands, however these are less preferred since the alumoxane activators are less temperature stable at or above about 160° C. The alumoxane component includes all those useful as a catalyst activator, typically such will be an oligomeric aluminum compound represented by the general formula (R--Al--O)n, which is a cyclic compound, or R(R--Al--O)n AlR2, which is a linear compound. In the general alumoxane formula R is a C1 to C5 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and "n" is an integer from 1 to about 50. Most preferably, R is methyl and "n" is at least 4. Alumoxanes can be prepared by various procedures known in the art. For example, an aluminum alkyl may be treated with water dissolved in an inert organic solvent, or it may be contacted with a hydrated salt, such as hydrated copper sulfate suspended in an inert organic solvent, to yield an alumoxane. Generally, however prepared, the reaction of an aluminum alkyl with a limited amount of water yields a mixture of the linear and cyclic species of the alumoxane.
A preferred process of polymerization is that conducted at high pressure, that is at from 200 to 3000 bar, preferably from 500 to 2500 bar in a homogeneous single phase or two fluid phases, with or without unreactive diluents or sulvents at temperatures generally above the melting point of the polymer being produced. Such processes are typically known and may include the use of scavenger compounds and catalyst deactivation or killing steps, see for example U.S. Pat. No. 5,408,017, WO 95/07941, and WO 92/14766. Each of these documents and their U.S. counterparts are incorporated by reference for purposes of U.S. patent practice. Preferred catalyst deactivators, or killers, include high molecular weight, non-recyclable compounds, such as poly vinyl alcohol which exhibit the functional capacity to complex with the catalysts so as to deactivate them while not forming volatile polar by-products or residual unreacted compounds.
Another preferred process in which any of the catalyst, cocatalyst and scavenger selections disclosed in this application can be advantageously practiced is that of a continuous, solution process operated at or above 90° C. to 120° C., even above 150° C. or above 160° C., up to about 300° C. Typically this process is conducted in an inert hydrocarbon solvent, linear, cyclic or branched aliphatic, or aromatic, at a pressure of from 20 to 200 bar. The disclosures of U.S. patent applications Ser. No. 08/426,363, filed Apr. 21, 1995, and Ser. No. 08/545,973 (Atty. Docket 95B059), filed Oct. 20, 1995, provide relevant description, even when operated at the elevated temperature ranges under supercritical conditions disclosed in this application. These documents also are incorporated by reference for purposes of U.S. patent practice.
For optimal polymerization results the processes should be designed or conducted such that the cocatalyst components, that is the transition metal compounds and the anion precursor compounds, are maintained separately until just prior to or during polymerization use in the chosen reactor. An example is the use of dual injection of each catalyst component directly into the reactor or the use of T- or multi-joint mixing chambers just prior to injection into the reactor. Alternatively the catalyst may be formed in-situ by the independent addition of ionic activator, ligand stabilized metal halide, and scavenger directly into the reactor or the use of T- or multi-joint mixing chambers just prior to injection into the reactor. Additional optimization can be achieved when the scavenger compound is introduced into the reactor independently of the catalyst system, or compounds.
Though directed specifically for high temperature, particularly high pressure or solution, processes, it will be apparent that the use of heterogeneous support material such as polymeric and metal or metalloid oxide supports will enable slurry or gas phase use of the process steps and components described and will likely achieve similar benefits of higher productivities, higher molecular weights, and higher levels of comonomer incorporation for the ethylene copolymer products capable of production using the disclosed copolymerizable monomers. Illustrative support methods appear in WO 91/09882, WO 94/00500, WO 94/03506, WO 94/07928, and in WO 96/04319 based on U.S. application Ser. No. 08/474,948 filed Jun. 7, 1995, in turn based on U.S. Ser. No. 08/285,380 filed Aug. 3, 1994. A suitable slurry process is described in U.S. Pat. No. 5,229,478. Each of the foregoing are incorporated by reference for purposes of U.S. patent practice.
The following examples are presented to illustrate the foregoing discussion. All parts, proportions and percentages are by weight unless otherwise indicated. Although the examples may be directed to certain embodiments of the present invention, they are not to be viewed as limiting the invention in any specific respect. Methods of determining MW and monomer contents by GPC and NMR for the illustrative EPC examples of the invention are described in U.S. Pat. No. 5,229,478 which is incorporated by reference for purposes of U.S. patent practice. For the following examples certain abbreviations have been utilized for convenience: Cp (cyclopentadienyl), Me(methyl), Ind (indenyl), Ph (phenyl), pfp (pentafluorophenyl), r-(racemic), Et (ethyl), Cp* (permethylated cyclopentadienyl), Cod (cyclododecyl), TOA (tri-n-octyl aluminum), TEAL (triethyl aluminum) and TIBA (triisobutyl aluminum).
Part 1: Laboratory Screening Experiments
The data from batch laboratory tests is summarized in Table 1. All polymerizations in Table 1 were carried out in a one liter stainless steel autoclave in 400 cc hexane with 45 cc hexene under 75 psi (517.11 kPa) ethylene head pressure at 60° C.
In each case the autoclave was filled with the solvent and hexene and heated under 75 psi (517.11 kPa) of ethylene until equilibrium was reached under rapid stirring. The catalyst was introduced into the reactor under these conditions and the temperature was maintained at 60° C.±/-5° C. for the duration of the run. The product was recovered and analyzed by GPC and 13 C NMR spectroscopy to determine the molecular weight and comonomer content. An example of continuous process use of the information contained in Table 1 follows Example 1.1.
A one liter mechanically stirred stainless steel autoclave was filled with 400 ml dry and deoxygenated hexane, 45 ml dry and deoxygenated hexene. The reactor was stirred rapidly, pressurized to 75 psi (517.11 kPa) with ethylene, and heated to 60° C. A catalyst solution in toluene containing 1.42×10-5 moles of r-Me2 Si(Ind)2 HfMe2 and 4.99×10-5 PhMe2 NH! B(pfp)4 ! was added to the reactor causing a polymerization reaction to occur. After 30 minutes the reactor was vented and the contents were poured into a flask. The solvent was evaporated to yield 5 grams of and ethylene/hexene copolymer having a Mw =151,000 Daltons, a Mn =74,000 Daltons, and 47.4 wt. % hexene. This represents a productivity of 714 grams PE/gram metallocene.
The results of the screening experiments collected in Table 1 demonstrate several important trends. These include the following observations.
Bridged vs. Unbridged Metallocenes
Bridged have 2-3 times the comonomer incorporation (see Cp2 HfMe2 vs. Et2 SiCp2 HfMe2 or CpCp*HfMe2 vs. Me2 SiCpCp*HfMe2).
Bridged complexes produce higher MW products.
Bridged complexes typically show higher activities.
PhMe2 NH! Bpfp)4 ! vs. Ph3 C!Bpfp)4 ! vs. Li·H2 O! Bpfp)4 !
All appear to produce the same polymer at similar rates.
The Effect of Scavengers on Catalyst Performance
High levels cause lower MW and comonomer content.
Low levels improve productivity without affecting product.
TIBA better than TEAL in terms of effect on product at high levels of scavenger.
high levels depress productivity.
2 Si(Ind)2 HfMe2 vrs. Me2 Si(4-Me,2-PhInd)2 HfMe2
Substituted system shows higher MW even at high comonomer content.
Substituted system shows significant increases in comonomer incorporation.
The metallocene dichloride route vrs. the metallocene dialkyl route
The chloride free approach produces high MW and comonomer content products.
Zr vrs. Hf
Hf systems superior in terms of MW and comonomer incorporation.
Mono-Cp Ti vrs. bis-Cp Hf Catalysts
The bis-Cp Hf systems can be modified to have similar performance to the mono-Cp systems.
Part 2: Continuous High Pressure Operation
The polymerization reactions in Table 2 were performed in a stirred 1.5 L steel autoclave reaction vessel which was equipped to perform continuous Ziegler polymerization reactions at pressures up to 2000 bar and temperatures up to 300° C. 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. Pressure was controlled by pressure reduction valve. Equipment for continuously introducing a measured flow of catalyst 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 ability to add scavenger to the fresh feed prior to the reactor was provided by a high pressure pump. The polymerization was performed with a specified molar ratio of ethylene to comonomer and without the addition of a solvent. The temperature of the reactor containing ethylene and comonomer was equilibrated at the desired reaction temperature. The catalyst solution was prepared by mixing a specified amount of solid metallocene component with the activator component 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. The reactor contents were stirred at 1000 rpm and the reactor feed mass flow rate typically used was 40 kg/hr. Exact run conditions including catalyst preparation metallocene component (M) (g), activator component (A) (g), and total volume of solution (L) scavenger aluminum compound to transition metal compound with molar rate (Al:M), catalyst production polymer production rate (kg polymer/hr) average, comonomer molar feed ratio (e.g. C4 /C2), reactor mass flow rate (kg/hr), and polymer characteristics including melt index (g/10 minutes at 190° C.), and weight percent comonomer (determined by IR), are also collected in Table 2. All polymerizations were carried out at 225° C. and 1300 bar. The catalyst solutions were prepared using dry and deoxygenated toluene. An example of how to use the information contained in Table 2 follows Example 2.1.
Using the reactor design as described above, and using a molar ratio of the ethylene to 1-butene of 0.55 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 225° C. The catalyst solution was prepared by mixing 0.496 g of solid compound r-Me2 Si(Ind)2 HfMe2 with 0.9788 activator compound (Ph3 C)+ B(pfp)4 - in 20 liter toluene. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate which resulted in a temperature of 225° C. in the reactor. During this run, ethylene and 1-butene was pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm, and the mass feed flow rate through the reactor was held constant at 40 kg/hr. Polymerization was conducted for a 60 to 90 sec. residence time. The yield of polymer product was 6.6 kg/hr. of an ethylene-1-butene copolymer which had a MI of 2.85 and a comonomer incorporation of 13 weight percent butene as measured by IR. Transition metal productivity was calculated at 267 kg polymer/g metallocene.
TABLE 1__________________________________________________________________________ Mole MoleExp # Metallocene Activator Met Act. Scav. A1:M__________________________________________________________________________1.1 r-Me2 Si(Ind)2 HfMe2 PhMe2 NH! B(pfp4 ! 7.28E-05 2.50E-06 none none1.2 r-Me2 Si(Ind)2 HfMe2 Ph3 C! B(pfp)4 ! 1.46E-05 4.88E-06 none none1.3 r-Me2 Si(Ind)2 HfMe2 LiB(pfp)4.H2 O 9.10E-05 2.91E-05 none none1.4 r-Me2 Si(Ind)2 HfMe2 LiB(pfp)4.H2 O 2.83E-05 1.16E-05 TIBA 1Comp 1.5 r-Me2 Si(Ind)2 HfMe2 Ph3 C! B(pfp)4 ! 3.44E-06 3.25E-06 TEAL 6Comp 1.6 r-Me2 Si(Ind)2 HfMe2 Ph3 C! B(pfp)4 ! 7.89E-06 7.59E-06 TEAL 76Comp 1.7 r-Me2 Si(Ind)2 HfMe2 Ph3 C! B(pfp)4 ! 8.90E-06 8.68E-06 TEAL 335Comp 1.8 r-Me2 Si(Ind)2 HfMe2 Ph3 C! B(pfp)4 ! 1.21E-06 1.08E-06 TIBA 18Comp 1.9 r-Me2 Si(Ind)2 HfMe2 Ph3 C! B(pfp)4 ! 2.22E-06 2.17E-06 TIBA 50Comp 1.10 r-Me2 Si(Ind)2 HfMe2 Ph3 C! B(pfp)4 ! 6.67E-06 6.51E-06 TIBA 335Comp 1.11 r-Me2 Si(Ind)2 HfMe2 Ph3 C! B(pfp)4 ! 7.89E-06 7.59E-06 TIBA 569*Comp 1.12 r-Me2 Si(Ind)2 HfCl2 PhMe2 NH! B(pfp)4 ! 1.87E-05 6.24E-06 TEAL 16*Comp 1.13 FMe2 Si(Ind)2 HfCl2 Ph3 C! B(pfp)4 ! 9.34E-06 3.58E-08 TEAL 321.14 Cp2 HfMe2 Ph3 C! B(pfp)4 ! 2.65E-05 8.68E-06 none none*Comp 1.15 Cp2 HfCl2 PhMe2 NH! B(pfp)4 ! 4.08E-05 9.99E-06 TEAL 51.16 Et2SiCp2 HfMe2 Ph3 C! B(pfp)4 ! 3.20E-05 3.15E-05 none none1.17 CpCp*HfMe2 Ph3 C! B(pfp)4 ! 9.55E-06 3.25E-06 none none1.18 Me2 SiCpCp*HfMe2 Ph3 C! B(pfp)4 ! 1.44E-05 5.42E-06 none none1.19 r-Me2 Si(4Me,2PhInd)2 HfMe2 PhMe2 NH! B(pfp)4 ! 1.48E-05 4.99E-06 none none1.20 r-Me2 Si(4MeInd)2 ZrMe2 Ph3 C! B(pfp)4 ! 1.84E-05 1.52E-05 none none1.21 Me2 SiCp*N(Cod)TiMe2 Ph3 C! B(pfp)4 ! 3.09E-05 2.49E-05 none none__________________________________________________________________________ T Yield MwExp # (min.) (gr) (K) Mn MW Wt % C6 Productivity__________________________________________________________________________1.1 30 7 149 79 1.8 46.8 19441.2 30 9 148 78 1.8 49.2 12861.3 1 26 74 34 2.1 55.5 5781.4 30 19 141 75 1.8 51.4 1357Comp 1.5 30 40 120 53 2.2 50.2 23529Comp 1.6 30 3 51 23.4 2.1 39 769Comp 1.7 30 3.5 34.8 17.5 1.9 31.5 750Comp 1.8 30 17 161 82.7 1.9 44.3 31667Comp 1.9 30 12 138 70.8 1.9 52.4 10909Comp 1.10 30 3.5 92.8 44.8 2.0 47 1061Comp 1.11 30 8 89.1 47.4 1.8 46.8 2051*Comp 1.12 30 20 77.2 34.8 2.2 36 2000*Comp 1.13 30 15 96.3 46.7 2.0 40.8 21571.14 30 1.5 351 147 2.3 24.4 170*Comp 1.15 30 13 36.6 22.8 1 11.4 8551.16 30 13 86.1 43.7 1.9 43.1 9631.17 30 3 113.9 57.7 1.9 11.1 7691.18 30 8 140.5 35.6 3.9 32 12311.19 30 32 220 108 2.0 56.2 32001.20 30 5 87.7 46.3 1.8 38.5 6251.21 30 8 247 96.7 2.5 71.9 593__________________________________________________________________________ *In-situ activation, dual functioning of alkylaluminum. Comp indicates comparative example.
TABLE 2__________________________________________________________________________ Produc- Volume M:A tionExp Weight Weight Toluene Mole Rate wt KgPE/# Metallocene (M) M (gr) Activator (A) A (gr) (L) Ratio Scav A1:M C4 :C2 MI (Kg/hr) C4 gM__________________________________________________________________________2.1 r-Me2 Si(Ind)2 HfMe2 0.496 trityl+ B(pfp)4 - 0.978 20 0.94 TOA 33 0.55 2.85 6.6 13 267K2.2 r-Me2 Si(Ind)2 HfMe2 0.552 DMAH+ B(pfp)4 - 0.957 20 0.93 TOA 34 0.55 3.02 6.1 13.7 251K2.3 r-Me2 Si(Ind)2 HfMe2 0.662 DMAH+ B(pfp)4 - 0.932 20 1.1 TOA 32 1 25.1 6.3 25.4 178K2.4 r- 0.891 DMAH+ B(pfp)4 1.063 20 0.99 TOA 55 1 63.3 6 38.5 290K Me2 Si(2Me,4PhInd)2 HfMe22.5 r- 0.891 DMAH+ B(pfp)4 1.063 20 1 TOA 9 0.6 9.95 6.8 28.5 55K Me2 Si(2Me,4PhInd)2 HfMe22.6 r-Me2 Si(2MInd)2 HfMe2 0.497 DMAH+ B(pfp)4 - 0.86 10 1 TOA 0.76 24 24__________________________________________________________________________
Part 3: Continuous High Temperature Solution Process
The polymerization reaction was performed in a stirred, liquid filled 2 L jacketed steel reactor equipped to perform continuous insertion polymerization in presence of an inert C6 hydrocarbon (naphta) solvent at pressures up to 120 bar and temperatures up to 240° C. The reactor was typically stirred at 1000 rpm during the polymerization. The reaction system was supplied with a thermocouple and a pressure transducer to monitor changes in temperature and pressure continuously, and with means to supply continuously purified ethylene, 1-octene, and solvent. In this system, ethylene dissolved in the hydrocarbon solvent, 1-octene, tri-n-octyl aluminum (TOA) used as a scavenger, and optionally H2, are pumped separately, mixed, and fed to the reactor as a single stream, refrigerated to -40° C. using liquid NH3 as a coolant. The transition metal component (TMC) was dissolved in a solvent/toluene mixture (9/1 vol/vol) whereas the non-coordinating anion (NCA) activator was dissolved in toluene or slurried in the hydrocarbon solvent. Both components were pumped separately, mixed at ambient temperature, and cooled to -1° C. prior to entering the reactor. The reactor temperature was set by adjusting the temperature of an oil bath used as a reservoir for the oil flowing through the reactor wall jacket. Next, the polymer molecular weight (MW) or MI was controlled independently by adjusting the ethylene conversion (% C2) in the reactor via the catalyst flow rate. Finally, the polymer density was controlled by adjusting the ethylene/1-octene weight ratio in the feed.
The results of ten polymerization experiments performed in the reactor described above with three different TMC's (A=rac-dimethylsilyl bis(1-indenyl) hafnium dimethyl, B=dimethylsilyl bis(2-methyl-4-phenyl-1-indenyl) hafnium dimethyl, and C=dimethylsilyl (tetramethylcyclopentadienyl)butylamino titatium dimethyl) and PhMe2 NH!B(pfp)4 ! used as the activator (NCA) are summarized in Table 1. For example, the polymerization reaction in run #1 was carried out at 150° C. and 86.4 bar with A. Solvent, ethylene, and 1-octene were continuously fed to the reactor at a rate of 7 kg/hr., and 0.53 kg/hr., respectively, The 1-octene/ethylene weight ratio in the feed was 0.431 in this case. 3.5 mg/hr. of A dissolved in a 9/1 solvent/toluene (vol/vol) mixture and 4.9 mg/hr. of NCA dissolved in toluene were continuously fed to the reactor, resulting in an ethylene conversion of 80.5% and a 1-octene conversion of 43%. For a reactor residence time of 8 minutes, the polymer yield was 1.22 kg/hr. under these conditions. By adding TOA at a rate of 0.08 mmol/hr. to the feed, the catalyst productivity lined out around 348 kgPE/g A. This experiment resulted in an ethylene/1-octene copolymer containing 18.77 weight % comonomer (FTIR) with a weight-average MW of 88,000 g/mol (GPC), a polydispersity index of 2.1 (GPC), a MI of 1.4 dg/min., a density of 0.8991 g/cc, and a MIR (I21.6/I2) of 34.
At constant reactor temperature and feed composition, the polymer MW can be adjusted in this low pressure/high temperature polymerization process by controlling the ethylene conversion in the reactor via the catalyst flow rate; typically, the higher the ethylene conversion, the lower the polymer MW (the higher the MI). The above examples showed that surprisingly both bridged bis (Cp) hafnocenes (A and B) exhibit superior MW and comonomer incorporation capability than the bridged mono(Cp) titanocene (C) does. For example, at 140° C. and with a 1-octene/ethylene weight ratio in the feed equal to about 0.43 to 0.44, A and B produced, respectively, a 1.6 MI/0.8937 g/cc copolymer at 87.9% ethylene conversion (run #3) and a 0.62 MI/0.8880 g/cc copolymer at 80.7% ethylene conversion (run #6), whereas (C) produced a 1.5 MI/0.9035 g/cc copolymer at a substantially lower ethylene conversion of 77.1% (run #9). Similarly, at 130° C. and with a 1-octene/ethylene weight ratio in the feed equal to about 0.93 to 0.94, A produced a 1.23 MI/0.8761 g/cc copolymer at 73.9% ethylene conversion (run #4), whereas (C) made a 3.2 MI/0.8866 g/cc copolymer at a lower ethylene conversion of 69.2% (run #10).
TABLE 3__________________________________________________________________________ MW(TM) TM ACT ACT/TM AIR3 T P C6 sol C2 C8 C8 /C2run # TM g/mol mg/hr mg/hr mol/mol mmol/hr °C. bar kg/hr kg/hr kg/hr kg/hr__________________________________________________________________________1 A 494.5 3.5 4.9 0.86 0.08 150.0 86.4 7.0 1.23 0.530 0.4312 A 494.5 2.6 3.7 0.88 0.08 159.9 86.3 6.9 1.23 0.530 0.4313 A 494.5 4.0 5.3 0.82 0.11 142.8 86.6 7.1 1.20 0.530 0.4424 A 494.5 1.4 2.0 0.88 0.11 130.3 86.9 6.9 1.21 1.140 0.9425 B 674.5 5.5 6.7 1.03 0.08 149.1 86.4 7.0 1.21 0.510 0.4216 B 674.5 5.0 6.1 1.03 0.08 139.9 86.6 7.3 1.22 0.520 0.4267 C 329.9 2.9 7.2 1.02 0.08 159.2 86.5 7.1 1.21 0.520 0.4308 C 329.9 2.5 6.0 0.99 0.08 150.5 86.5 7.0 1.23 0.520 0.4239 C 329.9 2.1 5.1 1.00 0.08 140.9 86.7 7.0 1.22 0.530 0.43410 C 329.9 1.8 4.4 1.01 0.10 131.5 86.6 6.9 1.23 1.140 0.927__________________________________________________________________________C2 C8 Rt yield cat prod MI MIR density C8 inc. Mw PDI% conv % conv min kg/hr kg PE/g TM dg/min 121.6/12 g/cc wt. % g/mol Mw/Mn__________________________________________________________________________80.5 43.0 8.0 1.22 348 1.40 34.0 0.8991 18.77 88000.00 2.173.1 33.1 8.0 1.047 413 1.20 32.2 0.9038 16.30 85000.00 2.187.9 54.9 7.9 1.35 336 1.60 53.7 0.8947 21.49 84000.00 2.073.9 34.8 7.9 1.29 922 1.23 31.6 0.8761 30.6873.6 53.9 8.1 1.17 212 1.40 50.0 0.8915 23.65 95000.00 3.680.7 66.5 7.8 1.33 266 0.62 65.8 0.8880 26.05 3.369.0 22.5 7.9 .095 328 2.10 23.8 0.9121 12.22 91000.00 2.573.8 28.3 8.0 1.05 422 1.90 25.3 0.9082 13.98 91000.00 2.577.1 33.1 8.1 1.12 531 1.50 26.7 0.9035 15.66 97000.00 2.469.2 26.3 7.8 1.15 639 3.20 24.5 0.8866 25.97__________________________________________________________________________ Notes: (1) For all runs the catalyst activator was DMAH! B(pfp)4! and the scavenger was trin-octyl aluminum. (2) Other abbreviations above include: A = rMe2 Si(Ind)2 HfMe2 B = Me2 Si(2Me-4PhInd)2 HfMe2 C = Me2 SiCp*NbutyITiMe2 C2 = ethylene C8 = 1octene C6 = hydrocarbon (naphta)solvent
|Brevet cité
|Date de dépôt
|Date de publication
|7 sept. 1989
|21 mai 1991
|Exxon Chemical Patents Inc.
|Silicon-bridged transition metal compounds
|16 oct. 1990
|19 nov. 1991
|Ethyl Corporation
|Hydrocarbon solutions of alkylaluminoxane compounds
|10 sept. 1987
|28 janv. 1992
|Exxon Chemical Patents, Inc.
|High pressure, high temperature polymerization of ethylene
|20 mars 1990
|6 oct. 1992
|Exxon Chemical Patents Inc.
|Catalyst system of enhanced productivity
|30 juil. 1991
|30 mars 1993
|Exxon Chemical Patents Inc.
|Ionic metallocene catalyst compositions
|13 mars 1992
|23 nov. 1993
|Exxon Chemical Patents Inc.
|Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalysts
|28 avr. 1992
|11 janv. 1994
|Exxon Chemical Patents Inc.
|Catalysts, method of preparing these catalysts, and polymerization processes wherein these catalysts are used
|14 oct. 1992
|19 avr. 1994
|Hoechst Aktiengesellschaft
|Process for the preparation of an olefin polymer using metallocenes having specifically substituted indenyl ligands
|29 oct. 1993
|14 juin 1994
|Mitsui Petrochemical Industries, Ltd.
|Olefin polymerization catalyst and process for the polymerization of olefins
|30 aoűt 1991
|28 juin 1994
|Exxon Chemical Patents Inc.
|Process and catalyst for polyolefin density and molecular weight control
|14 juin 1993
|18 avr. 1995
|Exxon Chemical Patents Inc.
|High temperature polymerization process using ionic catalysts to produce polyolefins
|19 mai 1993
|18 juil. 1995
|Tosoh Corporation
|Process for producing olefin polymer
|18 déc. 1996
|16 juin 1998
|Exxon Chemical Patents Inc.
|High temperature olefin polymerization process
|29 nov. 1991
|3 juin 1993
|Basf Ag
|Catalyst system for polymerisation of alkene(s) - contg. metallocene, oligomeric aluminium oxide cpd. and organic aluminium cpd. leads to prod. with lower levels of aluminium residue
|24 juil. 1991
|7 oct. 1998
|Mitsui Chemicals, Inc.
|Catalyst for alpha-olefin polymerization and production of poly-alpha-olefin therewith
|21 mai 1993
|24 nov. 1993
|Tosoh Corporation
|Catalysts and process for producing olefin polymers
|21 févr. 1994
|31 aoűt 1994
|Tosoh Corporation
|Process for producing ethylene/alpha-olefin copolymer
|5 oct. 1993
|14 avr. 1994
|Exxon Chemical Patents Inc
|Catalyst system of enhanced productivity and its use in polymerization process
|16 sept. 1994
|23 mars 1995
|Norbert Baron
|Olefin polymerisation process
|19 avr. 1996
|24 oct. 1996
|Exxon Chemical Patents Inc
|ETHYLENE-α-OLEFIN/DIOLEFIN POLYMER SOLUTION POLYMERIZATION PROCESS
|"High Temperature Olefin Polymerization Process", Research Disclosures, vol. 388, No. 035, Aug. 10, 1996.
|"Production of Polyacetylene", Patent Abstracts of Japan, Matsushita Electric Ind. Co., Ltd., vol. 14, No. 475, (C-0770), Oct. 17, 1990.
|High Temperature Olefin Polymerization Process , Research Disclosures, vol. 388, No. 035, Aug. 10, 1996.
|Production of Polyacetylene , Patent Abstracts of Japan, Matsushita Electric Ind. Co., Ltd., vol. 14, No. 475, (C 0770), Oct. 17, 1990.
|Brevet citant
|Date de dépôt
|Date de publication
|29 déc. 2000
|18 nov. 2003
|Imperial Chemical Industries Plc
|Process for preparing vinylic polymers with catalyst system containing metal complex and Lewis acid
|5 nov. 2002
|14 juin 2005
|Dow Global Technologies Inc.
|Isotactic propylene copolymer fibers, their preparation and use
|15 aoűt 2003
|19 juil. 2005
|Dow Global Technologies Inc.
|Blends and sealant compositions comprising isotactic propylene copolymers
|5 nov. 2002
|9 aoűt 2005
|Dow Global Technologies Inc.
|Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent
|15 déc. 2003
|30 aoűt 2005
|Univation Technologies, Llc
|High tear films from hafnocene catalyzed polyethylenes
|5 nov. 2002
|13 sept. 2005
|Dow Global Technologies Inc.
|Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers
|18 oct. 2004
|20 sept. 2005
|Dow Global Technologies Inc.
|Films comprising isotactic propylene copolymers
|5 mai 2002
|1 nov. 2005
|Dow Global Technologies Inc.
|Isotactic propylene copolymers, their preparation and use
|10 janv. 2005
|11 avr. 2006
|Chevron Phillips Chemical Company, Lp
|Polymerization catalysts for producing high melt index polymers without the use of hydrogen
|5 nov. 2002
|9 mai 2006
|Dow Global Technologies Inc.
|Films comprising isotactic propylene copolymers
|10 aoűt 2004
|13 juin 2006
|Dow Global Technologies Inc.
|Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent
|19 juin 2000
|18 juil. 2006
|Symyx Technologies, Inc.
|High throughput screen for identifying polymerization catalysts from potential catalysts
|2 juil. 2004
|19 sept. 2006
|Dow Global Technologies Inc.
|Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers
|24 mai 2005
|6 févr. 2007
|Univation Technologies, Llc
|High tear films from hafnocene catalyzed polyethylenes
|4 avr. 2005
|20 févr. 2007
|Univation Technologies, Llc
|High tear films from hafnocene catalyzed polyethylenes
|9 juin 2005
|3 avr. 2007
|Dow Global Technologies, Inc.
|Isotactic propylene copolymer fibers, their preparation and use
|15 sept. 2005
|5 juin 2007
|Chevron Phillips Chemical Company, L.P.
|Polymerization catalysts and process for producing bimodal polymers in a single reactor
|22 févr. 2006
|31 juil. 2007
|Dow Global Technologies Inc.
|Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent
|22 févr. 2006
|31 juil. 2007
|Dow Global Technologies Inc.
|Impact resistance polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers
|22 aoűt 2005
|25 déc. 2007
|Chevron Phillips Chemical Company Lp
|Polymerization catalysts and process for producing bimodal polymers in a single reactor
|17 oct. 2003
|26 févr. 2008
|Dow Global Technologies, Inc.
|Highly filled polymer compositions
|31 janv. 2007
|18 mars 2008
|Dow Global Technologies Inc.
|Isotactic propylene copolymer fibers, their preparation and use
|5 mai 2003
|2 déc. 2008
|Dow Global Technologies Inc.
|Thermoplastic elastomer compositions
|12 févr. 2007
|21 avr. 2009
|Chevron Phillips Chemical Company, Lp
|Polymerization catalysts and process for producing bimodal polymers in a single reactor
|3 mai 2003
|25 aoűt 2009
|Dow Global Technologies Inc.
|Thermoplastic elastomer compositions
|22 févr. 2006
|17 nov. 2009
|Chevron Phillips Chemical Company, Lp
|Dual metallocene catalysts for polymerization of bimodal polymers
|2 nov. 2005
|1 déc. 2009
|Chevron Phillips Chemical Company Lp
|Multimodal polyethylene compositions and pipe made from same
|27 nov. 2007
|24 aoűt 2010
|Dow Global Technologies Inc.
|Highly filled polymer compositions
|1 oct. 2003
|14 sept. 2010
|Dow Global Technologies Inc.
|Liquid and gel-like low molecular weight ethylene polymers
|13 févr. 2006
|21 déc. 2010
|Exxonmobil Chemical Patents Inc.
|Propylene olefin copolymers
|22 mars 2011
|Chevron Phillips Chemical Company Lp
|Process for preparing a monocyclopentadienyl compound
|14 mai 2007
|17 mai 2011
|Exxonmobil Chemical Patents Inc.
|Ethylene elastomer compositions
|1 oct. 2009
|14 juin 2011
|Chevron Phillips Chemical Company Lp
|Dual metallocene catalysts for polymerization of bimodal polymers
|19 avr. 2007
|27 sept. 2011
|Exxonmobil Chemical Patents Inc.
|Propylene ethylene polymers and production process
|18 oct. 2005
|10 janv. 2012
|Dow Global Technologies Llc
|Method of controlling a polymerization reactor
|26 avr. 2011
|20 mars 2012
|Chevron Phillips Chemical Company Lp
|Dual metallocene catalysts for polymerization of bimodal polymers
|15 févr. 2012
|18 sept. 2012
|Chevron Phillips Company, L.P.
|Dual metallocene catalysts for polymerization of bimodal polymers
|3 févr. 2011
|27 nov. 2012
|Chevron Phillips Chemical Company Lp
|Polymerization process for producing bimodal polymers
|26 aoűt 2011
|6 aoűt 2013
|Exxonmobil Chemical Patents Inc.
|Propylene ethylene polymers and production process
|30 oct. 2012
|13 aoűt 2013
|Chevron Phillips Chemical Company Lp
|Polymerization process for producing bimodal polymers
|12 déc. 2012
|3 juin 2014
|Dow Global Technologies Llc
|Method of controlling a polymerization reactor
|17 juin 2010
|30 sept. 2014
|Dow Global Technologies Llc
|Liquid and gel-like low molecular weight ethylene polymers
|29 janv. 2013
|4 nov. 2014
|Chevron Phillips Chemical Company Lp
|Catalyst compositions and methods of making and using same
|25 oct. 2012
|25 nov. 2014
|Chevron Phillips Chemical Company Lp
|Catalyst compositions and methods of making and using same
|25 oct. 2012
|20 janv. 2015
|Chevron Phillips Chemical Company Lp
|Catalyst compositions and methods of making and using same
|29 janv. 2013
|19 mai 2015
|Chevron Phillips Chemical Company Lp
|Polymer compositions and methods of making and using same
|5 nov. 2002
|18 sept. 2003
|Stevens James C.
|Isotactic propylene copolymer fibers, their preparation and use
|5 nov. 2002
|16 oct. 2003
|Li-Min Tau
|Films comprising isotactic propylene copolymers
|5 nov. 2002
|16 oct. 2003
|Stevens James C.
|Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers
|5 nov. 2002
|16 oct. 2003
|Stevens James C.
|Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent
|5 mai 2002
|30 oct. 2003
|Stevens James C.
|Isotactic propylene copolymers, their preparation and use
|5 mai 2003
|6 mai 2004
|Li-Min Tau
|Thermoplastic elastomer compositions
|3 mai 2003
|2 déc. 2004
|Lin-Min Tau
|Thermoplastic elastomer compositions
|12 oct. 2004
|24 févr. 2005
|Exxonmobil Chemical Patents Inc.
|Elastic blends comprising crystalline polymer and crystallizable polymers of propylene
|15 déc. 2003
|17 mars 2005
|Szul John F.
|High tear films from hafnocene catalyzed polyethylenes
|4 avr. 2005
|4 aoűt 2005
|Szul John F.
|High tear films from hafnocene catalyzed polyethylenes
|1 févr. 2005
|8 sept. 2005
|Sudhin Datta
|Elastic blends comprising crystalline polymer and crystallizable polymers of propylene
|6 mai 2005
|15 sept. 2005
|Sudhin Datta
|Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
|6 mai 2005
|22 sept. 2005
|Sudhin Datta
|Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
|24 mai 2005
|29 sept. 2005
|Szul John F
|High tear films from hafnocene catalyzed polyethylenes
|1 oct. 2003
|2 févr. 2006
|Teresa Karjala
|Liquid and del-like low molecular weight ethylene polymers
|17 oct. 2003
|11 mai 2006
|Selim Yalvac
|Highly filled polymer compositions
|22 aoűt 2005
|22 févr. 2007
|Martin Joel L
|Polymerization catalysts and process for producing bimodal polymers in a single reactor
|2 nov. 2005
|22 févr. 2007
|Martin Joel L
|Multimodal polyethylene compositions and pipe made from same
|15 sept. 2005
|15 mars 2007
|Jayaratne Kumudini C
|Polymerization catalysts and process for producing bimodal polymers in a single reactor
|31 janv. 2007
|31 mai 2007
|Dow Global Technologies Inc.
|Isotactic Propylene Copolymer Fibers, Their Preparation and Use
|22 févr. 2006
|23 aoűt 2007
|Qing Yang
|Dual metallocene catalysts for polymerization of bimodal polymers
|18 oct. 2005
|22 mai 2008
|Dow Global Technologies Inc.
|Method Of Controlling A Polymerization Reactor
|1 oct. 2009
|18 févr. 2010
|Chevron Phillips Chemical Company Lp
|Dual metallocene catalysts for polymerization of bimodal polymers
|4 aoűt 2011
|Chevron Phillips Chemical Company Lp
|Polymerization process for producing bimodal polymers
|18 aoűt 2011
|Chevron Phillips Chemical Company Lp
|Dual metallocene catalysts for polymerization of bimodal polymers
|17 sept. 2004
|2 avr. 2008
|Dow Gloval Technologies Inc.
|Interpolymers suitable for use in hot melt adhesives and processes to prepare same
|17 oct. 2003
|3 sept. 2008
|Dow Global Technologies, Inc.
|Highly filled polymer compositions
|18 juin 2001
|27 déc. 2001
|Symyx Technologies Inc
|High throughput screen for identifying polymerization catalysts from potential catalysts
|4 avr. 2008
|27 nov. 2008
|Exxonmobil Chem Patents Inc
|Ethylene elastomer compositions
|Classification aux États-Unis
|526/160, 526/132, 526/348.6, 526/348.2, 526/152, 526/151, 526/127, 526/133
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Full Bloom
Amber clearly has a high threshold for pain, but even she admits that her blooming rose tattoo on her lower abdomen (creatively mirroring the shape of a uterus) was a killer. "That's a very sensitive area. I teared up a little," she said.
(Photo: Inked Magazine, November 2011)
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Kim Kardashian's Sexiest Magazine Covers07/09/2015
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subset: commoncrawl


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Preimplantation genetic diagnosis (PGD) is the screening of individual embryos for genetic disorders or gender determination during the IVF process. At ART Reproductive Center, part of SCRC, the PGD procedure is a primary focus, and director Dr. David Hill is a nationally recognized expert in its use.
The preimplantation genetic diagnosis (PGD) procedure allows the screening of embryos for specific genetic traits before an embryo is implanted in a patient's uterus. Also known as "embryo biopsy," PGD enables couples at risk for certain genetic diseases to determine which of their embryos are affected, and which are not, before the embryos are used to establish a pregnancy.
We use PGD at the Southern California Reproductive Center to detect abnormalities in chromosomes, hereditary conditions, and for gender selection.
PGD can increase the chance of pregnancy because the pre-screening process identifies poor-quality embryos that are unlikely to survive implantation and a normal pregnancy. This also leads to a significant reduction in the chance of miscarriage. PGD can reduce the risk of multiple pregnancy because fewer embryos are needed for implantation. In addition, the patients who can benefit from PGD include:
Family balancing is one of several issues that can arise with the concept of gender determination. Our SCRC physicians will be glad to discuss the options available to couples that include determination of gender of their pre-embryos as part of the preimplantation genetic screening panel.
PGD requires patients to undergo an in vitro fertilization (IVF) cycle in order to produce pre-embryos available for testing.
Before the transfer of a pre-embryo back to a woman's uterus, some cells (called blastomeres) are removed from the available pre-embryos. These blastomeres are evaluated for abnormalities. Following completion of the evaluation (typically one to two days), only the normal pre-embryos are transferred back to the woman's uterus to establish a pregnancy.
PGD can be used for determining chromosomal health (with PGD-FISH or PGD-CGH) or the presence or absence of specific genes related to hereditary disease (with PGD-PCR).
The most common chromosomal abnormalities occur when there is an incorrect number of chromosomes, a condition known as aneuploidy. Some chromosomes are more likely than others to become unpaired, which can lead to early embryonic demise (chromosomes 13, 16, 18, and 22) or affect term births, such as Down syndrome (trisomy 21). Numerical mistakes in the sex chromosomes can lead to Turner's syndrome (XO), or Klinefelter's syndrome (XXY). Sometimes, chromosomes can break apart and attach to other chromosomes, a condition known as translocation. Translocations have been associated with miscarriage as well as many serious diseases, including some forms of leukemia. Checking for normal chromosome pairing is done using a technique called fluorescent in situ hybridization (FISH), an established component of the preimplantation genetic diagnosis (PGD) testing at our clinics.
PGD-CGH is a recent advance in the screening of pre-embryos for chromosomal normality. Its primary advantage is that CGH looks at all 23 pairs of chromosomes instead of a maximum of 12 pairs using PGD-FISH. PGD-CGH may require the cryopreservation of embryos while their cells are being tested; normal embryos are identified, thawed and transferred to the patient typically at her next ovulation cycle.
The method of analysis for gene disorders is called polymerase chain reaction (PCR). PCR involves a technique that greatly amplifies the genetic code contained in a single blastomere, so that the specific gene or genes being looked for can be detected. Preimplantation genetic diagnosis is significantly enhanced by the use of PCR. Examples of hereditary conditions caused by gene disorders that PCR can help detect include:
Until the development of PGD, assisted reproductive technology labs could rely only on the appearance of pre-embryos to decide which ones were suitable for implantation into the patient's uterus. The advent of PGD proved that normal-appearing pre-embryos frequently have an abnormal number of chromosomes, rendering them incompatible with the development of a normal pregnancy.
In summary:
Indeed, the use of PGD by the fertility specialists at the Southern California Reproductive Center has been instrumental in bringing many babies into the world.
While manipulating and handling embryos will always have some measure of risk, it is important to note that our center has the most extensive experience of any in the USA. The real risk is in NOT using PGD, and then having a miscarriage or carrying a child to term with a serious genetic disorder that could have been detected through PGD testing.
The cost of PGD depends on the specific types of tests desired or requested (see above for the variety of genetic tests that comprise the PGD process). At SCRC, we are able to offer you several different financing plans to make the cost manageable and affordable. Please talk to one of our staff members for details.
In 1999, the genetic code of an entire human chromosome was sequenced (mapped). This revolutionary development in medical science allowed the continuing discovery of the sequence of the code that comprises specific units of genetic information. Genes are responsible for directing the construction of every cell in our body, down to the tiniest molecular detail. Therefore, it is reasonable to expectthat the function of all genes, and the detection of abnormal genes, eventually will be categorized. This knowledge may in turn be used to reduce or eliminate susceptibility to hereditary disorders, infectious diseases, and cancer. Someday, only a single pre-embryo will be needed to establish a pregnancy — and it will be a healthy pregnancy.
Fertility 101 450 North Roxbury Drive
6th Floor Screening Room
Beverly Hills, CA 90210 Make a reservation


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Critics' Pick
(No longer in theaters)
Daryl Wein, David Oliver Cohen
Regent Releasing/here! Films
Aug 15, 2008
LA (Academy Run)
Riveting portrait of Richard Berkowitz, the S&M hustler turned AIDS activist who sounded the alarm bell in the eighties. Despite the important issues being tackled, the larger-than-life Berkowitz carries the most weight.


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Lions Hosting Free Agent DL Mike Patterson For A Visit
Jason La Canfora of CBS Sports reports that the Lions are meeting with free DL Mike Patterson on Wednesday. La Canfora mentions that Patterson would give them some interior defensive line depth while also being reunited with DL coach Jim Washburn. This the first reported interest in Patterson since free agency opened well over two months ago. ... The post Lions Hosting Free Agent...
Via NFL Trade Rumors
May 27, 2015 | Discuss
Does the New York Giants' Defense have a Leader?
Mike Patterson #93 and Johnathan Hankins #95 of the New York Giants celebrate a stop against the Washington Redskins during their game at MetLife Stadium on December 14, 2014 in East Rutherford, New Jersey. (Getty Images) Over the past two offseasons, the New York Giants have lost both of their defensive captains. Last year, they lost veteran and fan favorite, defensive end Justin...
Via The Sports Journal
April 22, 2015 | Discuss
Giants re-sign Patterson, ink Bowman
EAST RUTHERFORD, N.J. (AP) The New York Giants re-signed defensive tackle Mike Patterson and added cornerback Zack Bowman on Monday.
Via FOXSports.com
March 31, 2014 | Discuss
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Science Olympiad Competition
Science Olympiad Delegate Registration Form
Teachers, print this form, fill it out, and mail it to Tina Gilliland.
To provide delegates a fun, hands-on Olympiad style activity and give recognition to students and schools that excel.
One team of two students from each school, referred to as "Olympiad delegates."
The Science Olympiad Competition for this year will be Physics Lab. Download the competition rules
- Top two teams will receive certificates.
- First place team will receive plaques.


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Carrera Sprint Top
Code: WCST2
Price: $78.00
Click on the smaller images to view as large.
Click on large image to view close-up.
This newly designed full-length top for our 2015 line covers the mid-section and extends down to the hips with subtle ruching on the hips. It has three pockets on the lower back panel. More fitted than previous years, designed to hold objects securely in pockets, even while running. Lower neckline allows for less constriction, along with T back for maximum flexibility while swimming. Provides a flattering look for all body types.
Made of breathable Carrera™ Skin body, Skin Cooler™ Stretch, and Microlock™ stitching (see Fabric Facts) provide coverage while keeping you cool. The built-in bra suspended from the shoulders is made of Carrera™ Skin, the same fabric from which the entire garment is made, therefore it is very supportive, yet the second layer of mesh provides breathability.
Although support is very individual, this top is generally considered moderate support, and is recommended for up to a C cup. The lycra finish around the neck and armholes provide additional support, comfort and style.
This item is not designed for repeated use as a swim suit in a chlorinated pool.
Fit: Form, Support: Moderate
Colors: Black; Black/ShellRainbow Print; White/Shell Rainbow Print; Fijian Teal; Orange Dream


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The Two Americas 1900 (iPad Idea #9) by DaFreak47Watch
- AB Absaroka
CA - California
CO - Colorado
CT - Connecticut
CU - Columbia
DA - Dakota
DE - Delaware
EI – Edward Island
GP - Gaspesia
HD - Hudson
HU - Huron
IA - Iowa
ID - Idaho
IL - Illinois
IN - Indiana
KA - Kanawha
KS - Kansas
MA - Massachusetts
MB - Manitoba
MD - Maryland
ME - Maine
MI - Michigan
MN - Minnesota
MO - Missouri
MO - Montreal (Oops I'm too lazy to change it to ML)
MT - Montana
NB - New Brunswick
NE - Nebraska
NH - New Hampshire
NJ - New Jersey
NS - New Scotland
NV - Nevada
NY - New York
OH - Ohio
ON - Ontario
OR - Oregon
PA - Pennsylvania
QC - Quebec
RI - Rhode Island
SK - Saskatchewan
SU - Superior
UT - Utah
VC - Vancouver
VT - Vermont
WA - Washington
WI - Wisconsin
AL - Alabama
AR - Arkansas
CH - Chihuahua
CR - Costa Rica
DG - Durango
ES - El Salvador
FL - Florida
GA - Georgia
GU - Guatemala
HS - Honduras
KY - Kentucky
LA - Louisiana
MS - Mississippi
NA - Nicaragua
NC - North Carolina
OZ - Ozark
RG - Rio Grande
SC - South Carolina
SO - Sonora
TN - Tennessee
TX - Texas
VA - Virginia
YU - Yucatan
had Texas remained outside the Confederacy it would have immediately retaken its prior claim to all land on the east side of the Rio Grande in 'New MEXICO and Arizona' , would definitely taken the Northern Mexico provinces save Baja, but I'm doubtful of Durango being included.
the Republic of California would have added Nevada and Western Idaho, while the free state of Utah would have taken eastern Nevada and maybe that part of Arizona state above the divide line, with Santa Fe area being added to the state of Colorado.
thus there would be four to six United States.
or, if the French had made peace with Germany before 1870, then the Brits may have sold western canada to the North allowing the north to reannex California and forcing Utah back into its fold, while the Confederacy would have reacted by annexing Texas back and forcing Georgia-Florida back into its fold.
Once one gets started on this there are so many wonderful variables.
1) in 1842 the Yucatan was a separate republic and the USA actually discussed annexing it instead of Texas. Thus had that happened, you might have a separate republic of Texas, albeit tied economically with the Confederacy.
2) in the 1850's there was serious talk by the USA annexing 'Santo Domingo', this would have been the Spanish side of the island of Hispaniola. It would be interesting if the North had managed to hold onto it while the Confederacy annexed Haiti.
3) had the so- called Pig War in the Puget Sound allowed the British to take over what is Washington state and the panhandle of Idaho, then Russian dominance in alaska would have kept Ft. Ross (Mendocino) in California but lost the the Alaskan panhandle islands to the Brits,who, thru their Hudson Bay Company would have kept the prairie Provinces. The lower Canadian provinces would probably have elected to be annexed by the US, otherwise a war would have to have been won by the North against the Brits, which would seem unlikely unless the North gave concessions to France such as Newfoundland and islands in the Caribbean.
4) it is unlikely that Kentucky east of the Kentucky river and Tennessee northeast of Knoxville would have remained in the Confederacy as these areas were extremely pro-Union. Your divide line of Missouri seems correct but the far northeast corner of Oklahoma would have stayed with the North. Also Georgia and Florida were never 100% loyal to the idea of a Confederacy and they may have indeed bowed out probably by 1880 due to economic reasons.
5)I don't believe the Confederacy would have moved across the Atlantic and taken Spanish Sahara, but Sierre Leone would be feasible, along with Gabon and flexing its muscle against the German activity along the Gold Coast.
6) The Republic of California would have pulled out of the USA after the war taking Baja and Oregon with it. It would have moved into the Pacific and taken Hawaii, Phillippines, Samoa, and again some of the German islands off Australia.
7) Doubtful the USA would have put up with Quebec, allowing it to be a puppet state tied economically to it.
8)all this assumes that France was rightly kicked out of Mexico, and the British interests in Belize and the Mosquito Coast were
taken over by an expansive Confederacy. One that would have (whether it retained Texas or not) a sizeable Spanish speaking minority. The Confederate Constitution stated that slavery was perpetual, but no slaves could be imported into the states, however, annexation of slave holding areas was allowed. The Mexican provinces outlawed slavery as did the Spanish. However, it remained in Portugal which took hold of the Amazon area when they realized the Spanish had no interest in it. A Confederate move into Amazon against a rather poor Portugal is feasible.
9) Lincoln (assuming he lived) may have wanted to keep the Capital in DC but it is unlikely his successors would have, Philadelphia being the best spot. until some time had healed some wounds and the capital moved back to DC, probably in time for the 1900 elections.
overall, very good concept. look forward to your next effort.
2) Could have been, but it wouldn't have been extremely smart. It would have to enter waters dominated by the Confederates, British, and French, and there wasn't exactly an external motivation to annex it, seeing as how they didn't need a place to send the freed slaves.
3) Also not really relevant. Sorry, its been a while and I'm not really up to a lot of speculation at the moment.
4) Nothing is 100%. Sorry, I'm lazy right now.
5) Western Sahara was the only thing that it really could take. It wasn't about to start snatching up colonies from the British and French, its' powerful allies.
6) Seriously though. You can make a map. I've actually made multiple maps of this sort of scenario, but I'm just so tired right now.
7) Sure. Sounds good.
Sorry man. You might have to wait until the summer to get a real discussion out of me. I sadly don't have the time at the moment.
Philadelphia is the most likely new capital for the Union, away from the Confederate border to full of American history.
I would say that Atlanta would be the most likely new capital of the CSA. It was proposed before it was moved to Richmond, it was at the relative center of the country, and it wasn't a state capital.
Atlanta, in terms of today's standards, would be a good choice for a capital after the war. It is an economic power in the South today.
Thanks for the insight!
Same name and everything (not that I'm implying you copied me or anything)! I think I like yours better though.


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Anime and Manga
- Ranma ½
- Kasumi confront Ranma after he'd once again insulted Akane on her appearance, saying he needed to apologize and cheer her up. When he needs to know why, she replies that while Akane may be stubborn, awkward and tomboyish... "she's still a girl."
- Ranma himself is an excellent example. Though he believes himself handsome in either form, insulting his looks as a man will merely annoy him. Insulting his looks as a woman will send him into an absolute berserker rage.
- Mumu Momoyama in ChocoMimi is the girliest-looking member in the group and also the vainest character in the series. He's often at odds with Mimi over who is The Cutie, and even told off Bambi when he noticed she looked more feminine with long hair.
- Vandread: Men and women both exist on two seperate planets, one with an abundance of resources, and one with hardly any. The men's world is therefore much less advanced and has no concept of holidays, luxury, or design as anything but practical. As such, they have become highly resourceful learning to do as much as they can with as little as they can. By contrast the womens planet is far more advanced and plentiful. However, they take their vanity to the extreme, wasting their resources thoughtlessly. One example is making their homes nicer looking than their neighbour's, which resulting in blackouts the likes of which caused many of the space pirates to lose their home.
Comic Books
- The Mighty Thor has The Enchantress, a Vain Sorceress whose entire identity (and much of her power set) flow directly from her epic, supernatural beauty, and its effect on both men and gods. Her vanity (though certainly not unfounded) is nearly as legendary as her beauty, and she never hesitates to mock women who are not as attractive (Jane Foster) or who she sees as too 'mannish' for any male to find appealing no matter what their actual appearance (The warrior goddess Sif). The comic itself seems to be of two minds regarding The Enchantress: On the one hand, she is most often treated as a shallow, selfish and bratty annoyance by many of the more powerful Asgardians. On the other hand, her exquisite face and body do give her immense influence over most males, be they god, human or superhuman, and even such wise individuals as Heimdal (and, occasionally Thor) have either succumbed to her wiles, or sought them out willingly. So, basically, the excessively vain girl is silly, petty, and should be dismissed accordingly... but she happens to be so genuinely, insanely hot that in practice she usually gets exactly who and what she wants.
- In the Sonic the Hedgehog issue where Sally cuts her hair and coyly asks Sonic if he likes it, he responds that he'd never known her to be "so... girly." (Ironically this was intended as a sign of her de-Chickification, which had had her mooning and crying and generally being passive and ineffective.)
- In Heroes And Villains, Buffy's pre-Sunnydale personality carries through, unchanged by her awakening powers and the trauma of her battles. As a result, we get a heroine who is conceited, bratty, and shamelessly obsessed with her beauty. That being said, she can still totally destroy you with her nothing but her dainty, perfectly manicured hands, so watch your step.
- Troop Beverly Hills uses this comedically and positively. Phyllis and all her girls are vain, and are able to charm a female judge by complimenting her. When Annie does her HeelFace Turn, it is accompanied by a new and more flattering wardrobe. The villainess Velda is plain, mannish, and cruel, plainly uncomfortable the one and only time she's seen in a very conservative dress. She is portrayed as a bad mother (who doesn't even like to be addressed as such), and her unattractiveness is made fun of.
"Or we could leave her here... to be toyed with by lonely mountain men. [Glances at Velda.] Really lonely mountain men."
- 10 Things I Hate About You:
Are you telling me I'm not a pretty guy?
- Used humorously when feared bad-boy Patrick (played by then-relatively-unknown Heath Ledger) is told Katerina prefers "pretty guys."
- The nastier version comes into play with male model Joey, a Jerk Jock who winds up getting his comeuppance via a thrashing from the petite Bianca.
- Dr. Frank N. Furter from the The Rocky Horror Picture Show. He's extremely vain and does have a feminine (if rather harsh and demanding) personality to him.
Whatever happened to Fay Wray?That delicate, satin-draped frame?As it clung to her thighHow I started to cry`cause I wanted to be dressed just the same.
- Genderflipped in Casino Royale (2006) with a scene of Bond checking himself out in the mirror after Vesper gets him an exquisitely-fitted dinner jacket.
- In Terminator 3: Rise of the Machines, the T-X (a female "Terminatrix") walks past a mirror while battling the male T-850, and her head immediately whips to the side for as long as she's reflected in it. There was no reason offered for why she'd do this in the middle of a fight (aside from the obvious point of this trope) and it happens so fast that many viewers likely missed it.
- In A Brother's Price Keifer Porter was very vain, and very evil, a gender-flipped variant A of the trope. Then it is somewhat inverted with Corelle, who lets her hair grow longer to impress the neighbour boy. Her elder sister tells her to cut it - only the boys are allowed to have impractical long hair.
- The Wheel of Time. Some women are more inclined to it than others, but this always bears out as a cultural thing, where some societies encourage or discourage such behavior. A great deal is made of female hypocrisy as the characters look down on women who blatantly play up to male desire, but ultimately they all do it, deliberately embracing it after circumstance or jealousy drives them to it. This is seen as the natural and correct state of the world, as women who don't cater to male attention are even more underhanded and often outright villainous.
- The Narnia books have a fair amount of this. The otherwise down to earth Polly immediately starts to trust Diggory's Obviously Evil uncle after he calls her pretty. Lucy, generally shown as more virtuous than her older and vainer sister Susan, is so tempted by the idea of being more beautiful and desirable than her that only the appearance of Aslan stops her from casting a spell allowing her to do so.
- Xanth takes the All Women Are Vain and All Men Are Perverts approach. Xanth's archaic prohibition against female rulers is presented as unfairly sexist, but the concept that all women desire to be considered beautiful more than almost anything else, and enjoy being seen as beautiful more than the promise of privacy, is inoffensive and simple truth.
A pretty girl could express shock and distress if someone saw her bare torso, but privately she would be pleased if the reaction were favorable.
- Harry Potter:
- Gender flipped with Gilderoy Lockhart who is extremely attractive and extremely vain. He's unable to get through a sentence without talking about how awesome he is. He eventually proves to be a lying, ineffectual coward whose triumphs are a scam. Vanity is bad, in this case, but not a specifically feminine quality.
- Inverted with Hermoine. She dresses up for The Yule Ball and considered it too much of a hassle to do again.
- The Belgariad plays with this trope. Certainly no female is established as neglecting her physical appearance when she had any other option available. While 7000-year-old Belgarath appears as an old man (and in fact takes care to look like a vagabond), his 3000-year-old daughter Polgara appears eternally 20 — by (subconsciousnote — the idea only comes up in The Malloreon, and it's explicitly just a theory) choice, since while an elderly male'' sorcerer may appear learned and formidable an elderly female sorceress would be seen as a crone. As a child she kept herself filthy and unkempt but after her sister's marriage she came out of her shell and went to the opposite extreme entirely; constantly bathing, preening, and dressing flatteringly.
- Joanne Bertin's The Last Dragonlord has the Lady Sherrine, her mother Anstella, and Mauryanna all be exceedingly interested in looks. Sherrine and Anstella have a rivalry based on who is the fairest, and all interactions between the three have clear jealous undertones. These are also the only female characters to display any sexuality; all others in the book are children, old, dwarfs, or more interested in food.
- In Sarah Addison Allen's The Girl Who Chased The Moon, Emily's mother Dulcie had squelched her objections to an ugly photo of her to discourage vanity.
- In Andre Norton's Warlock series, both heroines have brief moments of concern about their looks
- Ordeal in Otherwhere: the prospect of looking more feminine than was allowed on Demeter cheers Charis up, though she is effectively a slave. She objects to the notion of too garish an appearance.
- Forerunner Foray: Ziantha toys the notion of having her nondescript appearance changed for good as her reward.
- Journey to Chaos: This trope is averted by Ataidar's Royal Ordercraft Security and Compliance Team. They don't carry hand mirrors to check or correct their beauty. They are for monitoring their progression of silver-grey hairs which mark the level of ordercraft corruption within them. They are all professionals.
Live Action TV
- The hosts of What Not to Wear take clients (mostly female), who don't wear flattering clothes or apply makeup and then do their very best to assert that this lack of vanity is due to some very serious psychological issues and that the only cure is to take over their wardrobe and convince them otherwise. Men are given the treatment too, but without the psychological aspect. Men not caring about their appearance is just slovenly; Women not caring is a denial of their very gender.
- Queer Eye For The Straight Guy: Straight, "masculine" men are not expected to know about matters of style and taste, but gay men can be their tutors.
- Played with in Frasier, where not only Frasier and Niles' excessive vanity about their clothes and grooming, but simply the fact that they have good taste and style, is seen as effeminate and therefore undesirable. This is despite the fact that they always look good because of this — oh no, men are supposed to just accidentally throw on random clothes that they happen to look dashing in.
- Played with in Community: Jeff, while known for being obsessed with his appearance, tries to make said obsession look as casual as possible.
- In Star Trek: The Original Series, all of the female characters were very pretty, and Uhura was by far the most vain of the main cast. When they were all tempted into staying behind on a land run by robots, Spock was offered great knowledge and opportunity for learning, McCoy was offered great medical facilities, Chekov was offered beautiful robot women to obey his every command, and Uhura was offered eternal youth. Even more obviously, in And The Children Shall Lead the characters' worst fears were shown: Kirk's was losing command, Sulu's was facing certain death that he had to maneuver the ship out of, and Uhura's was...being old and ugly.
- Extreme Male Beauty: On the one hand, the presenter Tim Shaw examines how vanity has become more commonplace amongst men today and reveals that straight manly men can be just as vain as gay men. On the other hand it's criticising the model industry in every other scene and the final episode hammers home the Aesop that a man who takes pride in his appearance will come across as fake and arrogant and should have that kind of thinking stamped out of him.
- The Bridge Bunnies of UFO all carry a shiny metal pouch on the belt of their catsuits. In one episode it's revealed that the box contains not a high-tech Everything Sensor or repair tools for Zeerust computer equipment, but a pop-up mirror and makeup kit!
- Many of the versions of the Doctor in Doctor Who are ridiculously vain as a rule, and convinced whatever ridiculous crap they choose to wear looks absolutely amazing on someone as fantastically good-looking as them. This is not used in the show itself to feminise the character (besides some throwaway lines by the snarkier companions) and is mostly just a facet of his general weirdness, but some fans interpret it as Camp behaviour and consider it part of the reason for the show's legendary LGBT Fanbase.
- Shania Twain's song "That Don't Impress Me Much" says vanity in men is unattractive but in the next verse is says machoness is also a turn off.
I never knew a guy who carried a mirror in his pocketAnd a comb up his sleeve - just in caseAnd all that extra hold gel in your hair oughta lock it'Cause Heaven forbid it should fall outta place
- Katy Perry's "You're So Gay":
I can't believe I fell in love With someone that wears more make up and...Cue the chorus: You're so gay and you don't even like boys.
- Demi Lovato's "Heart Attack":
But you make me want to act like a girlPaint my nails and wear high heels
Religion and Mythology
- Narcissus of ancient Greek myth makes this Older Than Feudalism, in fact as the root of the word "Narcissist" he might even count as the Ur-Example. He is vain to the point of starving to death because he couldn't tear himself away from admiring his reflection.
- In some versions of the tale he drowned while trying to make love to his own reflection and his body became the first Daffodil (scientific name Narcissus).
Tabletop RPG
- Paranoia adventure "Send in the Clones". The Teela O'Malley clones in the final battle are dangerous opponents. However, they can be neutralized by giving them a small mirror, which causes them to primp and fuss with their hair and check their eyeliner and complexion.
- Warhammer and Warhammer 40,000: Followers of Slaanesh are the only ones who give any attention to their appearance, and are directly opposed by devotees of Khorne, who are of the brutal, real-men-don't-wear-makeup-or-wash-themselves persuasion (Sigvald the Magnificent has a special rule where his entire unit stops moving so he can admire his reflection on their polished shields). Slaanesh being both male and female (and not always at the same time), many of his champions and up partially hermaphroditic as well.
- Subverted in the case of Lucius the Eternal, 40K's champion of Slaanesh. He was once the prettiest of the Emperor's Children (the Legion that would eventually turn itself over to Slaanesh), but a fight with a Space Wolf broke his nose in a way that couldn't be fixed, and later acquired facial scars in battle. This pretty much broke his mind, now he actually seems to seek out disfiguring scars when fighting, and his face looks like it's been used as a tic-tac-toe board since.
Video Games
- Chrono Cross's Pierre is first met admiring himself in the mirror, and joins your party stating they will be the thorns decorating his lovely rose. He turns out to be Miles Gloriosus; a phony and all but useless in combat. However, if you get him a complete set of 'Hero' equipment, he becomes Agent Peacock. This only works for him.
- Sonic Lost World has Zeena of the Deadly Six, who largely cares more about doing her nails and makeup than helping her teammates take care of Sonic. Sonic, being Sonic, takes the time to mock her about it:
Zeena: "The last time we met, you ruined my nail art. Now I have to reapply a whole new coat."
Sonic: "Oh, my gosh, are you serious?! I am so, so sorry."
Zeena: "Oh! Well, in that case..."
Sonic: "Uh, no. What I meant to say is I am so sorry that you have nothing better to do in life!"
- Dynasty Warriors has Zhang He, the Ambiguously Gay officer of the Wei kingdom who is comically obsessed with beauty in almost all forms.
Western Animation
- The Smurfs: Vanity Smurf fits the bill; a narcissist never seen without a mirror at hand. Naturally, he is Ambiguously Gay.
- The narcisstic Peacock from Polish animated series Hip Hipand Hurra. While he has a very manly voice, he's not only very feminine but tends to faint every single time his beautiful tail gets dirty.
- A Hey Arnold! episode plays around with this when the girls throw a makeover party and deliberately exclude the tomboyish Helga. When Helga tries to play with the boys instead, they mock her for being ugly and unfeminine. Helga caves and dolls herself up, then joins the other girls at the party. After a while, she starts to realize how ridiculous the whole thing is, considering their age. "We're nine years old! We don't have signs of aging!" She persuades the other girls to her side... and they wind up administering the intended makeover to one of the unfortunate boys who tried to crash their party and found himself outmatched.
- Avatar: The Last Airbender: Toph is a complicated case. After joining The Team, she was the only one who wouldn't join the morning grooming session. Being blind, she's less concerned with visual appearances than most people. When Katara said that she was dirty, she called it a 'healthy coating of earth' (which also makes sense since she's a Earth-Bending prodigy that relies on the sensory aspect of her powers to compensate for her lack of sight). Despite this, she hides a side that wants to be pretty, was deeply hurt by girls mocking her appearance, and shared a bonding experience with Katara as they went to a spa.
- Neil, descendant of Narcissus, from Class of the Titans. Like his ancestor, he's exceedingly vain and spends half the episodes he's in admiring his own reflection. This coupled with his problems wielding weapons, fashion expertise and tendency to emit a high-pitched girlish scream when frightened makes him a part of this trope.