Title of Invention	A PROCESS TO OLIGOMERIZE OLEFINS
Abstract	A process to oligomerize olefins in the presence of an oligomerization catalyst sytem, comprising contacting said catalyst system with an alpha olefin, at a reaction temperature within a range from 0 C to 250 C and at a reaction pressure within a range from atmospheric to 2500 psig wherein said oligomerization catalyst system is prepared by contacting a halogenated alkylaluminum metal alkyl and a pyrrole-containing compound in the presence of a unsaturated hydrocarbon to form a halogenated alkylaluminum metal alkyl/pyrrole mixture; and contacting said halogenated alkylaluminum metal alkyl/pyrrole mixture with a chromium source to form said catalyst system.

Title of Invention

A PROCESS TO OLIGOMERIZE OLEFINS

Abstract

A process to oligomerize olefins in the presence of an oligomerization catalyst sytem, comprising contacting said catalyst system with an alpha olefin, at a reaction temperature within a range from 0 C to 250 C and at a reaction pressure within a range from atmospheric to 2500 psig wherein said oligomerization catalyst system is prepared by contacting a halogenated alkylaluminum metal alkyl and a pyrrole-containing compound in the presence of a unsaturated hydrocarbon to form a halogenated alkylaluminum metal alkyl/pyrrole mixture; and contacting said halogenated alkylaluminum metal alkyl/pyrrole mixture with a chromium source to form said catalyst system.

Full Text	- 1 - OLEFIN PRODUCTION This invention relates to olefin production. Olefins, primarily alpha-olefins, have many uses. For example, alpha-olefins, such as 1-hexene, can be used in hydro formulation (OXO processes). In addition to uses as specific chemicals, alpha-olefins also can be used in polymerization processes as either a monomer or comonomer to prepare polyolefins, or polymers. Several methods of producing olefins are known in the art These processes include catalyzed dimerization and trimenzation processes. Usually, these olefin production processes are exothermic reactions and can generate significant amounts of heat. Furthermore, preparation of dimerization and tnmerization catalyst systems are exothermic reactions and heat needs to be removed from the process Heat removal requires additional, often expensive, equipment and heat can be detrimental to the activity, productivity and selectivity of the resultant catalyst system Prior patents have taught in-situ catalyst system preparation, wherein the catalyst system is prepared in-situ in a tnmenzation reactor For example, see U.S 5,198,563 and U.S. 5,288,823 This invention provides improved olefin production processes, such as improved olefin oligomerization and tnmenzation processes. The invention further provides a more efficient catalyst system production process. The present invention yet further provides improved heat control of the catalyst system preparation process The invention also deals with a continuous process to prepare olefin oligomerization or tnmenzation catalyst systems In accordance with this invention, a process is provided which comprises prepanng an olefin oligomerization or tnmenzation catalyst system and producing olefins in the presence of the olefin oligomerization or trimenzaiion catalyst system and a solvent, wherein said catalyst system preparation comprises the steps of first contacting a chromium source and a pyrrole-contaming compound to form a chromium/pyrrole mixture; second, contacting said chromium/pyrrole mixture with a metal alkyl to form a catalyst system; and then contacting said -2-catalyst system with an alpha-olefin, preferably ethylene. In accordance with another embodiment of this invention, a process is provided which comprises preparing an olefin oligomerization or trimerization catalyst system and producing olefins in the presence of the olefin oligomerization or trimerization catalyst system and a solvent, wherein said catalyst system preparation comprises the steps of first contacting a metal alkyl and a pyrrole-containing compound to form a metal alkyl/pyrrole mixture; second, contacting said metal alkyl/pyrrole mixture with a chromium source to form a catalyst system; and then contacting said catalyst system with an alpha-olefin, preferably ethylene. In accordance with yet another embodiment of this invention, a process is provided which consists essentially of preparing an olefin oligomerization or trimerization catalyst system and producing olefins in the presence of the olefin ohgomenzation or trimerization catalyst system and a solvent, wherein said catalyst system preparation comprises the steps of first contacting a chromium source and a pyrrole-containing compound to form a chromium/pyrrole mixture; second, contacting said chromium/pyrrole mixture with a metal alkyl to form a catalyst system; and then contacting said catalyst system With an alpha-olefin, preferably ethylene In accordance with still another embodiment of this invention, a process is provides which consists essentially of preparing an olefin oligomerization or trimerization catalyst system and producing olefins in the presence of the olefin oligomerization or trimerization catalyst system and a solvent, wherein said catalyst system preparation comprises the steps of first contacting a metal alkyl and a pyrrole-containing compound to form a metal alkyl/pyrrole mixture, second, contacting said metal alkyl/pyrrole mixture with a chromium source to form a catalyst system; and then contacting said catalyst system with an alpha-olefin, preferably ethylene. Catalyst Systems Catalyst systems useful in accordance with this invention comprise a chromium source, a pyrrole-containing compound and a metal alkyl, all of which have been contacted and/or reacted in the presence of an unsaturated hydrocarbon. Optionally, these catalyst systems can be supported on an inorganic oxide support. - 3 - These catalyst systems are especially useful for the oligomerization of olefins, such as, for example, ethylene to 1-hexene. As used in this disclosure, the term "oligomerization" broadly encompasses the combination of two olefins (dimerization) to form an olefinic product, combination of three olefins (trimerization) to form an olefinic product and combination of more than three olefins to form an olefinic product, but does not include polymerization of olefins. An ohgomer can be defined as a compound made up of repeating units, whose properties can change with the addition or removal of one or a few repeating units. The properties of a polymer do not change markedly with such a modification The chromium source can be one or more organic or inorganic chromium compounds, wherein the chromium oxidation state is from 0 to 6. If the chromium oxidation state is 0, metallic chromium can be the chromium source. Generally, the chromium source can have a formula of CrXn, wherein X can be the same or different and can be any organic or inorganic radical, and n is an integer from 1 to 6. Exemplary organic radicals can have from about 1 to about 20 carbon atoms per radical, and are selected from the group consisting of alkyl, alkoxy, carboxy, ester, ketone, and/or amido radicals The organic radicals can be straight-chained or branched, cyclic or acyclic, aromatic or aliphatic, can be made of mixed aliphatic, aromatic, and/or cycloaliphatic groups. Exemplary inorganic radicals include, but are not limited to halides, sulfates, and/or oxides. Preferably, the chromium source is a chromium( II) -containing and/or a chromium(III)-containing compound which can yield a catalyst system with improved oligomerization and/or trimerization activity. Most preferably, the chromium source is a chromium(III) compound because of ease of use, availability, and enhanced catalyst system activity. Exemplary chromium(III) compounds include, but are not limited to, chromium carboxylates, chromium naphthenates, chromium halides, chromium pyrrolides, and/or chromium dionates Specific exemplary chromium(III) compounds include, but are not limited to, chromium(lll) 2,2,6,6,-tetramethylheptanedronate [Cr(TMHD)3], chromium(III) 2-ethylhexanoale also called chromium(III) tris(2-ethylhexanoate) [Cr(EH)3], chromium(IIl) naphthenate [Cr(Np)3], chromium(III) chloride, chromium (III) bromide (chromic bromide), chromium (III) fluoride (chromic fluoride), chromium(III) acetylacetonate, - 4 - chromium(III) acetate, chromium(III) butyrate, chromium(III) neopentanoate, chromium(III) laurate, chromium(III) stearate, chromium (III) pyrrolides and/or chromium(III) oxalate. Specific exemplary chromium(II) compounds include, but are not limited to, chromous bromide, chromous fluoride, chromous chloride, chromium(II) bis(2- ethylhexanoate), chromium(II) acetate, chromium(II) butyrate, chromium(II) neopentanoate, chromium(II) laurate, chromium(II) stearate, chromium(II) oxalate and/or chromium(II) pyrrolides. The pyrrole-containing compound can be any pyrrole-containing compound that will react with the chromium source to form a chromium pyrrohde complex. As used in this disclosure, the term "pyrrole-containing compound" refers to hydrogen pyrrohde, i.e., pyrrole (C4H5N), derivatives of hydrogen pyrrohde, substituted pyrrolides, as well as metal pyrrohde complexes. A "pyrrolide", as used in this disclosure, is defined as a compound comprising a 5-membered, nitrogen-containing heterocycle, such as for example, pyrrole, derivatives of pyrrole, and mixtures thereof. Broadly, the pyrrole-containing compound can be pyrrole and/or any heteroleptic or homoleptic metal complex or salt, containing a pyrrohde radical, or ligand. The pyrrole-containing compound can be either affirmatively added to the olefin production reaction, or generated in-situ. Generally, the pyrrole-containing compound "will have from about 4 to about 20 carbon atoms per molecule. Exemplary pyrrolides include, but are not limited to, and are selected from the group consisting of hydrogen pyrrolide (pyrrole), lithium pyrrohde, sodium pyrrohde, potassium pyrrolide, cesium pyrrolide, and/or the salts of substituted pyrrohdes, because of high reactivity and activity with the other reactants. Examples of substituted pyrrohdes include, but are not limited to, pyrrole-2-carboxyhc acid, 2-acetylpyrrole, pyrrole-2-carboxaldehyde, tetrahydromdole, 2,5-dimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 3-acetyl-2,4-dimethylpyrrole, ethyl-2,4-dimethyl-5-(ethoxycarbonyl)-3-pyrrole-propionateJ ethyl-3,5-dimethy)-2-pyrrolecarboxylate] and mixtures thereof When the pyrrole-containing compound contains chromium, the resultant chromium compound can be called a chromium pyrrohde. The most preferred pyrrole-containing compounds used in preparation -5 - of a trimerization catalyst system are selected from the group consisting of hydrogen pyrrolide, i.e., pyrrole (C4H5N), 2,5-dimethylpyrrole (2,5-DMP) and/or chromium pyrrolides because of enhanced olefin production activity, selectivity and/or purity. Optionally, for ease of use, a chromium pyrrolide can provide both the chromium source and the pyrrole-containing compound. As used in this disclosure, when a chromium pyrrolide is used to form a catalyst system, a chromium pyrrolide can be considered to provide both the chromium source and the pyrrole-containing compound. While all pyrrole-containing compounds can produce catalyst systems with high activity and productivity, use of pyrrole and/or 2,5-dimethylpyrrole can produce a catalyst system with enhanced activity and selectivity to a desired product The metal alkyl can be any heteroleptic or homoleptic metal alkyl compound. One or more metal alkyls can be used. The alkyl hgand(s) of the metal alkyl can be any aliphatic and/or aromatic radical. Preferably, the alkyl ligand(s) are any saturated or unsaturated aliphatic radical The metal alkyl can have any number of carbon atoms per molecule. However, due to commercial availability and ease of use, the metal alkyl usually will comprise less than about 70 carbon atoms per metal alkyl molecule and preferably less than about 20 carbon atoms per molecule Exemplary metal alkyl compounds include, but are not limited to, alkylaluminum compounds, alkylboron compounds, alkylmagnesium compounds, alkylzinc compounds and/or alkyl lithium compounds. Exemplary metal alkyls include, but are not limited to, n-butyl lithium, sec-butyllithium, tert-butyllithium, diethylmagnesium, diethylzinc, triethylaluminum, trimethylaluminum, trisobutyl-alumium, and mixtures thereof. Preferably, the metal alkyl is selected from the group consisting of non-hydrolyzed, i e., not pre-contacted with water, alkylaluminum compounds, derivatives of alkylaluminum compounds, halogenated alkylaluminum compounds, and mixtures thereof for improved product selectivity, as well as improved catalyst system reactivity, activity, and/or productivity. The use of hydrolyzed metal alkyls can result is decreased olefin, i e., liquid, production and increased polymer, i.e , solid, production. Most preferably, the metal alkyl is a non-hydrolyzed alkylaluminum -6- compound, expressed by the general formulae A1R3, A1R2X, A1RX2, A1R2OR, A1RXOR, and/or A12R3X3, wherein R is an alkyl group and X is a halogen atom. Exemplary compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylalumimim, diethyl aluminum chloride, diethylaluminum bromide, diethylaluminum ethoxide, diethylaluminum phenoxide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof for best catalyst system activity and product selectivity. The most preferred alkylaluminum compounds are triethylaluminum (TEA) and diethylaluminum chloride (DEAC); TEA is used for best results in catalyst system activity and product selectivity and DEAC is used for best results in catalyst product purity and selectivity. While not wishing to be bound by theory, it is believed that a chloride containing-compound can improve product purity and selectivity. Any chloride-containing compound can be used, such as, for example, DEAC and organo chlorides Exemplary organochlorides include, but are not limited to, carbon tetrachlonde,methylene chloride, chloroform, benzylchloride, l-hexachloroethane and mixtures thereof Usually, contacting and/or reacting of the chromium source, pyrrole-containing compound and metal alkyl is done in the presence of an unsaturated hydrocarbon. The unsaturated hydrocarbon can be any aromatic or aliphatic hydrocarbon, in a gas, liquid or solid state. Preferably, to affect thorough contacting of the chromium source, pyrrole-containing compound and metal alkyl, the unsaturated hydrocarbon will be in a liquid state. The unsaturated hydrocarbon can have any number of carbon atoms per molecule. Usually, the unsaturated hydrocarbon will comprise less than about 70 carbon atoms per molecule, and preferably, less than about 20 carbon atoms per molecule, due to commercial availability and ease of use. Exemplary unsaturated, aliphatic hydrocarbon compounds include, but are not limited to, ethylene, 1-hexene, 1,3-butadrene, and mixtures thereof. The most preferred unsaturated aliphatic hydrocarbon compound is 1-hexene, because of elimination of catalyst system preparation steps and 1-hexene can be a reaction product. Exemplary unsaturated aromatic hydrocarbons include, but are not limited to, benzene, toluene, ethylbenzene, xylene, rnesitylene, hexamethylbenzene, and mixtures thereof. Unsaturated, aromatic hydrocarbons are - 7- preferred in order to improve catalyst system stability, as well as produce a highly active and selective catalyst system. The preferred unsaturated aromatic hydrocarbon is selected from the group consisting of toluene, ethylbenzene, and mixtures thereof. The most preferred unsaturated aromatic hydrocarbon is ethylbenzene for best catalyst system activity, productivity and product selectivity. It should be recognized, however, that the reaction mixture comprising a chromium source, pyrrole-containing compound, metal alkyl and unsaturated hydrocarbon can contain additional components which do not adversely affect and can enhance the resultant catalyst system, such as, for example, transitions metals and/or halides. The order of combination of the catalyst system component during catalyst system preparation in accordance with this invention is critical. At all times, catalyst system components must be combined in the orders disclosed and claimed in this invention prior to contacting ethylene. In accordance with one embodiment of the invention, the first step of catalyst system preparation must be to combine the metal alkyl and the pyrrole-containing compound. These two components can be combined in accordance with any method known in the art and preferably in the presence of an unsaturated hydrocarbon, as disclosed Such a combination forms a metal alkyl/pyrrole solution. The amounts of each component used to form the metal alkyl/pyrrole solution can be any amount sufficient to form an active catalyst system when combined with a chromium-containing compound. Generally, a molar excess of the metal alkyl is used. Expressed as a molar ratio, in terms of moles of nitrogen (N) in the pyrrole compound to moles of metal (M) in the metal alkyl, usually at least a one-hundred-fold molar excess of metal is used As used in this disclosure, the metal (M) is aluminum. Preferably, the N:M molar ratio is within a range of about 3:3 to about 3:50. Most preferably, the N.M molar ratio is within a range of 1.3 to 1 7. Too much metal alkyl does not provide any significant economic improvement to catalyst system activity and too little metal alkyl can result in catalyst system with poor performance, i.e., insufficient activity and productivity Contacting of the metal alkyl and pyrrole-containing compound can be done under any conditions sufficient to thoroughly contact the two components, -8 - however, all contacting must be done in an inert atmosphere, such as, for example, nitrogen and/or argon. For ease of preparation, contacting usually is done under conditions of ambient temperature and pressure. Contact time can range from seconds to hours, preferably 1 second to 4 hours. Longer contacting times do not provide any additional catalyst system benefit. The second step for catalyst system preparation in accordance with this embodiment of the invention is to incrementally, or slowly, add the chromium-containing compound to the metal alkyl/pyrrole solution. The manner of addition of the chromium-containing compound to the metal alkyl/pyrrole solution is critical in that the chromium must be added slowly or incrementally. Such incremental addition of the chromium-containing compound to the solution provides better heat control of the catalyst system during catalyst system preparation. While not wishing to be bound by theory, it is believed that excess heat during catalyst system preparation can result in a less active catalyst system. The amounts of each component, chromium-containing compound and metal alkyl/pyrrole solution, used to form the final catalyst system can be any amount sufficient to form an active catalyst system. Generally, the amount of metal alkyl/pyrrole solution used is determined based on the moles of chromium. Expressed as a molar ratio, in terms of moles of chromium (Cr) to moles of nitrogen (N) in the pyrrole compound to moles of metal (M) in the metal alkyl, usually at least a fifteen-fold molar excess of pyrrole-containing compound and a one hundred fifty-fold molar excess of metal alkyl is used over the amount of chromium used. Preferably, the Cr N:M molar ratio is within a range of about 3:3:3 (also expressed as about 1:1:1) to about 1.3100. Most preferably, the Cr.N:M molar ratio is within a range of 1:39 to 1:3:21. Too much of any of the catalyst system components does not provide any significant economic improvement to catalyst system activity and too little of any of the catalyst system components can result in catalyst system with poor performance, i.e., insufficient activity and productivity It has been found that an increase in the amount of metal (aluminum) in the reactor can allow a decrease in the amount of chromium in the reactor. However, an increase of aluminum and decrease of chromium in the reactor can result in increased productivity, but decreased purity and increased polymer production. -9- As stated earlier, the catalyst synthesis prepared in a hydrocarbon solvent, also called a catalyst system solution. The resultant catalyst system, prior to introduction to any of the reactant, usually has a chromium concentration of about less than about 50 mg Cr/ml catalyst system solution, preferably within a range of about 0.01 mg Cr/mL catalyst system solution to about 25 mg Cr/ml catalyst system solution. Most preferably, the chromium concentration in the catalyst system solution is within a range of 1 mg Cr/ml catalyst system solution to 10 mg Cr/ml catalyst system solution for best catalyst system activity, selectivity and productivity. The metal alkyl/pyrrole solution and the chromium-containing compound solution must be combined prior to contacting any reactants. Any method of contacting known in the art can be used. For example, contacting of these two catalyst system components can be done in a batch process and stored for later use in a trimerization reactor or the two components can be continuously contacted and fed as one stream into an oligomenzation or tnmerization reactor. Contacting of the metal alkyl/pyrrole solution and the chromium solution can be done under any conditions sufficient to form an active tnmenzation catalyst system. All contacting must be done under an inert atmosphere, such as, for example, nitrogen and/or argon. Contacting conditions can be any conditions sufficient to form an active trimerization catalyst. Generally, conditions of ambient temperature and pressure are used. Contact time can be from less than a second to several hours. Preferably, contact time is about 1 second to 4 hours. Contact times of greater than 4 hours do not result in any additional catalyst system enhancement In a second embodiment of the invention, the first step of catalyst system preparation must be to combine the chromium compound and the pyrrole-containing compound These two components can be combined in any method known in the art and preferably in the presence of an unsaturated hydrocarbon, as disclosed Such a combination forms a chromium/pyrrole solution Reactants Trimerization, as used in this disclosure, is defined as the combination of any two, three, or more olefins, wherein the number of olefin, i.e., carbon-carbon double bonds is reduced by two. Reactants applicable for use in the - 10- trimerization process of this invention are olefinic compounds which can a) self-react, i.e., trimerize, to give useful products such as, for example, the self reaction of ethylene can give 1-hexene and the self-reaction of 1,3-butadiene can give 1,5-cyclooctadiene; and/or b) olefinic compounds which can react with other olefinic compounds, i.e., co-trimerize, to give useful products such as, for example, co-trimenzation of ethylene plus hexene can give 1-decene, co-trimerization of ethylene and 1-butene can give 1-octene, co-tnmerization of 1-decene and ethylene can give 1-tetradecene, 1-octadecene and/or 1-docosene. For example, the number of olefin bonds in the combination of three ethylene units is reduced by two, to one olefin bond, in 1-hexene In another example, the number of olefin bonds in the combination of two 1,3-butadiene units, is reduced by two, to two olefin bonds in 1,5-cyclooctadiene. As used herein, the term "trimerization" is intended to include dimenzation of drolefins, as well as "co-trimerization", both as defined above. Suitable trimerizable olefin compounds are those compounds having from about 2 to about 30 carbon atoms per molecule and having at least one olefinic double bond. Exemplary mono-1-olefin compounds include, but are not limited to acyclic and cyclic olefins such as, for example, ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-heptene, the four normal octenes, the four normal nonenes, vinylcyclohexane and mixtures of any two or more thereof. Exemplary mono-olefins include, but are not limited to, 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, cyclohexene and mixtures of two or more thereof. Exemplary diolefin compounds include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, and 1,5-hexadiene. If branched and/or cyclic olefins are used as reactants, while not wishing to be bound by theory, it is believed that stearic hindrance could hinder the trimenzation process Therefore, the branched and/or cyclic portion(s) of the olefin preferably should be distant from the carbon-carbon double bond Catalyst systems produced in accordance with this invention are particularly suitable for and preferably are employed as trimerization catalyst systems. Reaction Conditions The reaction products, i.e., olefin trimers as defined in this - 11 - specification, can be prepared from the catalyst systems of this invention by solution, slurry, and/or gas phase reaction techniques using conventional equipment and contacting processes. Contacting of the monomer or monomers with a catalyst system can be effected by any manner known in the art. One convenient method is to suspend the catalyst system in an organic medium and to agitate the mixture to maintain the catalyst system in solution throughout the trimenzation process. Other known contacting methods can also be employed. For example, the trimerization process can be carried out in a slurry of the catalyst components in an inert medium or diluent which is the process medium. Broadly, the common diluents are fluid paraffins, cycloparaffins, or aromatic hydrocarbons. Exemplary reactor diluents include, but are not limited to, isobutane, cyclohexane, and methylcyclohexane. Isobutane can be used for enhanced compatibility with known olefin polymerization processes However, a homogenous trimerization catalyst system is more easily dispersed in cyclohexane Therefore, a preferred diluent for a homogeneous catalyzed trimerization process is cyclohexane. In accordance with another embodiment of this invention, a slurry process can be carried out in a diluent (medium), which is a product of the olefin ohgomerization process. Therefor, the choice of reactor diluent, or medium, is based on the selection of the initial olefin reactant. For example, if the oligomerization catalyst is used to tnmerize ethylene to 1-hexene, the solvent for the oligomerization reaction would be 1-hexene. If ethylene and hexene were trimenzed to produce 1-decene, the oligomenzation reaction solvent would be 1-decene. If 1,3-butadiene was trimenzed to 1,5-cyclooctadiene, the trimerization reactor solvent would be 1,5-cyclooctadiene Optionally, based on economics, a solvent different than one of the oligomenzation process products can be used during startup, or initiation, of the oligomerization process A different inert diluent, such as a paraffin, cycloparaffin, or aromatic hydrocarbon, can be used during the oligomenzation process initiation Exemplary initial reactor diluents include, but are not limited to, isobutane and cyclohexane. Once the reactor has been charged with catalyst, reactant and optional diluent, additional diluent can be added to the reactor, as needed. During the course - 12 - of the oligomerization reaction, the added, inert diluent will become diluted and ultimately removed from the oligomerization process reactor. Reaction temperatures and pressures can be any temperature and pressure which can trimerize the olefin reactants. Generally, reaction temperatures are within a range of about 0° to about 250°C Preferably, reaction temperatures within a range of about 60° to about 200°C and most preferably, within a range of 80° to 150°C are employed Too low of a reaction temperature can produce too much undesirable insoluble product, such as, for example, polymer, and too high of a temperature can cause decomposition of the catalyst system and reaction products. Generally, reaction pressures are within a range of about atmospheric to about 2500 psig. Preferably, reaction pressures within a range of about atmospheric to about 1000 psig and most preferably, within a range of 300 to 800 psig are employed. Too low of a reaction pressure can result in low catalyst system activity. Optionally, hydrogen can be added to the reactor to accelerate the reaction and/or increase catalyst system activity. If desired, hydrogen also can be added to the reactor to control, i.e. minimize, solids (polymer) production. Catalyst systems of this invention are particularly suitable for use in trimerization processes. Products The olefinic products of this invention have established utility in a wide variety of applications, such as, for example, as monomers for use in the preparation of homopolymers, copolymers, and/or terpolymers. Further understanding of the present invention and its advantages will be provided by reference to the following examples EXAMPLES EXAMPLE I This example demonstrates regular chromium addition and flow chromium addition. Catalyst systems were prepared under an inert atmosphere (nitrogen or helium) at ambient temperatures, according to the following procedure. To a clean, nitrogen purged, 5 gallon reactor, 14.14 lbs of dry, nitrogen purged, - 13- ethylbenzene were added Then 389 mls of 2,5-dimethylpyrrole (2,5-DMP) was added to the reactor With mixing and cooling, an aluminum alkyl mixture comprising 1599.9 g of triethylaluminum (TEA) and 1228.7 g of diethylaluminum chloride (DEAC) is pressured by nitrogen into the same 5 gallon reactor. With coolint, the temperature increased about 11°C The reactor was stirred and cooled by an internal cooling coil during addition of the aluminum alkyl mixture. The lines containing the alkylaluminum mixture were flushed with 0.2 lbs of ethylbenzene into the reactor. In a separate container, 630.9 grams of chromium(III)ethylhexanoate (Cr(EH)3) were dissolved in 750 ml of ethylbenzene ir a flask purged with nitrogen The Cr(EH)3/ethylbenzene mixture was allowed to cool. After cooling, the CrEH3/ethylbenzene material was added to the reactor and a temperature rise of 14°C was observed. The reactor was stirred and cooled by an internal cooling coil dunng this addition. Then, the Cr(EH)3 lines were flushed with 1 pound of ethylbenzene. After about 15 minutes of mixing and cooling, the reactor was allowed to set without stiring prior to filtration and dilution with either cyclohexane or methylcyclohexane, the reaction driuent Slow, or incremental, addition of the chromium compound followed the procedure as described above except that the chromium solution was added in 19 or 20 50 gram increments. The temperature rise after each incremental addition was only about 1oC. The data in Table 1, Runs 101-104, provide the results of the regular chromium addition. Runs 105-108 show the results of the incremental chromium addition. - 15 - The data in Table 1 show that the slow, or incremental, addition of the chromium solution results in a higher conversion of olefins per gram of chromium per hour, as well as increased 1-hexene selectivity and purity. Furthermore, the advantage of first combining the pyrrole and the alkylaluminum compound and then subsequently adding the chromium compound and finally introducing the ethylene into the reactor is economically advantageous because an operator can decrease the amounts of pyrrole and aluminum alkyl needed for the reaction In addition, an advantage of this catalyst system preparation reaction order is that the amount of precipitate produced is decreased While not wishing to be bound by theory, it is believed that the amount of precipitate produced by catalyst system production can impact the amount of polymer produced in the reactor; an increase in the amount of precipitate usually can result in an increase in the amount of polymer production. It is known that an increased amount of polymer produced during the trimerization process can cause the reactor to foul more frequently and require more down time for cleaning of the reactor EXAMPLE II Catalyst systems in this Example were prepared by making two slock solutions The first stock solution was prepared by dissolving 23.8 grams of Cr(EH)3 in a 100 ml toluene. Then 8.8 ml of 2,5-DMP was added and the total mixture was diluted to 500 ml with toluene. The second stock solution was prepared by mixing 66.9 ml of 1.8 M ethylaluminum dichlonde (EADC), in toluene, with 58.8 ml of neat TEA and diluting this stock mixture to 500 ml with toluene. 28 ml of the chromium and pyrrole stock solution combined in a first container and diluted to 50 ml with toluene; 28 ml of the aluminum alkyl stock solution was added to a second container and diluted to 50 ml with toluene Both containers were emptied at the same rale through a mixing tee (T) into a third container where the two solutions were mixed for 5 minutes. Solvent was removed by vacuum and the residue was diluted to 25 ml with cyclohexane Aliquots of this catalyst system were tested in a 1 liter batch reactor at a reaction temperature of 110°C, with 450 ml cyclohexane as the solvent. Then, 50 psig hydrogen was added and ethylene was fed on demand to maintain a reactor pressure of 750 psig for 30 minutes. Four runs using the above-described catalyst - 16 - system are shown below in Table 2 as Runs 201-204. Runs 205-208 provide the results in which the catalyst components were added sequentially. The data in Table 2 show that even without cooling, continuous preparation of catalyst system produces good trimerization product and has good commercial potential. EXAMPLE III The following example demonstrates continuous catalyst system preparation at low concentrations Continuous catalyst preparation at low concentration The following three solutions were prepared in advance. 116 g of diethylaluminum chloride (DEAC), 151 g triethylaluminum (TEA) and 178 g ethylbenzene were added to a 1 gallon cylinder under nitrogen 2,5-Dimethylpyrrole (16 8 g) was diluted to 250 mL with ethylbenzene and added to a 300 mL cylinder under an inert atmosphere Chromium(III)2-ethylhexanoate (16.6 g) was dissolved in 375 g ethylbenzene and rinsed into a 1 gallon cylinder with 44 g ethylbenzene and purged with nitrogen Ethylbenzene (225 mL) was added to a 1 liter autoclave reactor to - 17 - provide material to reach the stirrer. The reactor was purged with dry nitrogen to avoid the presence of air or moisture. For three hours the TEA and DEAC solution was pumped simultaneously with the 2,5-dimethylpyrrole solution into the 1 liter reactor at 50 mL/hour. The temperature ranged from 9.7°C to 21°C. The reactor pressure was 95 to 107 psig. The reactor was stirred for 15 minutes after all the reactants had been pumped into the reactor. The contents of the reactor contained a pyrrole/aluminum alkyl mixture and was pressured with nitrogen into a 1 gallon cylinder. The pyrrole/aluminum alkyl mixture was then pumped into the 1-liter reactor simultaneously with the chromium(III)2-ethylhexanoate solution for three hours at 50 mL/hr. Cooling was added to the reactor and the temperature ranged between 25.3°C and 26.5°C. The pressure was 110-113 psig. The material was stirred for 15 minutes after all the reactants had been pumped into the reactor This catalyst was tested and found to be active as shown in Table 3. This demonstrates that continuous catalyst preparation (Run 301) is comparable to the slow addition catalyst preparation (Run 302) and may have advantages on a commercial scale EXAMPLE IV The following example demonstrates continuous catalyst system preparation at high concentrations. - 18 - Continuous catalyst preparation at high concentration The following three solutions were prepared in advance. 154 g of diethylaluminum chloride (DEAC), 200 g triethylaluminum (TEA) and 100 g ethylbenzene were added to a 1 gallon cylinder under nitrogen. 2,5-Dimethylpyrrole (76.9 g) was diluted to 250 mL with ethylbenzene and added to a 300 mL cylinder under an inert atmosphere. Chromium(III)2-ethylhexanoate (130.2 g) was dissolved in 280 g ethylbenzene and rinsed into a 1 gallon cylinder with 40 g ethylbenzene and purged with nitrogen. Ethylbenzene (225 mL) was added to a 1 liter autoclave reactor to provide matenal to reach the stirrer. The reactor was purged with dry nitrogen to avoid the presence of air or moisture. For three hours the TEA and DEAC solution was pumped simultaneously with the 2,5-dimethylpyrrole solution into the 1 liter reactor. The aluminum alkyls were pumped at 100 mL/hour while the pyrrole solution was pumped at the rate of 30 mL/hr. The temperature ranged from 12.5°C to 23.5°C. The reactor pressure was 89 to 119 psig The reactor was stirred for 15 minutes after all the reactants had been pumped into the reactor. The contents of the reactor contained a pyrrole/aluminum alkyl mixture and was pressured with nitrogen into a 1 gallon cylinder. The pyrrole/aluminum alkyl mixture was then pumped into the 1 liter reactor simultaneously with the chromium(III)2ethyl-hexanoate solution for three hours. The pyrrole/aluminum alkyl mixture was pumped at 100 mL/hr and the chromium solution was pumped in at a rate of 30 mL/hr. Cooling was added to the reactor and the temperature ranged between 230oC and 25.2°C. The pressure was 10614 psig The material was stirred for 15 minutes after all the reactants had been pumped into the reactor. This catalyst was tested and found to be active and demonstrated comparable activity as in Example III While this invention has been described in detail for the purpose of illustration, it is not to be construed as limited thereby but is intended to cover all changes and modifications within the spirit and scope thereof 19 We Claim; 1. A process to oligomerize olefins in the presence of an oligomerization catalyst sytem, comprising contacting said catalyst system with an alpha olefin, at a reaction temperature within a range from 0 C to 250 C and at a reaction pressure within a range from atmospheric to 2500 psig wherein said oligomereation catalyst system is prepared by contacting a halogenated alkylaluminum metal alkyl and a pyrrole-containing compound in the presence of a unsaturated hydrocarbon to form a halogenated alkylaluminum metal alkyl/pyrrole mixture; and contacting said halogenated alkylaluminum metal alkyl/pyrrole mixture with a chromium source to form said catalyst system. 2. A process as claimed in claim 1, wherein said oligomerization process is atrimerization process. 3. A process as claimed in any of the preceding claims, wherein said catalyst system further comprises a halide source. 4. A process as claimed in any of the preceding claims, wherein said olefin has from 2 to 30 carbon atoms per molecule. 5. A process as claimed in claim 4, wherein said olefin is ethylene. 6. A process as claimed in any of the preceding claims, wherein said unsaturated hydrocarbon has less than 20 carbon atoms per molecule. 7. A process as claimed in any of the preceding claims, wherein said chromium source is a chromium (II)-containing compound, a chromium (III)-containing compound, or a mixture of any two or more of said chromium sources. 20 8. A process as claimed in claim 7, wherein said chromium source is a chromium (III)-containmg compound which is a chromium carboxylate, a chromium naphthanate, a chromium halide, a chromium pyrrolide, a chromium dionate or a mixture of any two or more of said chromium (III)-containing compounds. 9. A process as claimed in claim 8, wherein said chromium source is chromium (III)2,2,6,6-tetram ethylheptanedionate [Cr(TMHD)3], chromium (III)2-ethylhexanoate or chromium (III) tris(2- ethyihexanoate) [Cr(EH)a], [chromium(III)naphthanate] [Cr(Np)3], chromium (III) chloride, chromium (III) bromide, chrom ium (III) fluoride, chrom ium (III) acetylacetonate, chrom ium (III) acetate, chrom ium (III) butyrate, chromium(III) neopentanoate, chrom ium (III) laurate, chrom ium (III) stearate, a chromium (III) pyrrolide, chromium(III) oxalate, or a mixture of any two or more of said chromium(III)-containing compounds. 10. A process as claimed in any one of preceding claims, wherein said metal alkyl is anon-hydrolyzed metal alky!. 11. A process as claimed in any of the preceding claims, wherein said pyrrole-containing compound is pyrrole, a derivative of pyrrole, an alkali metal pyrrolide, a salt of an alkali metal pyrrolide, or a mixture of any two or more of said pyrrole-containing compounds. 12. A process as claimed in claim 11, wherein said pyrrole-containing compound is hydrogen pyrrolide, 2,5-dimethylpyrrole, or a mixture thereof, 13. A process to oligomerize olefins substantially as hereinbefore described with reference to any one of the Examples. A process to oligomerize olefins in the presence of an oligomerization catalyst sytem, comprising contacting said catalyst system with an alpha olefin, at a reaction temperature within a range from 0 C to 250 C and at a reaction pressure within a range from atmospheric to 2500 psig wherein said oligomerization catalyst system is prepared by contacting a halogenated alkylaluminum metal alkyl and a pyrrole-containing compound in the presence of a unsaturated hydrocarbon to form a halogenated alkylaluminum metal alkyl/pyrrole mixture; and contacting said halogenated alkylaluminum metal alkyl/pyrrole mixture with a chromium source to form said catalyst system.

Full Text

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OLEFIN PRODUCTION
This invention relates to olefin production. Olefins, primarily alpha-olefins, have many uses. For example, alpha-olefins, such as 1-hexene, can be used in hydro formulation (OXO processes). In addition to uses as specific chemicals, alpha-olefins also can be used in polymerization processes as either a monomer or comonomer to prepare polyolefins, or polymers. Several methods of producing olefins are known in the art These processes include catalyzed dimerization and trimenzation processes. Usually, these olefin production processes are exothermic reactions and can generate significant amounts of heat.
Furthermore, preparation of dimerization and tnmerization catalyst systems are exothermic reactions and heat needs to be removed from the process Heat removal requires additional, often expensive, equipment and heat can be detrimental to the activity, productivity and selectivity of the resultant catalyst system Prior patents have taught in-situ catalyst system preparation, wherein the catalyst system is prepared in-situ in a tnmenzation reactor For example, see U.S 5,198,563 and U.S. 5,288,823
This invention provides improved olefin production processes, such as improved olefin oligomerization and tnmenzation processes.
The invention further provides a more efficient catalyst system production process.
The present invention yet further provides improved heat control of the catalyst system preparation process
The invention also deals with a continuous process to prepare olefin oligomerization or tnmenzation catalyst systems
In accordance with this invention, a process is provided which comprises prepanng an olefin oligomerization or tnmenzation catalyst system and producing olefins in the presence of the olefin oligomerization or trimenzaiion catalyst system and a solvent, wherein said catalyst system preparation comprises the steps of first contacting a chromium source and a pyrrole-contaming compound to form a chromium/pyrrole mixture; second, contacting said chromium/pyrrole mixture with a metal alkyl to form a catalyst system; and then contacting said

-2-catalyst system with an alpha-olefin, preferably ethylene.
In accordance with another embodiment of this invention, a process is provided which comprises preparing an olefin oligomerization or trimerization catalyst system and producing olefins in the presence of the olefin oligomerization or trimerization catalyst system and a solvent, wherein said catalyst system preparation comprises the steps of first contacting a metal alkyl and a pyrrole-containing compound to form a metal alkyl/pyrrole mixture; second, contacting said metal alkyl/pyrrole mixture with a chromium source to form a catalyst system; and then contacting said catalyst system with an alpha-olefin, preferably ethylene.
In accordance with yet another embodiment of this invention, a process is provided which consists essentially of preparing an olefin oligomerization or trimerization catalyst system and producing olefins in the presence of the olefin ohgomenzation or trimerization catalyst system and a solvent, wherein said catalyst system preparation comprises the steps of first contacting a chromium source and a pyrrole-containing compound to form a chromium/pyrrole mixture; second, contacting said chromium/pyrrole mixture with a metal alkyl to form a catalyst system; and then contacting said catalyst system With an alpha-olefin, preferably ethylene
In accordance with still another embodiment of this invention, a process is provides which consists essentially of preparing an olefin oligomerization or trimerization catalyst system and producing olefins in the presence of the olefin oligomerization or trimerization catalyst system and a solvent, wherein said catalyst system preparation comprises the steps of first contacting a metal alkyl and a pyrrole-containing compound to form a metal alkyl/pyrrole mixture, second, contacting said metal alkyl/pyrrole mixture with a chromium source to form a catalyst system; and then contacting said catalyst system with an alpha-olefin, preferably ethylene.
Catalyst Systems
Catalyst systems useful in accordance with this invention comprise a chromium source, a pyrrole-containing compound and a metal alkyl, all of which have been contacted and/or reacted in the presence of an unsaturated hydrocarbon. Optionally, these catalyst systems can be supported on an inorganic oxide support.

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These catalyst systems are especially useful for the oligomerization of olefins, such as, for example, ethylene to 1-hexene. As used in this disclosure, the term "oligomerization" broadly encompasses the combination of two olefins (dimerization) to form an olefinic product, combination of three olefins (trimerization) to form an olefinic product and combination of more than three olefins to form an olefinic product, but does not include polymerization of olefins. An ohgomer can be defined as a compound made up of repeating units, whose properties can change with the addition or removal of one or a few repeating units. The properties of a polymer do not change markedly with such a modification The chromium source can be one or more organic or inorganic chromium compounds, wherein the chromium oxidation state is from 0 to 6. If the chromium oxidation state is 0, metallic chromium can be the chromium source. Generally, the chromium source can have a formula of CrXn, wherein X can be the same or different and can be any organic or inorganic radical, and n is an integer from 1 to 6. Exemplary organic radicals can have from about 1 to about 20 carbon atoms per radical, and are selected from the group consisting of alkyl, alkoxy, carboxy, ester, ketone, and/or amido radicals The organic radicals can be straight-chained or branched, cyclic or acyclic, aromatic or aliphatic, can be made of mixed aliphatic, aromatic, and/or cycloaliphatic groups. Exemplary inorganic radicals include, but are not limited to halides, sulfates, and/or oxides.
Preferably, the chromium source is a chromium( II) -containing and/or a chromium(III)-containing compound which can yield a catalyst system with improved oligomerization and/or trimerization activity. Most preferably, the chromium source is a chromium(III) compound because of ease of use, availability, and enhanced catalyst system activity. Exemplary chromium(III) compounds include, but are not limited to, chromium carboxylates, chromium naphthenates, chromium halides, chromium pyrrolides, and/or chromium dionates Specific exemplary chromium(III) compounds include, but are not limited to, chromium(lll) 2,2,6,6,-tetramethylheptanedronate [Cr(TMHD)3], chromium(III) 2-ethylhexanoale also called chromium(III) tris(2-ethylhexanoate) [Cr(EH)3], chromium(IIl) naphthenate [Cr(Np)3], chromium(III) chloride, chromium (III) bromide (chromic bromide), chromium (III) fluoride (chromic fluoride), chromium(III) acetylacetonate,

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chromium(III) acetate, chromium(III) butyrate, chromium(III) neopentanoate, chromium(III) laurate, chromium(III) stearate, chromium (III) pyrrolides and/or chromium(III) oxalate.
Specific exemplary chromium(II) compounds include, but are not limited to, chromous bromide, chromous fluoride, chromous chloride, chromium(II) bis(2- ethylhexanoate), chromium(II) acetate, chromium(II) butyrate, chromium(II) neopentanoate, chromium(II) laurate, chromium(II) stearate, chromium(II) oxalate and/or chromium(II) pyrrolides.
The pyrrole-containing compound can be any pyrrole-containing compound that will react with the chromium source to form a chromium pyrrohde complex. As used in this disclosure, the term "pyrrole-containing compound" refers to hydrogen pyrrohde, i.e., pyrrole (C4H5N), derivatives of hydrogen pyrrohde, substituted pyrrolides, as well as metal pyrrohde complexes. A "pyrrolide", as used in this disclosure, is defined as a compound comprising a 5-membered, nitrogen-containing heterocycle, such as for example, pyrrole, derivatives of pyrrole, and mixtures thereof. Broadly, the pyrrole-containing compound can be pyrrole and/or any heteroleptic or homoleptic metal complex or salt, containing a pyrrohde radical, or ligand. The pyrrole-containing compound can be either affirmatively added to the olefin production reaction, or generated in-situ.
Generally, the pyrrole-containing compound "will have from about 4 to about 20 carbon atoms per molecule. Exemplary pyrrolides include, but are not limited to, and are selected from the group consisting of hydrogen pyrrolide (pyrrole), lithium pyrrohde, sodium pyrrohde, potassium pyrrolide, cesium pyrrolide, and/or the salts of substituted pyrrohdes, because of high reactivity and activity with the other reactants. Examples of substituted pyrrohdes include, but are not limited to, pyrrole-2-carboxyhc acid, 2-acetylpyrrole, pyrrole-2-carboxaldehyde, tetrahydromdole, 2,5-dimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 3-acetyl-2,4-dimethylpyrrole, ethyl-2,4-dimethyl-5-(ethoxycarbonyl)-3-pyrrole-propionateJ ethyl-3,5-dimethy)-2-pyrrolecarboxylate] and mixtures thereof When the pyrrole-containing compound contains chromium, the resultant chromium compound can be called a chromium pyrrohde.
The most preferred pyrrole-containing compounds used in preparation

-5 -
of a trimerization catalyst system are selected from the group consisting of hydrogen pyrrolide, i.e., pyrrole (C4H5N), 2,5-dimethylpyrrole (2,5-DMP) and/or chromium pyrrolides because of enhanced olefin production activity, selectivity and/or purity. Optionally, for ease of use, a chromium pyrrolide can provide both the chromium source and the pyrrole-containing compound. As used in this disclosure, when a chromium pyrrolide is used to form a catalyst system, a chromium pyrrolide can be considered to provide both the chromium source and the pyrrole-containing compound. While all pyrrole-containing compounds can produce catalyst systems with high activity and productivity, use of pyrrole and/or 2,5-dimethylpyrrole can produce a catalyst system with enhanced activity and selectivity to a desired product
The metal alkyl can be any heteroleptic or homoleptic metal alkyl compound. One or more metal alkyls can be used. The alkyl hgand(s) of the metal alkyl can be any aliphatic and/or aromatic radical. Preferably, the alkyl ligand(s) are any saturated or unsaturated aliphatic radical The metal alkyl can have any number of carbon atoms per molecule. However, due to commercial availability and ease of use, the metal alkyl usually will comprise less than about 70 carbon atoms per metal alkyl molecule and preferably less than about 20 carbon atoms per molecule Exemplary metal alkyl compounds include, but are not limited to, alkylaluminum compounds, alkylboron compounds, alkylmagnesium compounds, alkylzinc compounds and/or alkyl lithium compounds. Exemplary metal alkyls include, but are not limited to, n-butyl lithium, sec-butyllithium, tert-butyllithium, diethylmagnesium, diethylzinc, triethylaluminum, trimethylaluminum, trisobutyl-alumium, and mixtures thereof.
Preferably, the metal alkyl is selected from the group consisting of non-hydrolyzed, i e., not pre-contacted with water, alkylaluminum compounds, derivatives of alkylaluminum compounds, halogenated alkylaluminum compounds, and mixtures thereof for improved product selectivity, as well as improved catalyst system reactivity, activity, and/or productivity. The use of hydrolyzed metal alkyls can result is decreased olefin, i e., liquid, production and increased polymer, i.e , solid, production.
Most preferably, the metal alkyl is a non-hydrolyzed alkylaluminum

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compound, expressed by the general formulae A1R3, A1R2X, A1RX2, A1R2OR, A1RXOR, and/or A12R3X3, wherein R is an alkyl group and X is a halogen atom. Exemplary compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylalumimim, diethyl aluminum chloride, diethylaluminum bromide, diethylaluminum ethoxide, diethylaluminum phenoxide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof for best catalyst system activity and product selectivity. The most preferred alkylaluminum compounds are triethylaluminum (TEA) and diethylaluminum chloride (DEAC); TEA is used for best results in catalyst system activity and product selectivity and DEAC is used for best results in catalyst product purity and selectivity.
While not wishing to be bound by theory, it is believed that a chloride containing-compound can improve product purity and selectivity. Any chloride-containing compound can be used, such as, for example, DEAC and organo chlorides Exemplary organochlorides include, but are not limited to, carbon tetrachlonde,methylene chloride, chloroform, benzylchloride, l-hexachloroethane and mixtures thereof
Usually, contacting and/or reacting of the chromium source, pyrrole-containing compound and metal alkyl is done in the presence of an unsaturated hydrocarbon. The unsaturated hydrocarbon can be any aromatic or aliphatic hydrocarbon, in a gas, liquid or solid state. Preferably, to affect thorough contacting of the chromium source, pyrrole-containing compound and metal alkyl, the unsaturated hydrocarbon will be in a liquid state. The unsaturated hydrocarbon can have any number of carbon atoms per molecule. Usually, the unsaturated hydrocarbon will comprise less than about 70 carbon atoms per molecule, and preferably, less than about 20 carbon atoms per molecule, due to commercial availability and ease of use. Exemplary unsaturated, aliphatic hydrocarbon compounds include, but are not limited to, ethylene, 1-hexene, 1,3-butadrene, and mixtures thereof. The most preferred unsaturated aliphatic hydrocarbon compound is 1-hexene, because of elimination of catalyst system preparation steps and 1-hexene can be a reaction product. Exemplary unsaturated aromatic hydrocarbons include, but are not limited to, benzene, toluene, ethylbenzene, xylene, rnesitylene, hexamethylbenzene, and mixtures thereof. Unsaturated, aromatic hydrocarbons are

- 7-
preferred in order to improve catalyst system stability, as well as produce a highly active and selective catalyst system. The preferred unsaturated aromatic hydrocarbon is selected from the group consisting of toluene, ethylbenzene, and mixtures thereof. The most preferred unsaturated aromatic hydrocarbon is ethylbenzene for best catalyst system activity, productivity and product selectivity.
It should be recognized, however, that the reaction mixture comprising a chromium source, pyrrole-containing compound, metal alkyl and unsaturated hydrocarbon can contain additional components which do not adversely affect and can enhance the resultant catalyst system, such as, for example, transitions metals and/or halides.
The order of combination of the catalyst system component during catalyst system preparation in accordance with this invention is critical. At all times, catalyst system components must be combined in the orders disclosed and claimed in this invention prior to contacting ethylene. In accordance with one embodiment of the invention, the first step of catalyst system preparation must be to combine the metal alkyl and the pyrrole-containing compound. These two components can be combined in accordance with any method known in the art and preferably in the presence of an unsaturated hydrocarbon, as disclosed Such a combination forms a metal alkyl/pyrrole solution.
The amounts of each component used to form the metal alkyl/pyrrole solution can be any amount sufficient to form an active catalyst system when combined with a chromium-containing compound. Generally, a molar excess of the metal alkyl is used. Expressed as a molar ratio, in terms of moles of nitrogen (N) in the pyrrole compound to moles of metal (M) in the metal alkyl, usually at least a one-hundred-fold molar excess of metal is used As used in this disclosure, the metal (M) is aluminum. Preferably, the N:M molar ratio is within a range of about 3:3 to about 3:50. Most preferably, the N.M molar ratio is within a range of 1.3 to 1 7. Too much metal alkyl does not provide any significant economic improvement to catalyst system activity and too little metal alkyl can result in catalyst system with poor performance, i.e., insufficient activity and productivity
Contacting of the metal alkyl and pyrrole-containing compound can be done under any conditions sufficient to thoroughly contact the two components,

-8 -
however, all contacting must be done in an inert atmosphere, such as, for example, nitrogen and/or argon. For ease of preparation, contacting usually is done under conditions of ambient temperature and pressure. Contact time can range from seconds to hours, preferably 1 second to 4 hours. Longer contacting times do not provide any additional catalyst system benefit.
The second step for catalyst system preparation in accordance with this embodiment of the invention is to incrementally, or slowly, add the chromium-containing compound to the metal alkyl/pyrrole solution. The manner of addition of the chromium-containing compound to the metal alkyl/pyrrole solution is critical in that the chromium must be added slowly or incrementally. Such incremental addition of the chromium-containing compound to the solution provides better heat control of the catalyst system during catalyst system preparation. While not wishing to be bound by theory, it is believed that excess heat during catalyst system preparation can result in a less active catalyst system.
The amounts of each component, chromium-containing compound and metal alkyl/pyrrole solution, used to form the final catalyst system can be any amount sufficient to form an active catalyst system. Generally, the amount of metal alkyl/pyrrole solution used is determined based on the moles of chromium. Expressed as a molar ratio, in terms of moles of chromium (Cr) to moles of nitrogen (N) in the pyrrole compound to moles of metal (M) in the metal alkyl, usually at least a fifteen-fold molar excess of pyrrole-containing compound and a one hundred fifty-fold molar excess of metal alkyl is used over the amount of chromium used. Preferably, the Cr N:M molar ratio is within a range of about 3:3:3 (also expressed as about 1:1:1) to about 1.3100. Most preferably, the Cr.N:M molar ratio is within a range of 1:39 to 1:3:21. Too much of any of the catalyst system components does not provide any significant economic improvement to catalyst system activity and too little of any of the catalyst system components can result in catalyst system with poor performance, i.e., insufficient activity and productivity It has been found that an increase in the amount of metal (aluminum) in the reactor can allow a decrease in the amount of chromium in the reactor. However, an increase of aluminum and decrease of chromium in the reactor can result in increased productivity, but decreased purity and increased polymer production.

-9-
As stated earlier, the catalyst synthesis prepared in a hydrocarbon solvent, also called a catalyst system solution. The resultant catalyst system, prior to introduction to any of the reactant, usually has a chromium concentration of about less than about 50 mg Cr/ml catalyst system solution, preferably within a range of about 0.01 mg Cr/mL catalyst system solution to about 25 mg Cr/ml catalyst system solution. Most preferably, the chromium concentration in the catalyst system solution is within a range of 1 mg Cr/ml catalyst system solution to 10 mg Cr/ml catalyst system solution for best catalyst system activity, selectivity and productivity.
The metal alkyl/pyrrole solution and the chromium-containing compound solution must be combined prior to contacting any reactants. Any method of contacting known in the art can be used. For example, contacting of these two catalyst system components can be done in a batch process and stored for later use in a trimerization reactor or the two components can be continuously contacted and fed as one stream into an oligomenzation or tnmerization reactor.
Contacting of the metal alkyl/pyrrole solution and the chromium solution can be done under any conditions sufficient to form an active tnmenzation catalyst system. All contacting must be done under an inert atmosphere, such as, for example, nitrogen and/or argon. Contacting conditions can be any conditions sufficient to form an active trimerization catalyst. Generally, conditions of ambient temperature and pressure are used. Contact time can be from less than a second to several hours. Preferably, contact time is about 1 second to 4 hours. Contact times of greater than 4 hours do not result in any additional catalyst system enhancement
In a second embodiment of the invention, the first step of catalyst system preparation must be to combine the chromium compound and the pyrrole-containing compound These two components can be combined in any method known in the art and preferably in the presence of an unsaturated hydrocarbon, as disclosed Such a combination forms a chromium/pyrrole solution
Reactants
Trimerization, as used in this disclosure, is defined as the
combination of any two, three, or more olefins, wherein the number of olefin, i.e., carbon-carbon double bonds is reduced by two. Reactants applicable for use in the

- 10-
trimerization process of this invention are olefinic compounds which can a) self-react, i.e., trimerize, to give useful products such as, for example, the self reaction of ethylene can give 1-hexene and the self-reaction of 1,3-butadiene can give 1,5-cyclooctadiene; and/or b) olefinic compounds which can react with other olefinic compounds, i.e., co-trimerize, to give useful products such as, for example, co-trimenzation of ethylene plus hexene can give 1-decene, co-trimerization of ethylene and 1-butene can give 1-octene, co-tnmerization of 1-decene and ethylene can give 1-tetradecene, 1-octadecene and/or 1-docosene. For example, the number of olefin bonds in the combination of three ethylene units is reduced by two, to one olefin bond, in 1-hexene In another example, the number of olefin bonds in the combination of two 1,3-butadiene units, is reduced by two, to two olefin bonds in 1,5-cyclooctadiene. As used herein, the term "trimerization" is intended to include dimenzation of drolefins, as well as "co-trimerization", both as defined above.
Suitable trimerizable olefin compounds are those compounds having from about 2 to about 30 carbon atoms per molecule and having at least one olefinic double bond. Exemplary mono-1-olefin compounds include, but are not limited to acyclic and cyclic olefins such as, for example, ethylene, propylene, 1-butene, isobutylene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-heptene, the four normal octenes, the four normal nonenes, vinylcyclohexane and mixtures of any two or more thereof. Exemplary mono-olefins include, but are not limited to, 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, cyclohexene and mixtures of two or more thereof. Exemplary diolefin compounds include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, and 1,5-hexadiene. If branched and/or cyclic olefins are used as reactants, while not wishing to be bound by theory, it is believed that stearic hindrance could hinder the trimenzation process Therefore, the branched and/or cyclic portion(s) of the olefin preferably should be distant from the carbon-carbon double bond
Catalyst systems produced in accordance with this invention are particularly suitable for and preferably are employed as trimerization catalyst systems.
Reaction Conditions The reaction products, i.e., olefin trimers as defined in this

- 11 -
specification, can be prepared from the catalyst systems of this invention by solution, slurry, and/or gas phase reaction techniques using conventional equipment and contacting processes. Contacting of the monomer or monomers with a catalyst system can be effected by any manner known in the art. One convenient method is to suspend the catalyst system in an organic medium and to agitate the mixture to maintain the catalyst system in solution throughout the trimenzation process. Other known contacting methods can also be employed.
For example, the trimerization process can be carried out in a slurry of the catalyst components in an inert medium or diluent which is the process medium. Broadly, the common diluents are fluid paraffins, cycloparaffins, or aromatic hydrocarbons. Exemplary reactor diluents include, but are not limited to, isobutane, cyclohexane, and methylcyclohexane. Isobutane can be used for enhanced compatibility with known olefin polymerization processes However, a homogenous trimerization catalyst system is more easily dispersed in cyclohexane Therefore, a preferred diluent for a homogeneous catalyzed trimerization process is cyclohexane.
In accordance with another embodiment of this invention, a slurry process can be carried out in a diluent (medium), which is a product of the olefin ohgomerization process. Therefor, the choice of reactor diluent, or medium, is based on the selection of the initial olefin reactant. For example, if the oligomerization catalyst is used to tnmerize ethylene to 1-hexene, the solvent for the oligomerization reaction would be 1-hexene. If ethylene and hexene were trimenzed to produce 1-decene, the oligomenzation reaction solvent would be 1-decene. If 1,3-butadiene was trimenzed to 1,5-cyclooctadiene, the trimerization reactor solvent would be 1,5-cyclooctadiene
Optionally, based on economics, a solvent different than one of the oligomenzation process products can be used during startup, or initiation, of the oligomerization process A different inert diluent, such as a paraffin, cycloparaffin, or aromatic hydrocarbon, can be used during the oligomenzation process initiation Exemplary initial reactor diluents include, but are not limited to, isobutane and cyclohexane. Once the reactor has been charged with catalyst, reactant and optional diluent, additional diluent can be added to the reactor, as needed. During the course

- 12 -
of the oligomerization reaction, the added, inert diluent will become diluted and ultimately removed from the oligomerization process reactor. Reaction temperatures and pressures can be any temperature and pressure which can trimerize the olefin
reactants.
Generally, reaction temperatures are within a range of about 0° to about 250°C Preferably, reaction temperatures within a range of about 60° to about 200°C and most preferably, within a range of 80° to 150°C are employed Too low of a reaction temperature can produce too much undesirable insoluble product, such as, for example, polymer, and too high of a temperature can cause decomposition of the catalyst system and reaction products.
Generally, reaction pressures are within a range of about atmospheric to about 2500 psig. Preferably, reaction pressures within a range of about atmospheric to about 1000 psig and most preferably, within a range of 300 to 800 psig are employed. Too low of a reaction pressure can result in low catalyst system activity.
Optionally, hydrogen can be added to the reactor to accelerate the reaction and/or increase catalyst system activity. If desired, hydrogen also can be added to the reactor to control, i.e. minimize, solids (polymer) production.
Catalyst systems of this invention are particularly suitable for use in trimerization processes.
Products
The olefinic products of this invention have established utility in a wide variety of applications, such as, for example, as monomers for use in the preparation of homopolymers, copolymers, and/or terpolymers.
Further understanding of the present invention and its advantages will be provided by reference to the following examples
EXAMPLES EXAMPLE I
This example demonstrates regular chromium addition and flow chromium addition. Catalyst systems were prepared under an inert atmosphere (nitrogen or helium) at ambient temperatures, according to the following procedure. To a clean, nitrogen purged, 5 gallon reactor, 14.14 lbs of dry, nitrogen purged,

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ethylbenzene were added Then 389 mls of 2,5-dimethylpyrrole (2,5-DMP) was added to the reactor With mixing and cooling, an aluminum alkyl mixture comprising 1599.9 g of triethylaluminum (TEA) and 1228.7 g of diethylaluminum chloride (DEAC) is pressured by nitrogen into the same 5 gallon reactor. With coolint, the temperature increased about 11°C The reactor was stirred and cooled by an internal cooling coil during addition of the aluminum alkyl mixture. The lines containing the alkylaluminum mixture were flushed with 0.2 lbs of ethylbenzene into the reactor. In a separate container, 630.9 grams of chromium(III)ethylhexanoate (Cr(EH)3) were dissolved in 750 ml of ethylbenzene ir a flask purged with nitrogen The Cr(EH)3/ethylbenzene mixture was allowed to cool. After cooling, the CrEH3/ethylbenzene material was added to the reactor and a temperature rise of 14°C was observed. The reactor was stirred and cooled by an internal cooling coil dunng this addition. Then, the Cr(EH)3 lines were flushed with 1 pound of ethylbenzene. After about 15 minutes of mixing and cooling, the reactor was allowed to set without stiring prior to filtration and dilution with either cyclohexane or methylcyclohexane, the reaction driuent
Slow, or incremental, addition of the chromium compound followed the procedure as described above except that the chromium solution was added in 19 or 20 50 gram increments. The temperature rise after each incremental addition was only about 1oC. The data in Table 1, Runs 101-104, provide the results of the regular chromium addition. Runs 105-108 show the results of the incremental chromium addition.

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The data in Table 1 show that the slow, or incremental, addition of the chromium solution results in a higher conversion of olefins per gram of chromium per hour, as well as increased 1-hexene selectivity and purity. Furthermore, the advantage of first combining the pyrrole and the alkylaluminum compound and then subsequently adding the chromium compound and finally introducing the ethylene into the reactor is economically advantageous because an operator can decrease the amounts of pyrrole and aluminum alkyl needed for the reaction In addition, an advantage of this catalyst system preparation reaction order is that the amount of precipitate produced is decreased While not wishing to be bound by theory, it is believed that the amount of precipitate produced by catalyst system production can impact the amount of polymer produced in the reactor; an increase in the amount of precipitate usually can result in an increase in the amount of polymer production. It is known that an increased amount of polymer produced during the trimerization process can cause the reactor to foul more frequently and require more down time for cleaning of the reactor
EXAMPLE II
Catalyst systems in this Example were prepared by making two slock solutions The first stock solution was prepared by dissolving 23.8 grams of Cr(EH)3 in a 100 ml toluene. Then 8.8 ml of 2,5-DMP was added and the total mixture was diluted to 500 ml with toluene. The second stock solution was prepared by mixing 66.9 ml of 1.8 M ethylaluminum dichlonde (EADC), in toluene, with 58.8 ml of neat TEA and diluting this stock mixture to 500 ml with toluene. 28 ml of the chromium and pyrrole stock solution combined in a first container and diluted to 50 ml with toluene; 28 ml of the aluminum alkyl stock solution was added to a second container and diluted to 50 ml with toluene Both containers were emptied at the same rale through a mixing tee (T) into a third container where the two solutions were mixed for 5 minutes. Solvent was removed by vacuum and the residue was diluted to 25 ml with cyclohexane
Aliquots of this catalyst system were tested in a 1 liter batch reactor at a reaction temperature of 110°C, with 450 ml cyclohexane as the solvent. Then, 50 psig hydrogen was added and ethylene was fed on demand to maintain a reactor pressure of 750 psig for 30 minutes. Four runs using the above-described catalyst

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system are shown below in Table 2 as Runs 201-204. Runs 205-208 provide the results in which the catalyst components were added sequentially.

The data in Table 2 show that even without cooling, continuous preparation of catalyst system produces good trimerization product and has good commercial potential.
EXAMPLE III
The following example demonstrates continuous catalyst system preparation at low concentrations
Continuous catalyst preparation at low concentration
The following three solutions were prepared in advance. 116 g of diethylaluminum chloride (DEAC), 151 g triethylaluminum (TEA) and 178 g ethylbenzene were added to a 1 gallon cylinder under nitrogen 2,5-Dimethylpyrrole (16 8 g) was diluted to 250 mL with ethylbenzene and added to a 300 mL cylinder under an inert atmosphere Chromium(III)2-ethylhexanoate (16.6 g) was dissolved in 375 g ethylbenzene and rinsed into a 1 gallon cylinder with 44 g ethylbenzene and purged with nitrogen
Ethylbenzene (225 mL) was added to a 1 liter autoclave reactor to

- 17 -
provide material to reach the stirrer. The reactor was purged with dry nitrogen to avoid the presence of air or moisture. For three hours the TEA and DEAC solution was pumped simultaneously with the 2,5-dimethylpyrrole solution into the 1 liter reactor at 50 mL/hour. The temperature ranged from 9.7°C to 21°C. The reactor pressure was 95 to 107 psig. The reactor was stirred for 15 minutes after all the reactants had been pumped into the reactor. The contents of the reactor contained a pyrrole/aluminum alkyl mixture and was pressured with nitrogen into a 1 gallon cylinder. The pyrrole/aluminum alkyl mixture was then pumped into the 1-liter reactor simultaneously with the chromium(III)2-ethylhexanoate solution for three hours at 50 mL/hr. Cooling was added to the reactor and the temperature ranged between 25.3°C and 26.5°C. The pressure was 110-113 psig. The material was stirred for 15 minutes after all the reactants had been pumped into the reactor This catalyst was tested and found to be active as shown in Table 3.

This demonstrates that continuous catalyst preparation (Run 301) is comparable to the slow addition catalyst preparation (Run 302) and may have advantages on a commercial scale
EXAMPLE IV
The following example demonstrates continuous catalyst system preparation at high concentrations.

- 18 -
Continuous catalyst preparation at high concentration The following three solutions were prepared in advance. 154 g of diethylaluminum chloride (DEAC), 200 g triethylaluminum (TEA) and 100 g ethylbenzene were added to a 1 gallon cylinder under nitrogen. 2,5-Dimethylpyrrole (76.9 g) was diluted to 250 mL with ethylbenzene and added to a 300 mL cylinder under an inert atmosphere. Chromium(III)2-ethylhexanoate (130.2 g) was dissolved in 280 g ethylbenzene and rinsed into a 1 gallon cylinder with 40 g ethylbenzene and purged with nitrogen.
Ethylbenzene (225 mL) was added to a 1 liter autoclave reactor to provide matenal to reach the stirrer. The reactor was purged with dry nitrogen to avoid the presence of air or moisture. For three hours the TEA and DEAC solution was pumped simultaneously with the 2,5-dimethylpyrrole solution into the 1 liter reactor. The aluminum alkyls were pumped at 100 mL/hour while the pyrrole solution was pumped at the rate of 30 mL/hr. The temperature ranged from 12.5°C to 23.5°C. The reactor pressure was 89 to 119 psig The reactor was stirred for 15 minutes after all the reactants had been pumped into the reactor. The contents of the reactor contained a pyrrole/aluminum alkyl mixture and was pressured with nitrogen into a 1 gallon cylinder. The pyrrole/aluminum alkyl mixture was then pumped into the 1 liter reactor simultaneously with the chromium(III)2ethyl-hexanoate solution for three hours. The pyrrole/aluminum alkyl mixture was pumped at 100 mL/hr and the chromium solution was pumped in at a rate of 30 mL/hr. Cooling was added to the reactor and the temperature ranged between 230oC and 25.2°C. The pressure was 10614 psig The material was stirred for 15 minutes after all the reactants had been pumped into the reactor. This catalyst was tested and found to be active and demonstrated comparable activity as in Example III
While this invention has been described in detail for the purpose of illustration, it is not to be construed as limited thereby but is intended to cover all changes and modifications within the spirit and scope thereof

19
We Claim;
1. A process to oligomerize olefins in the presence of an
oligomerization catalyst sytem, comprising contacting said catalyst
system with an alpha olefin, at a reaction temperature within a
range from 0 C to 250 C and at a reaction pressure within a range
from atmospheric to 2500 psig wherein said oligomereation
catalyst system is prepared by contacting a halogenated
alkylaluminum metal alkyl and a pyrrole-containing compound in
the presence of a unsaturated hydrocarbon to form a halogenated
alkylaluminum metal alkyl/pyrrole mixture; and contacting said
halogenated alkylaluminum metal alkyl/pyrrole mixture with a
chromium source to form said catalyst system.
2. A process as claimed in claim 1, wherein said oligomerization
process is atrimerization process.
3. A process as claimed in any of the preceding claims, wherein said
catalyst system further comprises a halide source.
4. A process as claimed in any of the preceding claims, wherein said
olefin has from 2 to 30 carbon atoms per molecule.
5. A process as claimed in claim 4, wherein said olefin is ethylene.
6. A process as claimed in any of the preceding claims, wherein said
unsaturated hydrocarbon has less than 20 carbon atoms per
molecule.
7. A process as claimed in any of the preceding claims, wherein said
chromium source is a chromium (II)-containing compound, a
chromium (III)-containing compound, or a mixture of any two or
more of said chromium sources.

20
8. A process as claimed in claim 7, wherein said chromium source is
a chromium (III)-containmg compound which is a chromium
carboxylate, a chromium naphthanate, a chromium halide, a
chromium pyrrolide, a chromium dionate or a mixture of any two
or more of said chromium (III)-containing compounds.
9. A process as claimed in claim 8, wherein said chromium source is
chromium (III)2,2,6,6-tetram ethylheptanedionate [Cr(TMHD)3],
chromium (III)2-ethylhexanoate or chromium (III) tris(2-
ethyihexanoate) [Cr(EH)a], [chromium(III)naphthanate] [Cr(Np)3],
chromium (III) chloride, chromium (III) bromide, chrom ium (III)
fluoride, chrom ium (III) acetylacetonate, chrom ium (III) acetate,
chrom ium (III) butyrate, chromium(III) neopentanoate,
chrom ium (III) laurate, chrom ium (III) stearate, a chromium (III)
pyrrolide, chromium(III) oxalate, or a mixture of any two or more
of said chromium(III)-containing compounds.
10. A process as claimed in any one of preceding claims, wherein said
metal alkyl is anon-hydrolyzed metal alky!.
11. A process as claimed in any of the preceding claims, wherein said
pyrrole-containing compound is pyrrole, a derivative of pyrrole, an
alkali metal pyrrolide, a salt of an alkali metal pyrrolide, or a
mixture of any two or more of said pyrrole-containing compounds.
12. A process as claimed in claim 11, wherein said pyrrole-containing
compound is hydrogen pyrrolide, 2,5-dimethylpyrrole, or a mixture
thereof,
13. A process to oligomerize olefins substantially as hereinbefore
described with reference to any one of the Examples.
A process to oligomerize olefins in the presence of an oligomerization catalyst sytem, comprising contacting said catalyst system with an alpha olefin, at a reaction temperature within a range from 0 C to 250 C and at a reaction pressure within a range from atmospheric to 2500 psig wherein said oligomerization catalyst system is prepared by contacting a halogenated alkylaluminum metal alkyl and a pyrrole-containing compound in the presence of a unsaturated hydrocarbon to form a halogenated alkylaluminum metal alkyl/pyrrole mixture; and contacting said halogenated alkylaluminum metal alkyl/pyrrole mixture with a chromium source to form said catalyst system.

Documents:

in-pct-2002-00869-kol abstract.pdf

in-pct-2002-00869-kol claims.pdf

in-pct-2002-00869-kol correspondence.pdf

in-pct-2002-00869-kol description (complete).pdf

in-pct-2002-00869-kol form-1.pdf

in-pct-2002-00869-kol form-18.pdf

in-pct-2002-00869-kol form-2.pdf

in-pct-2002-00869-kol form-5.pdf

in-pct-2002-00869-kol g.p.a.pdf

in-pct-2002-00869-kol letters patent.pdf

IN-PCT-2002-869-KOL-FORM-27.pdf

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Patent Number

202595

Indian Patent Application Number

IN/PCT/2002/869/KOL

PG Journal Number

09/2007

Publication Date

02-Mar-2007

Grant Date

02-Mar-2007

Date of Filing

27-Jun-2002

Name of Patentee

PHILLIPS PETROLEUM COMPANY

Applicant Address

4th and Keeler, Bartlesville, OK 74004, USA.

Inventors:

#	Inventor's Name	Inventor's Address
1	COWAN GLYNDAL D,	3921 NE Nebraska, Bartlesville, OK 74006,USA.
2	FREEMAN JEFFREY W	1726 NE SONYA CT.BEND, OR 97701
3	EWERT WARREN M	3606 E Mountain Road, Bartlesville, OK 74003-6943, USA.
4	KREISCHER BRUCE E	504 Dorsett Court, Bartlesville, OK 74006, USA
5	KNUDSEN RONALD D	1412 Meadow Lane Bartlesville, OK 74006, USA.

PCT International Classification Number

B01J31/02

PCT International Application Number

PCT/US00/35078

PCT International Filing date

2000-12-21

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/474.067	1999-12-29	U.S.A.