Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

• This invention relates to a new catalyst composition useful for initiating and promoting polymerization of one or more a-olefins and to a polymerization process employing such a catalyst composition.
• olefins such as ethylene, propylene, and 1-butene in the presence of metallic catalysts, particularly the reaction products of organometallic compounds and transition metal compounds can be polymerized to form substantially linear polymers of relatively high molecular weight. Typically such polymerizations are carried out at relatively low temperatures and pressures.
• the catalyst employed is obtained by admixing a compound of a transition metal of Groups 4b, 5b, 6b and 8 of Mendeleev's Periodic Table of Elements with an organometallic compound.
• the halides, oxyhalides and alkoxides or esters of titanium, vanadium and zirconium are the most widely used transition metal compounds.
• the organometallic compounds include the hydrides, alkyls and haloalkyls of aluminum, alkylaluminum halides, Grignard reagents, alkali metal aluminum hydrides, alkali metal borohydrides, alkali metal hydrides, alkaline earth metal hydrides and the like.
• the polymerization is carried out in a reaction medium comprising an inert organic liquid, e.g., an aliphatic hydrocarbon and the aforementioned catalyst.
• One or more olefins may be brought into contact with the reaction medium in any suitable manner, and a molecular weight regulator, such as hydrogen, is often added to the reaction vessel in order to control the molecular weight of the polymers.
• a molecular weight regulator such as hydrogen
• Such polymerization processes are either carried out at slurry polymerization temperatures (i.e., wherein the resulting polymer is not dissolved in the hydrocarbon reaction medium) or at solution polymerization temperatures (i.e., wherein the temperature is high enough to solubilize the polymer in the reaction medium).
• catalyst residues from the polymer by repeatedly treating the polymer with alcohol or other deactivating agent such as an aqueous basic solution.
• alcohol or other deactivating agent such as an aqueous basic solution.
• the present invention in one aspect is a catalyst support which is the solid reaction product formed by reacting in an inert hydrocarbon diluent (1) the reaction product of (a) an organomagnesium compound or a hydrocarbyl or hydrocarbyloxy aluminum, zinc or boron mixture or complex thereof with (b) an oxygencontaining and/or nitrogen-containing compound; and (2) a halide source which is free of a transition metal.
• the organomagnesium compound and the mixture or complex of the organomagnesium compound and the hydrocarbyl or hydrocarbyloxy aluminum, zinc or boron compounds are represented by the formula MgR 2 'xMeR' x' as hereinafter defined.
• the oxygen-containing and/or nitrogencontaining compound is present in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (1-a) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25°C.
• the halide source is present in a quantity sufficient to convert essentially all of the groups which are attached to a magnesium atom in component (la) to a halide group.
• Another aspect of the present invention is the hydrocarbon insoluble solid reaction product of
• the components are employed in quantities so as to provide a sufficient quantity of component (1-b) to lower the amount of hydrocarbyl groups present in component (1-a) such that the resultant product will not substantially reduce TiCl 4 at 25°C.
• At least a sufficient amount of halogen from component (2) is employed to convert essentially all of the groups attached to a magnesium atom in component (1) to a halide group.
• the quantity of component (B) is that which is sufficient to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1 preferably from about 0.1:1 to about 5:1 and most preferably from about 0.2:1 to about 1:1.
• Sufficient quantities of component (C) are employed so as to theoretically reduce essentially all of the transition metal.
• the present invention concerns solid, hydrocarbon insoluble catalysts which when employed with an activator or cocatalyst are suitable for polymerizing a-olefins which catalysts are the inert diluent washed product resulting from the admixture of: (I) the reaction product of (A) the reaction product of
• magnesium component or a mixture of such components represented by the formula MgR 2 "xMeR' x , wherein each R is independently a hydrocarbyl group having from 1 to about
• each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20, preferably from 1 to about 10 carbon atoms
• Me is Al, Zn or B
• x has a value from zero to 10
• x' has a value equal to the valence of Me
• an oxygen-containing and/or nitrogen- containing compound in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25°C
• a suitable halide source or mixture thereof represented by the formulas
• each X is independently a . halogen, a hydrocarbyloxy group having from 1 to about 20, preferably from 1 to about 10 carbon atoms or an NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms; m has a value from zero to 2; said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1 preferably from 1:1 to about 10:1 and most preferably from about 1:1 to about 3:1.
• the halide source is a reducing halide source
• the reducing agent (III) can be omitted resulting in still another aspect of the present invention which is the inert diluent washed hydrocarbon insoluble catalyst which comprises: (I) The reaction product of
• each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20, preferably from 1 to about 10 carbon atoms
• Me is Al, Zn or B
• x has a value from zero to 10
• x' has a value equal to the valence of Me
• a further aspect of the present invention is a process for preparing a hydrocarbon insoluble catalyst which comprises:
• x has a value from zero to 10
• x' has a value equal to the valence of Me
• each R is independently hydrogen, a hydrocarbyl group or a hydrocarbyloxy group as hereinbefore defined, R4 is hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms; each X is a halogen atom such as chlorine or bromine; a has a value of from 1 to 3; b has a value of from 1 to 4; Tm is a metal selected from groups IV-B, V-B or VI-B of the Periodic Table of Elements; Y is oxygen, OR", or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, z has a value equal to the valence of said transition metal, n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in a quantity sufficient to
• each X is independently a halogen, a hydrocarbyloxy group having from 1 to about 20, preferably from 1 to about 10 carbon atoms or a NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms; m has a value from zero to 2 , said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1 preferably from 1:1 to about 10:1 and most preferably from about 1:1 to about 3:1; and (V) recovering and washing with fresh inert diluent the resultant solid hydrocarbon insoluble catalyst produced in step (IV).
• the recovery step II and the reducing agent (IV) can be omitted resulting in still another aspect of the present invention which is a process for preparing a hydrocarbon insoluble catalyst which comprises: (I) reacting in an inert diluent
• each R is independently a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20, preferably from 1 to about 10 carbon atoms;
• Me is Al, Zn or B;
• x has a value from zero to 10 and x' has a value equal to the valence of Me;
• each X is a halogen atom, preferably chlorine, R 3 is hydrogen or a hydrocarbyl group as defined above and a has a value from 1 to less than 3; in a quantity so as to provide an R 3 :Ti ratio of from 1:1 to about 50:1, preferably from about 1:1 to about 10:1 and to provide sufficient halogen atoms to convert essentially all of the groups attached to a magnesium atom in component
• Tm a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B or VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about
• a further aspect of the invention is a process for polymerizing a-olefins or mixtures thereof which comprises conducting the polymerization in the presence of the aforementioned catalysts.
• hydrocarbyl refers to a monovalent hydrocarbon radical such as alkyl, cycloalkyl, aryl, aralkyl, alkenyl and similar hydrocarbon radicals having from 1 to about 20 carbon atoms with alkyl having from 1 to 10 carbon atoms being preferred.
• hydrocarbyloxy refers to monovalent oxyhydrocarbon radicals such as alkoxy, cycloalkoxy, aryloxy, aralkoxy, alkenoxy and similar oxyhydrocarbon atoms having from 1 to about 20 carbon atoms with alkoxy groups having from 1 to 10 carbon atoms being the preferred hydrocarbyloxy radicals
• the quantity of MeR' x is preferably the minimum amount which is sufficient to render the magnesium compound soluble in the inert solvent or diluent which is usually a hydrocarbon or mixture of hydrocarbons.
• the value of x therefore is from zero to about 10, usually from about 0.2 to about 2.
• organomagnesium compounds include, for example, di-(n-butyl) magnesium, n-butyl-sec-butyl magnesium, diisopropyl magnesium, di-n-hexyl magnesium, isopropyl-n-butyl magnesium, ethyl-n-hexyl magnesium, ethyl-ri-butyl magnesium, di-(n-octyl) magnesium, butyl octyl and such complexes as di-n-butyl magnesium"1/3 aluminum triethyl, di-(n-butyl) magnesium"1/.6 aluminum triethyl, mixtures thereof and the like.
• Suitable oxygen-containing compounds include, for example, water, carbon dioxide, carbon monoxide, sulfur dioxide, hydroxyl-containing organic compounds such as alcohols, glycols, polyoxyalkylene glycols and the like, aldehydes, ketones, acetals, ketals, carboxylic acids, carboxylic acid esters, orthoesters or halides, carboxylic acid anhydrides, organic carbonates, mixtures thereof and the like.
• Suitable nitrogen-containing compounds which can be employed herein include, for example, ammonia, amines, nitriles, amides, oximes, imides, isocyanates, mixtures thereof and the like.
• Suitable hydroxyl-containing compounds include those represented by the formulas wherein each R is a hydrocarbyl group having from 1 to about 20 preferably from 1 to about 10 carbon atoms or a halogen, NHR or NH 2 substituted hydrocarbyl group having from 1 to about 20 preferably from 1 to about 10 carbon atoms, each R' is independently a divalent hydrocarbyl group having from 1 to about 20 preferably from 1 to about 10 carbon atoms, each R" is independently hydrogen, a hydrocarbyl group having from 1 to about 20 preferably from 1 to 10 carbon atoms or a halogen, NHR or NH 2 substituted hydrocarbyl group having from 1 to about 20 preferably from 1 to about 10 carbon atoms, at least one of which is hydrogen, Z is a multivalent organic radical containing from 2 to about 20 carbon atoms, n has a value from zero to about 10 and n' has a value of from 2 to about 10.
• Particularly suitable hydroxyl-containing compounds include alcohols such as for example methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, glycols, 1,2-butylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexane diol, other hydroxyl containing compounds such as, for example, glycerine, trimethylol propane, hexane triol, phenol, 2,6-di-tert-butyl-4-methylphenol, mixtures thereof and the like.
• alcohols such as for example methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, glycols, 1,
• Suitable aldehydes which can be employed herein include those aldehydes represented by the formula I)
• R is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably an aliphatic hydrocarbyl group having from 1 to about 10 carbon atoms.
• aldehydes include, for example, formaldehyde, acetaldehyde, propionaldehyde, butryaldehyde, benzaldehyde, mixtures thereof and the like.
• Suitable ketones which can be employed herein include, for example, those represented by the formula
• each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms.
• Particularly suitable ketones include, for example, acetone, methyl ethyl ketone, 2, 6-dimethyl-4-heptanone, mixtures thereof and the like.
• the oxygen-containing compounds particularly the alcohols, aldehydes and ketones can contain up to about 50 percent, preferably about 1 percent or less water by weight.
• Suitable carboxylic acids which can be employed herein include those represented by the formulas
• each R is a hydrocarbyl group having from 1 to about 20 carbon atoms, particularly from about 1 to about 10 carbon atoms.
• Particularly suitable carboxylic acids include, for example, formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid, 2-ethylhexanoic acid, acrylic acid, methacrylic acid, mixtures thereof and the like.
• Suitable acetals which can be employed herein include, for example, those represented by the formula
• each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms.
• Particularly suitable acetals which can be employed includes, for example, acetal, 1,1-diethoxypropane, mixtures thereof and the like.
• Suitable ketals which can be employed herein include, for example, those represented by the formula
• each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms.
• Particularly suitable ketals include, for example, 2,2-dimethoxypropane, 2,2-dimethoxyhexane, 2,2-diethoxypropane, mixtures thereof and the like.
• Suitable esters of carboxylic acids which can be employed herein include, for example, those represented by the formulas
• each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms.
• Particularly suitable esters include, for example, ethyl acetate, ethyl formate, ethyl benzoate, methyl acetate, methyl formate, mixtures thereof and the like.
• Suitable orthoesters which can be employed herein include, for example, those represented by the formula
• each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms.
• Particularly suitable orthoesters include, for example, triethylorthoformate, triethylorthoacetate, mixtures thereof and the like.
• Suitable carboxylic acid halides include those represented by the formulas
• each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms and each X is a halogen, preferably chlorine or bromine.
• Particularly suitable acid halides include, for example, acetyl chloride, oxalyl chloride, propionyl chloride, benzoyl chloride, mixtures thereof and the like.
• Suitable organic carbonates which can be employed herein include, for example, those represented by the formulas
• each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms.
• Particularly suitable carbonates include, for example, diethylcarbonate, ethylene carbonate, dipropylcarbonate, propylene carbonate, styrene carbonate, mixtures thereof and the like.
• Suitable carboxylic acid anhydrides include, for example, those represented by the fomirulas
• each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, preferably from 1 to about 10 carbon atoms.
• Particularly suitable anhydrides include, for example, acetic anhydride, propionic anhydride, mixtures thereof and the like.
• Suitable amines which can be employed herein include, for example, those represented by the formula
• each R is independently hydrogen, a hydroxyl or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms.
• Particularly suitable amines include, for example, ammonia, ethylamine, diethylamine, diisopropylamine, isopropylamine, hydroxylamine, mixtures thereof and the like.
• Suitable amides which can be employed herein include, for example, those represented by the formula,
• each R is independently hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms.
• Particularly suitable amides include, for example, formamide, N,N-dimethylformamide, mixtures thereof and the like.
• Suitable imides which can be employed herein include, for example, those represented by the formula
• each R is independently hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms.
• Particularly suitable imides include, for example, succinimide, phthalimide, mixtures thereof and the like.
• Suitable oximes which can be employed herein include, for example, those represented by the formulas
• each R is independently hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms.
• Particularly suitable oximes include, for example dimethylglyoxime, formam ⁇ idoxime, acetoxime, acetaldoxime, methyl ethyl ketoxime, mixtures thereof and the like.
• Suitable nitriles which can be employed herein include, for example, those represented by the formula XXI I ) R-CXN
• R is hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms.
• Particularly suitable nitriles include, for example, hydrocyanic acid, acetonitrile, propionitrile, acrylonitrile, mixtures thereof and the like.
• Suitable isocyanates which can be employed herein include, for example, those represented by the formulas
• each R is independently a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms and y has an average value from about 1.01 to about 6.
• Particularly suitable isocyanates which can be employed herein include, for example, methyl isocyanate, ethyl isocyanate, methyl diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate, polymethylene polyphenylisocyanate, mixtures thereof and the like.
• the oxygen- or nitrogen-containing compound can have dissolved or finely dispersed therein one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups IV-B, V-B, VI-B, VII-B, VIII, I-B of the Periodic Table of the Elements; Y is oxygen, OR" or NR ; R" is hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms; X is a halogen atom, preferably chlorine or bromine; z has a value corresponding to the valence of the transition metal, Tm' ; n has a value of from zero to 5; and the value of z-n is from zero up to the valence of the transition metal, Tm'.
• Tm' is a transition metal selected from groups IV-B, V-B, VI-B, VII-B, VIII, I-B of the Periodic Table of the Elements
• transition metal compounds include, for example, CoCl 2 , CoCl 2 "6H 2 O , NiCl 2 , NiCl 2 "6H 2 O , FeCl 3 "6H 2 O , FeCl 3 , FeCl 2 , CrCl 3 , CrCl 2 , CrCl 3 "6H 2 O , MoCl 5 , WCX 6 2rCl4 ,
• the transition metal compound when employed, is in a quantity so as to provide a Tm' :Tm atomic ratio of from about 0.01:1 to about 0.5:1, preferably from about 0.02:1 to about 0.2:1.
• the transition metals represented by Tm and Tm' are different.
• the transition metal portion of the compound dissolved or finely dispersed in the oxygenor nitrogen- containing compound is different from the transition metal portion of the transition metal compound subsequently employed in preparing the catalyst of the present invention.
• Suitable halide sources which can be employed herein include those prepresented by the formulas AlR 3-a X a ' SiR 4-b X b ' SnR 4-b X b ' POX 3 ' PX 3 ' PX 5 ' SO 2 X 2 , GeX 4 , HX, R(CO)X and RX wherein each R is independently hydrogen, a hydrocarbyl group or a hydrocarbyloxy group as hereinbefore defined, each X is a halogen atom such as chlorine or bromine, a has a value of from 1 to 3 and b has a value of 1 to 4.
• the halide source is a hydrocarbyl halide
• it should contain a labile halogen at least as active i.e., easily lost to another compound, as the halogen of sec-butyl chloride, preferably as active as t-butyl chloride.
• Particularly suitable halide sources include, for example, silicon tetrachloride, tin tetrachloride, aluminum trichloride, trichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, methyldichlorosilane, ethylaluminum dichloride, diethylaluminum chloride, ethylaluminumsesquichloride, phosphorus oxytrichloride, phosphorus trichloride, hydrogen chloride, t-butyl chloride, benzyl chloride, benzoyl chloride, acetyl chloride, mixtures thereof and the like.
• Suitable halide sources also include hydrocarbon soluble transition metal halide compounds represented by the formula TmY n X z-n wherein Tm is a transition metal selected from groups IV-B, V-B and VI-B of the Periodic Table of the Elements, Y is oxygen, OR" or NR ; each R" is independently hydrogen or a hydrocarbyl group as previously defined; X is a halogen, preferably chlorine or bromine; z has a value corresponding to the valence of the transition metal, Tm; n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence state of the transition metal, Tm.
• transition metal halide compounds include, those compounds of titanium, zirconium, vanadium and chromium such as, for example, titanium tetrachloride, titanium tetrabromide, dibutoxy titanium dichloride, monoethoxy titanium trichloride, isopropoxy titanium trichloride, chromyl chloride, vanadium oxytrichloride, zirconium tetrachloride, vanadium tetrachloride, mixtures thereof and the like.
• titanium tetrachloride titanium tetrabromide
• dibutoxy titanium dichloride monoethoxy titanium trichloride
• isopropoxy titanium trichloride chromyl chloride
• vanadium oxytrichloride zirconium tetrachloride
• vanadium tetrachloride mixtures thereof and the like.
• Suitable reducing agents include those represented by the formulas Al(R 3 ) 3-m X m , B(R 3 ) 3-m X m ,
• Particularly suitable reducing agents include, for example, triethylaluminum, ethylaluminum dichloride, diethylaluminum chloride, triisobutylaluminum, ethylaluminum sesquichloride, diisobutylaluminum hydride, trimethy1aluminum, triethylboron, diethylzinc, dibutylmagnesium butylethyl magnesium, mixtures thereof and the like.
• the reducing agents are employed in quantities so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1, preferably from about 1:1 to about 10:1, and most preferably from about 1:1 to about 3:1. The ratio is the number of R 3 groups for each atom of transition metal.
• Suitable transition metal compounds which can be employed include those represented by the formula
• TmY n X z-n wherein Tm is a transition metal in its highest stable valence state and being selected from groups IV-B, V-B and VI-B of the Periodic Table of the Elements; Y is oxygen, OR" or NR"; R" is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen, preferably chlorine or bromine; z has a value corresponding to the valence of the transition metal, Tm; n has a value of from zero to 5 with the value of z-n being from zero up to a value equal to the valence state of the transition metal, Tm.
• transition metal compounds include, for example, titanium tetrachloride, titanium tetrabromide, dibutoxy titanium dichloride, monoethoxy titanium trichloride, isopropoxytitanium trichloride, tetraisopropoxytitanium, chromyl chloride, vanadium oxytrichloride, zirconium tetrachloride, tetrabutoxyzirconium, vanadium tetrachloride, mixtures thereof and the like.
• Suitable organic inert diluents in which the catalyst support and catalyst can be prepared and in which the a-olefin polymerization can be conducted include, for example, liquefied ethane, propane, isobutane, n-butane, isopentane, n-pentane, n-hexane, the various isomeric hexanes, isooctane, paraffinic mixtures of alkanes having from 8 to 12 carbon atoms, cyclohexane, methylcyclopentane dimethyleyelohexane, dodecane, eicosane industrial solvents composed of saturated or aromatic hydrocarbons such as kerosene, naphthas, etc., especially when freed of any olefin compounds and other impurities, and especially those having boiling points in the range from about -50° to about 200°C. Also included as suitable inert diluents are benzene, toluen
• the catalyst and catalyst supports of the present invention are advantageously prepared under an inert atmosphere such as nitrogen, argon or other inert gas at temperatures in the range of from about -50°C to about 200°C, preferably from about 0°C to about 100°C.
• the time of mixing the various components is not critical; however, times of from about one minute to about thirty-six hours are deemed to be most desirable. The time is ordinarily that which will permit completion of the reaction at the reaction temperature. Rapid mixing of the catalyst components or poor agitation produces a catalyst which is relatively non-uniform with respect to particle size distribution and produces polymers having an undesirably broad particle size distribution.
• the magnesium compound, the optional aluminum, zinc or boron compound, and the oxygen-containing and/or nitrogen-containing compound may be mixed in any order of addition.
• a precipitate sometimes forms, depending upon the oxygen- or nitrogen-containing compound employed, when the oxygen-containing and/or nitrogen-containing compound and magnesium compound are mixed and lumps will form if the reactants are mixed with poor agitation, too rapidly or in too concentrated a mixture.
• These lumps result in a final catalyst which contains lumps which in turn produces a polymer under slurry polymerization conditions having an undesirably broad particle size distribution with a significant percentage of particles unable to pass through a 40 mesh screen.
• Addition of an aluminum, zinc or boron compound may result in a hydrocarbon solution of the magnesium compound and oxygen-containing and/or nitrogen-containing compound mixture and eliminates those previously mentioned undesirable effects. It is preferable to add the oxygen-containing and/or nitrogen-containing compound to a solution of the magnesium compound and the aluminum, zinc or boron compound so as to obtain a desirably uniform polymer particle size distribu.tion.
• the above mentioned catalyst particle size distribution is not as important.
• an aluminum compound is added as a solubilizing agent the catalyst preparation is simplified when using closed metal vessels for the catalyst preparation, such as would be used in the commercial production of polymers and copolymers of ethylene.
• Suitable cocatalysts of activators with which the catalysts of the present invention can be reacted, contacted or employed in the polymerization of a-olefins includes those aluminum, boron, zinc or magnesium compounds represented by the formulas Al(R 3 ) 3- a X a , B(R 3 ) 3- a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 or mixtures thereof wherein X and R 3 are as previously defined and a has a value of from zero to 2, preferably zero to 1 and most preferably zero.
• Particularly suitable cocatalysts or activators include, for example, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, triethylaluminum, triisobutylaluminum, diethylzinc, dibutylmagnesium, butylethylmagnesium, butylmagnesium chloride, diisobutylaluminum hydride, isoprenylaluminum, triethylboron, trimethylaluminum, mixtures thereof and the like.
• the cocatalysts or activators are employed in quantities such that the Al, B, Mg, Zn:Ti or mixtures thereof atomic ratio is from about 0.1:1 to about
• the catalyst and cocatalyst or activator may be added separately to the polymerization reactor or they may be mixed together prior to addition to the polymerization reactor.
• Olefins which are suitably homopolymerized or copolymerized in the practice of this invention are generally any one or more of the aliphatic a-olefins such as, for. example, ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, 4-methylpehtene-1, hexene-1, octene-1, dodecene-1, octadecene-1, 1,7-octadiene and the like.
• aliphatic a-olefins such as, for. example, ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, 4-methylpehtene-1, hexene-1, octene-1, dodecene-1, octadecene-1, 1,7-octadiene and the like.
• a-olefins may be copolymerized with one or more other a-olefins and/or with small amounts i.e., up to about 25 weight percent based on the polymer of other ethylenically unsaturated monomers such as styrene, a-methylstyrene and similar ethylenically unsaturated monomers which do not destroy conventional Ziegler catalysts.
• aliphatic a-mono- olefins particularly ethylene and mixtures of ethylene and up to 50 weight percent, especially from about 0.1 to about 40 weight percent of propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, 1,7-octadiene or similar a-olefin or a-diolefin based on total monomer.
• polymerization is effected by adding a catalytic amount of the above catalyst composition to a polymerization zone containing a-olefin monomer, or vice versa.
• the polymerization zone is maintained at temperatures in the range from about 0° to about 300°C, preferably at slurry polymerization temperatures, e.g., from about 0° to about 95°C, more preferably from about 50° to 90°C, for a residence time of about 15 minutes to 24 hours, preferably 30 minutes to 8 hours.
• a catalytic amount of the catalytic reaction product is generally within the range from about 0.0001 to about 0.1 milligram-atoms titanium per liter of diluent. It is understood, however, that the most advantageous catalyst concentration will depend upon polymerization conditions such as temperature, pressure, diluent arid presence of catalyst poisons and that the foregoing range is given to obtain maximum catalyst yields.
• a carrier which may be an inert organic diluent or excess monomer is generally employed.
• care must be taken to avoid oversaturation of the diluent with polymer. If such saturation occurs before the catalyst becomes depleted, the full efficiency of the catalyst is not realized.
• the amount of polymer in the carrier not exceed about 50 weight percent based on the total weight of the reaction mixture.
• inert diluents employed in the polymerization recipe are suitable as defined as hereinbefore.
• the polymerization pressures preferably employed are relatively low, e.g., from about 10 to about 500 psig. However, polymerization within the scope of the present invention can occur at pressures from atmospheric up to pressures determined by the capabilities of the polymerization equipment. During polymerization it is desirable to agitate the polymerization recipe to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone.
• Hydrogen is often employed in the practice of this invention to control the molecular weight of the resultant polymer.
• hydrogen can be added with a monomer stream to the polymerization vessel or separately added to the vessel before, during or after addition of the monomer to the polymerization vessel, but during or before the addition of the catalyst.
• the polymerization reactor may be operated liquid full or with a gas phase and at solution or slurry polymerization conditions.
• the monomer or mixture of monomers is contacted with the catalytic reaction product in any conventional manner, preferably by bringing the catalyst composition and monomer together with intimate agitation provided by suitable stirring or other means. Agitation can be continued during polymerization. In the case of more rapid reactions with more active catalysts, means can be provided for refluxing monomer and solvent, if any of the latter is present and thus remove the heat of reaction. In any event, adequate means should be provided for dissipating the exothermic heat of polymerization, e.g., by cooling reactor walls, etc. If desired, the monomer can be brought in the vapor phase into contact with the catalytic reaction product, in the presence or absence of liquid material.
• the polymerization can be effected in a batch manner, or in a continuous manner, such as, for example, by passing the reaction mixture through an elongated reaction tube which is contacted externally with suitable cooling medium to maintain the desired reaction temperature, or by passing the reaction mixture through an equilibrium overflow reactor or a series of the same.
• the polymer is readily recovered from the polymerization mixture by driving off unreacted monomer and solvent if any is employed. No further removal of impurities is required.
• a significant advantage of the present invention is the elimination of the catalyst residue removal steps. In some instances, however, it may be desirable to add a small amount of a catalyst deactivating reagent. The resultant polymer is found to contain insignificant amounts of catalyst residue.
• melt index values I 2 and I 10 were determined by ASTM D 1238 conditions E and N respectively.
• the apparent bulk density was determined as an unsettled bulk density according to the procedure of ASTM 1895 employing a paint volumeter from the Sargent-Welch Scientific Company (catalog no. S-64985) as the cylinder instead of the one specified by the ASTM procedure.
• the dibutylmagnesium was a commercial material obtained as a solution in a heptanehexane mixture from the Lithium Corporation of America
• the dihexylmagnesium was a commercial material obtained as a hexane solution from the Ethyl Corporation
• the butylethylmagnesium was a commercial material obtained as a heptane solution from Texas Alkyls, Inc. All ratios are molar ratios unless otherwise indicated.
• the 1.46 molar diethylaluminum chloride, 0.616 molar triisobutylaluminum and 0.921 molar triethylaluminum were obtained as solutions in hexane from Ethyl
• Isopar E was obtained from Exxon Company USA and is a mixture of saturated paraffins having primarily 8 to 9 carbon atoms.
• the reactor contents were filtered and the polyethylene dried in a vacuum overnight at about 60°C to yield 283 grams of polyethylene with a melt index of 0.7 and a bulk density of 19.3 lbs/ft 3 (0.31 g/cc).
• the catalyst efficiency was 236,000 grams of polyethylene per gram of titanium.
• a portion of the supernatant liquid (600 ml) was removed by decantation.
• the solids were reslurried with fresh hexane (600 ml).
• the decantation was repeated two more times to remove hexane soluble reaction products.
• the hydrocarbon insoluble products were allowed to settle and the supernatant liquid was removed by decantation to obtain a slurry having a volume of 450.
• a portion (45 ml) of this slurry was removed and found by analysis to have a Mg:Ti molar ratio of 3.2:1.
• the remaining slurry (405 ml) was mixed with 49 ml TiCl 4 (446 millimoles).
• a diethylaluminum chloride solution (370 ml of 1.46 molar, 540 millimoles) was added dropwise to the stirred slurry.
• the hydrocarbon insoluble products were allowed to settle for about 1/2 hour and the supernatant liquid was removed by decantation.
• the solids were reslurried with fresh hexane. The decantation was repeated five more times to remove hexane soluble reaction products.
• the reactor contents were filtered and the polyethylene dried in a vacuum overnight at about 60°C to yield 383 grams of polyethylene having a melt index of 2.7 and a bulk density of 15.4 lbs/ft 3 (0.25 g/cc).
• the catalyst efficiency was 295,000 grams of polyethylene per gram of titanium.
• the reactor was heated to 85°C, and the reactor pressure adjusted to 60 psig (4 kg/cm 2 ) with hydrogen. Ethylene was introduced and the reactor pressure maintained at 170 psig (12 kg/cm 2 ) with ethylene. Polymerization was allowed to continue for two hours at 85°C, after which the reactor was cooled to room temperature. The reactor contents were filtered and the polyethylene dried in a vacuum overnight at about 60°C. The polyethylene obtained weighed 117 grams. The melt index of the polyethylene was 0.64 and the polymer had a bulk density of 18.0 lbs/ft 3 (0.29 g/cc). The catalyst efficiency was 244,000 grams of polyethylene per gram of titanium and 58,000 grams of polyethylene per gram of total catalyst calculated as indicated in footnote 8 of Table I.
• a 100 ml hexane solution contining 37.6 ml of n-propylalcohol (500 millimoles) was added dropwise to a stirred 375 ml hexane solution containing 168.6. ml of .593 molar dibutylmagnesium (100 millimoles) and 162.3 ml of .616 molar trisobutylaluminum (100 millimoles).
• a 100 ml hexane solution containing 44.0 ml of TiCl 4 400 millimoles was added dropwise to the stirred magnesium alkyl-aluminum alkylalcohol mixture.
• a 100 ml hexane solution containing 39.0 ml of n-propylalcohol (519 millimoles) was added dropwise to a stirred 425 ml hexane solution containing 316.2 ml of .593 molar dibutylmagnesium (187.5 millimoles) and 75.0 ml of .616 molar triisobutylaluminum (46.2 millimoles).
• a 250 ml hexane solution containing 82.4 ml of TiCl 4 750 millimoles was added dropwise to the stirred magnesium alkyl-aluminum alkylalcohol mixture.
• the resulting hydrocarbon insoluble solid was allowed to settle for 20 mintues, followed by decantation of the supernatant. Seven additional decantations were made with fresh hexane. Then 81.4 ml TiCl 4 (750 millimoles) was added to the stirred slurry, followed by dropwise addition of a 600 ml hexane solution containing 513.7 ml of 1.46 molar diethylaluminum chloride (750 millimoles). The solid was allowed to settle for 30 mintues, followed by decan tation of the supernatant. Seven additional decantations were made with fresh hexane. Analysis of the final catalyst gave a Mg:Ti atomic ratio of 0.25:1.0.
• a 60 ml hexane solution containing 21.3 ml of n-propylalcohol (283 millimoles) was added dropwise to a stirred 200 ml hexane solution containing 126.5 ml of .593 molar dibutylmagnesium (75.0 millimoles) and 34.7 ml of 1.08 molar diethyl zinc (37.5 millimoles) solution in hexane.
• a 60 ml hexane solution containing 16.5 ml of TiCl 4 150 millimoles was added dropwise to the stirred magnesium alkyl-zinc alkyl-alcohol mixture.
• the resulting slurry was allowed to settle for 15 minutes, and the supernatant then decanted.
• Six additional decantations were made with fresh hexane.
• the solid was again slurried in hexane and 8.25 ml of TiCl 4 (75 millimoles) was added, followed by dropwise addition of a 150 ml hexane solution containing 51.4 ml of 1.46 molar diethyl aluminum chloride (75.0 millimoles). The solid was allowed to settle for 15 mintutes and the supernatant was decanted. Seven additional decantations were made with fresh hexane. Analysis of the catalyst slurry gave a Mg:Ti atomic ratio of 1.0:1.0.
• a 100 ml hexane solution containing 3.55 gm (50 millimoles) of ethyl isocyanate was added dropwise to a stirred 200 ml hexane solution of 42.2 ml of 0.593 molar dibutylmagnesium (25 millimoles).
• a 200 ml hexane solution containing 32.7 ml (50 millimoles) of 1.53 molar diethylaluminum chloride in hexane was added dropwise to the stirring magnesium alkyl-ethyl isocyanate reaction mixture.
• a 200 ml hexane solution containing 22.0 cc (200 millimoles) of TiCl 4 was added dropwise to the stirring hexane slurry of the solid made above. Successively, a 200 ml hexane solution containing 137.0 ml (200 millimoles) of 1.46 molar diethylaluminum chloride was added dropwise. The resultant slurry was allowed to stir for 20 minutes, the supernatant was decanted, and the remaining solid was slurried in fresh hexane. Seven additional decantations were made with fresh hexane. The final solid was slurried in fresh hexane and stored in a capped bottle. Analysis of the catalyst gave a Mg:Ti atomic ratio of 0.21:1.
• Example 3(B) The polymerization procedure of example 3(B) was repeated using 2.4 ml of 0.616 molar triisobutylaluminum (1.50 millimoles) and an aliquot of catalyst prepared in (A) above containing 0.030 millimoles of titanium.
• the polyethylene obtained weighed 115 grams, had a melt index of 0.19 and had a bulk density of 12.8 lbs/ft 3 (0.21 g/cc).
• the catalyst efficiency was 80,000 grams of polyethylene per gram of titanium.
• This material was washed and decanted several times to remove all hexane soluble compounds.
• the solid was slurried in 300 ml of hexane and TiCl 4 (60 millimoles) was added in a single portion. To this mixture was added, over a 30-minute period, diethylaluminum chloride (120 millimoles) dissolved in 100 cc of hexane. The resultant brown solid was washed and decanted several times to remove the hydrocarbon soluble products.
• Titanium tetrachloride (100 ml of 1.0 molar in hexane, 100 millimoles) was added.
• a 1.46 molar diethylaluminum chloride solution (68 ml, 100 millimoles) was added dropwise to the stirred slurry. The solids were allowed to settle and the supernatant liquid removed by decantation.
• a solution of 12.0 ml diethylcarbonate (100 millimoles) in 100 ml of hexane was added dropwise to a stirred solution of 84.3 ml of 0.593 molar dibutylmagnesium (50 millimoles).
• a hexane solution of ethylaluminum dichloride (49.0 ml of 1.53 molar, 75 millimoles) was added dropwise to the stirred mixture of dibutylmagnesium and diethylcarbonate. The solids were allowed to settle and the supernatant liquid was decanted. Fresh hexane was added and the decantation repeated until a total of 3 decants had been made.
• a titanium tetrachloride solution (25,0 ml of 1.0 molar, 25 millimoles) in hexane was added along with hexane to give a total volume of about 250 ml.
• the mixture was stirred while 17.1 ml of 1.46 molar diethylaluminum chloride solution (25 ml, 100 millimoles) was added dropwise.
• the solids were allowed to settle and the supernatant liquid removed by decantation. Fresh hexane was added and the decantation repeated a total of six times to remove the hexane soluble species.
• Succinimide (4.95 grams, 50 millimoles) was slowly added to a stirred solution of 42.2 ml (25 millimoles) of 0.593 molar dibutylmagnesium. After two hours of continuous stirring, 32.7 ml of 1.53 molar ethylaluminum dichloride (50 millimoles) in hexane was added dropwise, The solids were allowed to settle and the supernatant liquid was removed by decantation. Fresh hexane was added to the slurry and the decantation repeated until a total of 3 decants had been made. Fresh hexane was added to give a total volume of about 75 ml.
• a titanium tetrachloride (100 ml of 1.0 molar, 100 millimoles) in hexane was added along with hexane to give a total volume of about 300 ml.
• the mixture was stirred while 68.5 ml of 1.46 molar diethylaluminum chloride (100 millimoles) was added dropwise.
• the solids were allowed to settle and the supernatant liquid removed by decantaion.
• Fresh hexane was added and the decantation repeated a total of six times to remove the hexane soluble species.
• a mixture of 169 ml of 0.593 molar dibutylmagnesium (100 millimoles) and 325 ml of 0.616 molar triisobutylaluminum (200 millimoles) were added to a one-liter stainless steel stirred reactor. Carbon dioxide was added to the reactor to give a pressure of 30 psig. The reaction exotherm heated the reactor to 50-60°C. After two hours the reactor had cooled to ambient temperature. The carbon dioxide atmosphere in the reactor was replaced with nitrogen by purging and the reactor was taken into a gloved box. The reactor contents was made up to.500 ml with hexane to give a mixture which was 0.20 molar in magnesium.
• a 100 ml hexane solution containing 350 millimoles of a n-propyl alcohol was added dropwise to a stirred 500 ml hexane solution containing 168.6 ml of .593 molar dibutyl magnesium (100 millimoles) and 81.2 ml of .616 molar tri-isobutylaluminum (50 millimoles).
• a 100 ml hexane solution containing 22.0 ml of 9.1 molar TiCl 4 (200 millimoles) was added dropwise. The resultant solid was allowed to settle for 15 minutes and the supernatant was decanted off.
• the polymer obtained weighed 136 grams.
• the melt index of the polymer was 0.27 and the density, measured according to ASTM-D792-66, was .9444 gram per cm 3 .
• the catalyst efficiency was 145,000 grams of polymer per gram titanium and 35,000 grams of polymer per gram of total catalyst as calculated from the Mg:Ti ratio assuming a mixture of MgCl 2 and TiCl 3 .
• the polymer obtained weighed 158 grams, had a melt index of 0.15 and had a density, measured according to ASTM-D792-66, of .9304 gram per cm 3 .
• Catalyst efficiency was 165,000 grams polymer per gram titanium and 39,000 grams polymer per gram of total catalyst as calculated from the Mg:Ti ratio assuming a mixture of MgCl 2 and TiCl 3 .
• a solution of 30.1 ml n-propylalcohol (400 millimoles) and 100 ml hexane was added dropwise to a stirred solution of 157 ml of 0.637 molar butylethylmagnesium (100 millimoles) in heptane and 81 ml of 0.616 molar triisobutylaluminum (50 millimoles) hexane.
• the resultant solution was cooled to 30°C, and a solution of 44.0 ml titanium tetrachloride (400 millimoles) in 200 ml of hexane was added dropwise with continuous stirring.
• the slurry was stirred for one-half hour, the hydrocarbon insoluble products were allowed to settle, and the supernatant solution was removed by decantation. The solids were reslurried with fresh hexane. The decantation procedure was repeated two more times to remove most of the hexane soluble reaction products. The hydrocarbon insoluble products were slurried with hexane to give a total volume of 800 ml.
• a 1.8 liter stirred stainless steel reactor containing 1.0 liter of dry, oxygen-free Isopar E and 0.54 ml of 0.921 molar triethylaluminum (0.50 millimole) in hexane was vented to zero psig.
• the reactor was heated to 150°C and hydrogen added to give a reactor pressure of 25 psig.
• ethylene was added to the reactor to a pressure of 120 psig.
• the catalyst 25 ml of 0.001 molar slurry in Isopar ® E) prepared in Example 29(A) was pressured into the reactor using nitrogen.
• the reactor temperature was maintained at 150°C by heating or cooling and the reactor pressure was maintained at 145 psig by adding ethylene.
• a solution (4.14 parts by weight, pbw) of butylethylmagnesium containing 2.40 weight percent magnesium in heptane and a solution (2.19 pbw) of 20.3 weight percent triisobutylaluminum in hexane were mixed in a stirred, jacketed reactor.
• the solution temperature was maintained at below 40°C while 1.00 pbw of n-propylalcohol and 6.33 pbw of hexane were added.
• the resultant solution temperature was maintained at 35°C while 3.08 pbw of titanium tetrachloride was slowly added.
• the resultant slurry was cooled to about 25°C, the solids allowed to settle, and the supernatant liquid removed by decantation.
• the solids were reslurried with fresh hexane and the decantation procedure repeated until less than 10 mole percent of the total titanium content is in solution.
• the resultant slurry after the decantations was 140 millimolar in magnesium and had a total weight of 6.84 pbw.
• Titanium tetrachloride (0.59 pbw) was added to the stirred slurry.
• a 25 weight percent diethylaluminum chloride solution (1.64 pbw) in hexane was slowly added to the stirred mixture.
• the solids were allowed to settle and the supernatant liquid removed by decantation.
• the solids were reslurried with fresh hexane and the decantation procedure repeated several times to remove the hydrocarbon soluble species.
• Example 30(A) The catalyst prepared in Example 30(A) was diluted with hexane to 0.3 millimolar in titanium. This diluted catalyst was then added at a rate of about 12 pbw per hour to a partially full agitated reactor. Simultaneously, 100 pbw of ethylene per hour, 1 pbw of butene-1 per hour and 223 pbw of hexane per hour were added to the reactor while the reactor temperature and pressure were controlled at 85°C and 170 psig respectively. A two weight percent solution of triisobutylaluminum in hexane was added at a rate so as to give an Al/Ti atomic ratio of about 50:1 in the reactor.
• Hydrogen was added to the gaseous phase of the reactor so as to obtain the desired polymer melt index.
• the reactor contents were continuously removed, the polymer and hexane separated, and the dried polymer collected.
• the polymer had a melt index of 11.
• the catalyst efficiency was about 400,000 pounds of polymer per pound of titanium.
• a solution of 50 ml of 0.5 molar anhydrous cobalt dichloride (25 millimoles) in n-propylalcohol was added dropwise to 526 ml of a stirred solution of 0.475 molar dibutyImagesium (250 millimoles).
• a solution of 55 ml titanium tetrachloride (500 millimoles) in 100 ml of hexane was added dropwise to the resulting slurry. The solids were allowed to settle and the supernatant liquid removed by decantation. Fresh hexane was added and the decantation procedure was repeated five more times to remove the hexane soluble species.
• Titanium tetrachloride (55 ml, 500 millimoles) was added to the stirred hexane slurry and then 342 ml of a 1.46 molar diethylaluminum chloride solution was added dropwise. The solids were allowed to settle and the supernatant liquid removed by decantation. Fresh hexane was added and the decantation procedure was repeated five more times to remove the hexane soluble species.
• Triisobutylaluminum (0.49 ml of.0.616 molar; 0.30 millimole) and then an aliquot of catalyst containing 0.015 millimoles of Ti, prepared in (A) above, were added to a stirred 1.0 liter stainless steel reactor containing 0.5 liter of dry, oxygen-free hexane.
• the reactor was pressured to about 50 psig (4 kg/cm 2 ) with hydrogen at room temperature and then vented to 5 psig (0.4 kg/cm 2 ). The pressure venting with hydrogen was repeated 9 times. Then the reactor was heated to 85°C and the reactor pressure adjusted to 60 psig (4 kg/cm 2 ) by adding hydrogen.
• Ethylene was introduced and the reactor pressure maintained at 170 psig (12 kg/cm 2 ) with ethylene.
• the polymerization was allowed to continue for two hours at 85°C, after which the reactor was cooled to room temperature.
• the reactor contents were filtered and the polyethylene dried in a vacuum overnight at about 60°C.
• the polyethylene obtained weighed 219 grams, had a melt index of 0.35, and a bulk density of 24.0 lbs/ft 3 (0.39 g/cc).
• the catalyst efficiency was 305,000 grams of polyethylene per gram of titanium.
• Titanium tetrachloride (55 ml, 500 millimoles) was added to the stirred hexane slurry and then 342 ml of a 1.46 molar diethylaluminum chloride solution was added dropwise. The solids were allowed to settle and the supernatant liquid removed by decantation. Fresh hexane was added and the decantation procedure was repeated five more times to remove the hexane soluble species.
• Example 31(B) The procedure of Example 31(B) was repeated using 1.0 ml of 0.616 molar triisobutylaluminum

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