CA1190210A - Ultra high efficiency catalyst for polymerizing olefins prepared from organotitanium and alkylzinc compounds - Google Patents
Ultra high efficiency catalyst for polymerizing olefins prepared from organotitanium and alkylzinc compoundsInfo
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- CA1190210A CA1190210A CA000420064A CA420064A CA1190210A CA 1190210 A CA1190210 A CA 1190210A CA 000420064 A CA000420064 A CA 000420064A CA 420064 A CA420064 A CA 420064A CA 1190210 A CA1190210 A CA 1190210A
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Abstract
ABSTRACT OF THE DISCLOSURE
Alpha olefins are polymerized in the presence of catalyst compositions which are the catalytic reaction products of (A) the reaction product or complex resulting from the mixing of (1) a mixture of a transition metal compound such as tetraalkoxy titanium compound and an alcohol and (2) an essentially nonreducing alkylating agent such as a dialkyl zinc compound and (B) a magnesium halide.
Alpha olefins are polymerized in the presence of catalyst compositions which are the catalytic reaction products of (A) the reaction product or complex resulting from the mixing of (1) a mixture of a transition metal compound such as tetraalkoxy titanium compound and an alcohol and (2) an essentially nonreducing alkylating agent such as a dialkyl zinc compound and (B) a magnesium halide.
Description
32~
ULTRA HIGH EFFICIENCY
CATALYST FOR POLYMERIZING OLEFINS
This invention relates to new catalyst compositions for polymerization of ~-olefins and to a polymerization process employing such catalyst compositions.
It is well known that olefins such as ethy-lene, propylene and 1-butene in the presence of certain transition metal catalysts can be polymerized to form substantially unbranched polymers of relatively high molecular weight. Typically such polymerizations are carried out at relatively low temperatures and pressures.
- Among the methods o producing such linear olefin polymers, some of the most widely utilized are those described by Professor Karl Ziegler in U.S.
Patents 3,113,115 and 3,257,332. In these methods, the catalyst employed is obtained by admixing a compound of a transition metal of Groups IVB, VB, VIB and VIII of Mendeleev's Periodic Table of Elements with an organo-metallic compound. Generally, the halides, oxyhalides and alkoxides or esters of titanium, vanadium and 29,019A-F -1-.
--2~
zirconium are the most widely used transition metal compounds. Common examples of the organometallic compounds include the hydrides, alkyls and haloalkyls of aluminum, alkylaluminum halides, Grignard reagents, alkali metal aluminum hydrides, alkali metal borohy-drides, alkali metal hydrides, alkaline earth me-tal hydrides and the like. Usually, polymerization is carried ou-t in a reaction medium comprising an iner-t organic liquid, e.g. an aliphatic hydrocarbon, and the aforementioned ca-talyst. One or more olefins may be brought into contact with the reac-tion medium in any suitable manner. A molecular weight regulator, which is normally hydrogen, is usually present in the reaction vessel in order to suppress the formation of undesirable high molecular weight polymers.
Most of the aformentioned known catalyst systems are more efficient in preparing polyolefins in slurry (i.e., wherein the polymer is not dissolved in the carrier) than in solution (i.e., wherein the temperature is high enough to solubilize the polymer in the carrier). The lower efficiencies of such catalys-ts in solution polymerization is believed to be caused by deactivation of such catalysts by the higher temperatures employed in solution processes. In addition, processes involving the copolymerization of ethylene with higher ~-olefins exhibit catalyst efficiencies significantly lower than ethylene homopolymerization processes.
Recently, e.g. British 1,492,379, high efficiency catalysts have been disclosed which permit polymerization temperatures above 140C. Such high polymerization temperatures provide for reduced energy requirements in solution polymerization processes in 29,019A-F -2---3~
that the closer the polymerization temperature is to the boiling point of the polymerization solvent, the less energy is required in removing the solvent.
U.S. Paten~s 4,250,286 and 4,269,733 disclose the preparation of a catalyst for polymeriz.ing olefins in which the catalyst contains the product resulting from the admixture of a transition metal compound and a zinc compoundO
It has now been discovered that such catalyst can be impro~ed if the transition metal compound is first mixed with certain oxygen-containing materials beore addition of the zinc compound. The catalysts subsequently prepared therefrom have higher initial rates of reaction and higher efficiencies than do those catalysts prepared without the oxygen-containing material.
SUMMARY OF THE INVENTION
The present invention is a catalyst for the polymerization of -olefins under Ziegler polymerization conditions and comprising a magnesium halide, a transition metal compound an a zinc compound characterized by first forming:
(A) a reaction product or complex formed from the admixture of (1) a reaction product or complex formed by mixing (1.1) at least one transition metal compound represented by the empirical formulae Tm(OR)yXx y, TxOXx_2 or Tm(OR)x-20 wherein Tm is a transition metal selected from groups IV~, VB or VIB;
29,019A-F -3--3a- 1~9~ 2 ~ ~
each R is independently a hydrocarbyl group, having from 1 to 20 carbon atoms; each X
is independently a halogen; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm; and (1.2) at least one oxygen-contain-ing compound; and
ULTRA HIGH EFFICIENCY
CATALYST FOR POLYMERIZING OLEFINS
This invention relates to new catalyst compositions for polymerization of ~-olefins and to a polymerization process employing such catalyst compositions.
It is well known that olefins such as ethy-lene, propylene and 1-butene in the presence of certain transition metal catalysts can be polymerized to form substantially unbranched polymers of relatively high molecular weight. Typically such polymerizations are carried out at relatively low temperatures and pressures.
- Among the methods o producing such linear olefin polymers, some of the most widely utilized are those described by Professor Karl Ziegler in U.S.
Patents 3,113,115 and 3,257,332. In these methods, the catalyst employed is obtained by admixing a compound of a transition metal of Groups IVB, VB, VIB and VIII of Mendeleev's Periodic Table of Elements with an organo-metallic compound. Generally, the halides, oxyhalides and alkoxides or esters of titanium, vanadium and 29,019A-F -1-.
--2~
zirconium are the most widely used transition metal compounds. Common examples of the organometallic compounds include the hydrides, alkyls and haloalkyls of aluminum, alkylaluminum halides, Grignard reagents, alkali metal aluminum hydrides, alkali metal borohy-drides, alkali metal hydrides, alkaline earth me-tal hydrides and the like. Usually, polymerization is carried ou-t in a reaction medium comprising an iner-t organic liquid, e.g. an aliphatic hydrocarbon, and the aforementioned ca-talyst. One or more olefins may be brought into contact with the reac-tion medium in any suitable manner. A molecular weight regulator, which is normally hydrogen, is usually present in the reaction vessel in order to suppress the formation of undesirable high molecular weight polymers.
Most of the aformentioned known catalyst systems are more efficient in preparing polyolefins in slurry (i.e., wherein the polymer is not dissolved in the carrier) than in solution (i.e., wherein the temperature is high enough to solubilize the polymer in the carrier). The lower efficiencies of such catalys-ts in solution polymerization is believed to be caused by deactivation of such catalysts by the higher temperatures employed in solution processes. In addition, processes involving the copolymerization of ethylene with higher ~-olefins exhibit catalyst efficiencies significantly lower than ethylene homopolymerization processes.
Recently, e.g. British 1,492,379, high efficiency catalysts have been disclosed which permit polymerization temperatures above 140C. Such high polymerization temperatures provide for reduced energy requirements in solution polymerization processes in 29,019A-F -2---3~
that the closer the polymerization temperature is to the boiling point of the polymerization solvent, the less energy is required in removing the solvent.
U.S. Paten~s 4,250,286 and 4,269,733 disclose the preparation of a catalyst for polymeriz.ing olefins in which the catalyst contains the product resulting from the admixture of a transition metal compound and a zinc compoundO
It has now been discovered that such catalyst can be impro~ed if the transition metal compound is first mixed with certain oxygen-containing materials beore addition of the zinc compound. The catalysts subsequently prepared therefrom have higher initial rates of reaction and higher efficiencies than do those catalysts prepared without the oxygen-containing material.
SUMMARY OF THE INVENTION
The present invention is a catalyst for the polymerization of -olefins under Ziegler polymerization conditions and comprising a magnesium halide, a transition metal compound an a zinc compound characterized by first forming:
(A) a reaction product or complex formed from the admixture of (1) a reaction product or complex formed by mixing (1.1) at least one transition metal compound represented by the empirical formulae Tm(OR)yXx y, TxOXx_2 or Tm(OR)x-20 wherein Tm is a transition metal selected from groups IV~, VB or VIB;
29,019A-F -3--3a- 1~9~ 2 ~ ~
each R is independently a hydrocarbyl group, having from 1 to 20 carbon atoms; each X
is independently a halogen; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm; and (1.2) at least one oxygen-contain-ing compound; and
(2) at least one non-reducing alkylating agent represented by the empirical formulae ZnR2 or RZnX wherein X is a halogen, preferably chlorine or bromine and each R is independently an alkyl group having from 1 to 20 carbon atoms; and thereafter admixing (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical form~la MgR"2-xMR"y wherein M is aluminum or zinc, each R" is independently a hydrocarbyl or hydrocarbyloxy group having from 1 to 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (2.1) an active non-metallic halide, said non-metallic halide corres-ponding to the empirical formula R'X wherein R' is hydrogen or a - hydrocarbyl group such that the hydrocarbyl halide is at least as ac-tive as sec-butyl chloride and does not poison the catalyst, . and X is halogen or ... . .
~`~ 29,019A -3a-3b-.
(2.2) a metallic halide correspond-ing to the empirical formula MR~ aXa wherein M is a metal of Group IIIA or IVA of Mendel~
eev's Periodic Table o Elements, X is a monovalent hydrocarbyl radical, X is halogen, y is a number corresponding to the, valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound is added which is represented by the empirical formula AlRy,Xy,l wherein R and X are as defined above and y' and y"
each have a value of from zero to three with the sum of y' and y" being three;
and said components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from 1:1 to 200:1; Zn:Tm of from 0.1:1 to 10:1; O:Tm of from 0.1:1 to 4 1; Al:Tm of from 0.1:1 to 200:1 and an excess X:Al of from 0.0005:1 to 5:1.
Another aspect of the presen~ invention is a process for polymerizing ethylene and other ~-olefins under Ziegler polymerization conditions in the presence of a catalyst comprising a magnesium halide, a titanium compound, and a zinc compound characterized in that the catalyst is prepared by first forming a reaction product or complex (A) of a mixture of a titanium compound of the formula Ti(OR)4 where R is Cl-C10 alkyl and an alcohol in quantities to provide an atomic ratio of OoTi of 0.1:1 to 4:1 with an organo zinc compound of the formula ZnRx wherein R is Cl-C10 29,019A-F -3b-~3c-(A) of a mixture of a titanium com~ound of ~he formula Ti(OR~4 where R ls Cl-C10 alkyl and an alcohol in quantities to provide an atomic ratio of O:Ti of 0.1:1 to 4:1 with an organo zinc compound of the formula ZnR2 wherein R is Cl-C10 alkyl; and thereafter admi~cing (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR"2-xMR"y wherein M is aluminum or zinc, each R"
is independently a hydrocarbyl or hydro-carbyloxy group having from 1 to 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (2.1) an active non-metallic halide, , said non-metallic halide corres-ponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst, and X
. is halogen or (2.2) a metallic halide corresponding to ~he empirical formula MRy aXa wherein ~ is a metal of Group IIIA
or IVA of Mendeleev's Periodic Table of Elements, R is a mono-valent hydrocarbyl radical, X is halogen, y is a number corres-ponding to the valence of M and a is a number of 1 to y; and 29,019A-F -3c-(C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound is added which is represented by the empirical formula AlRy~Xyl~ wherein R
and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and said components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from 1:1 to 200:1; Zn:Tm of from 0.1:1 to 10:1; O:Tm of from 0.1:1 to 4:1; AloTm of from 0.1:1 to 200:1 and an excess X:Al of from 000005:1 to 501.
The components are employed in quantities which provide the composition with atomic ratios of the elements as follows.
29,010A-~ -4-2~D
Mg:Tm is from l:1 -to 200:1, preferably ~rom 2:1 to 100:1 and ~lost preerably from 5:1 -to 75:1.
, Al:Tm is from 0.1:1 to 200:1, preferably from 0.5:1 to 100:1 and most preferably from 1:1 to 75:1.
Excess X:Al is from 0.0005:1 to 5:1, preferably from 0.002:1 to 2:1 and most preferably from 0.01:1 to 1.4:1.
Excess X is the amount of halide above that amount which is theoretically required to convert the organomagnesium component to magnesium dihalide.
The present invention is most advantageously practiced in a polymerization process wherein an ~-olefin is polymerized, generally in the presence of hydrogen as a molecular weight control agent, in a polymerization zone containing an inert diluent and the catalytic reaction product as hereinbefore described. Especially advantageous is the copolymerization of ethylene and higher ~-olefins using the catalytic reaction product of this invention. The foregoing polymerization process is most beneficially carried out undex inert atmosphere and relatively low pressures, although very high pressures are optionally employed.
Olefins which are suitably homopolymeri~ed or copolymerized in the practice of this invention are generally the aliphatic ~-monoolefins or non-conjugated ~-diolefins having from 2 to 18 carbon atoms. Illustra-tively, such ~-olefins can include ethylene, propylene, butene-1, pentene-1, 3-methylbutene~ methylpentene-1, hexene-1, octene-l, dodecene-1, octadecene-1, 1,7 octadiene, 1,4-hexadiene, and mixtures thereof. It is understood 29,019A-F -5-2~) -that ~-olefins may be copolymerized with other ~-olefins and/or with small amounts, i.e., up to abou-t 25 weight perc~nt,based on the polymer, of other ethylenically unsaturated monomers such as styrene, ~-methylstyrene S and similar ethylenically unsaturated monomers which do not destroy conventional Ziegler catalysts. Mos-t benefits are realized in the polymerization of aliphatic ~-monoolefins, particularly ethylene and mixtures of ethylene with up to 50, especially from 0.1 to 40, weight percent of propylene, butene-1, hexene-1, octene-l, 4-methylpentene-1, 1,7-octadiene, 1,4-hexadiene or similar ~-olefin or non-conjugated ~-diolefins based on total monomer.
Suitable zinc compounds which can be employed as the essentially non-reducing alkylating agent are those represented by the empirical formulae R2Zn or RZnX wherein each R is independently a hydrocarbyl group having from l to 20, preferably from 1 to 10, carbon atoms and X is a halogen, preferably chlorine or bromine. Particularly suitable zinc compounds include, for example, diethyl zinc, dimethyl zinc, ethyl zinc chloride, diphenyl zinc and mixtures thereof.
~ y the term essentially non-reducing it is meant that simple mixing of the alkylating agent with the titanium species at normal conditions does not lead to a reduction in the oxidation state of the titanium compound.
Suitable non-metallic oxygen-containing compounds which can be employed herein include, for example, molecular oxygen, alcohols, ketones, alde-hydes, carboxylic acids, esters of carboxylic acids, 29,019A-F -6---7~
peroxides, and water. Those compounds which are so]uble in hydrocarbon solvent are especially preferred.
r Particularly suitable alcohols include, for example, n-butanol, sec-butanol, iso-propanol, n-pxopanol, and mixtures -thereof.
Particularaly suitable ketones which can be employed herein include, for example, acetone, methyl-ethyl ketone, methyl isobutyl ketone, and mixtures thereof.
Particularly suitable carboxylic acids which can be employed herein include, for example, formic acid, acetic acid, stearic acid, and mixtures thereof.
Particularly suitable ethers which can be employed include, for example, diethyl ether, ethyl vinyl ether, and mixtures thereof.
Particularly suitable aldehydes which can be employed herein include, for example, formalehyde, acetaldehyde, propionaldehyde, and mixtures thereof.
Particularly suitable peroxides which can be employed herein include, for example, hydrogen peroxide, t-butylperoxide, and mixtures thereof.
Suitable transition metal compounds which can be employed in the present invention include those represented by the empirical formulae Tm(OR)yXx y , Tm(OR)x 2 or TmOXx 2 wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is indepen-dently a hydrocarbyl group, preferably alkyl or aryl, 29,019A-F -7-312~
having from 1 to 20, preferably from 1 to 10, carbon atoms; each X is independently a halogen, preferably chlorin~ or bromine; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm.
Particularly suitable transition metal com-pounds include for example tetraethoxy titanium, tetra-isopropoxy titanium, tetra-n-bu-toxy titanium, di-n-butoxy titanium dichloride, tetraphenoxy titanium, tetra-n-propoxy titanium, tetra-(2-ethylhexoxy) titanium, tri-n-butoxy vanadium oxide, oxyvanadium trichloride, tri-isopropoxy vanadium oxide, zirconium tetra-n-butoxide, zirconium tetra-n-propoxide, zirconium tetra-isopropoxide, and mixtures thereof.
Suitable organomagnesium components which can be ~mployed in the present invention include those represented by the empirical formula MgR"2-xMR"y wherein each R" is independently hydrocarbyl or hydrocarbyloxy, M is aluminum, zinc or mixtures thereof and x is zero to 10, preferably zero to 5, most preferably from zero to 2.5; and y denotes the number of hydrocarbyl and/or hydrocarbyloxy groups which corresponds to the valence of M. As used herein, hydrocarbyl and hydrocarbyloxy are monovalent hydrocarbon radicals. Preferably, hydrocarbyl is alkyl, cycloalkyl, aryl, aralkyl, alkenyl and similar hydrocarbon radicals having 1 to 20 carbon atoms, with alkyl having 1 to 10 carbon atoms being especially preferred. Likewise, preferably, hydro-carbyloxy is alkoxy, cycloalkyloxy, aryloxy, aralkyloxy, alkenyloxy and similar oxyhydrocarbon radicals having 1 to 20 carbon atoms, with alkoxy having 1 to 10 carbon atoms b~ing preferred. Hydrocarbyl is preferred over hydrocarbyloxy.
29,019A-F -8-2~1D
`~ g Preferably the organomagnesium compound is a hydrocarbon soluble dihydrocarbylmagnesium such as the magnes~um dialkyls and the magnesium diaryls. Exemplary suitable ma~nesium dial]~yls include particularly n-butyl-sec-buty] magnesium, di.isopropyl magnesium, di-n-hexyl magnesium, isopropyl~n-butyl magnesium, ethyl-n-hexyl magnesium, ethyl-n-butyl magnesium, di-n-octyl magnesium and others wherein the alkyl has from 1 to 20 carbon atoms. Exemplary suitable magnesium diaryls include diphenylmagnesium, dibenzyl-magnesium, and ditolylmagnesium. Suitable organo-magnesium compounds include alkyl and aryl magnesium alkoxides and aryloxides and aryl and alkyl magnesium halides with the halogen-free organomagnesium compounds being more desirable.
Among the halide sources which can be employed herein are the active non-metallic halides and me-tallic halides.
Suitable non-metallic halides are represented by the empirical formula R'X wherein R' is hydrogen or an active monovalent organic radical and X is a halogen.
Particularly suitable non-metallic halides include, for example, hydrogen halides and active organic halides such as t-alkyl halides, allyl halides, benzyl halides and other active hydrocarbyl halides wherein hydro-carbyl is as defined hereinbefore. By an active organic halide is meant a hydrocarbyl halide that contains a labile halogen at least as active, i.e. as easily lost to another compound, as the halogen of sec-butyl chloride, preferably as active as t-butyl chloride. In addition to the organic monohalides, it is understood that organic dihalides, trihalides and other polyhalides 29,019A-F -9-that are ac-tive as defined hereinbefore are also suit-ably employed. Examples of preferred active non-metalli,c halides include hydrogen chloride, hydrogen bromide, t-butyl chloride, t-amyl bromide, allyl chloride, benzyl chloride, crotyl chloride, methylvinyl carbinyl chloride, ~phenylethyl bromide, and diphenyl methyl chloride. Most preferred are hydrogen chloride, t-butyl chloride, allyl chloride and benzyl chloride.
Suitable metallic halides which can be employed herein include those represented by the empirical formula MRy aXa wherein M is a metal of Groups IIIA or IVA, of Mendeleev's Periodic Table of Elements, R is a monovalent organic radical, X is a halogen, y has a value corresponding to the valence of M and a has a value from 1 to y. A suitable metallic halide is SnCl4, although the preferred metallic halides are aluminum halides of the empirical formula AlR3 aXa wherein each R is independently hydrocarbyl as herein-before defined such as alkyl, X is a halogen and a is a number from 1 to 3. Most preferred are alkylaluminum halides such as ethylaluminum sesquichloride, diethyl aluminum chloride, ethylaluminum dichloride, and diethylaluminum bromide, with e-thylaluminum dichloride being especially preferred. Alternatively, a metal halide such as aluminum trichloride or a combination of aluminum trichloride with an alkyl aluminum halide or a trialkyl aluminum compound may be suitably employed.
It is understood that the organic moieties of the aforementioned organomagnesium, e.g. R", and the organic moieties of the halide source, e.g. R and R', are suitably any other organic radical provided that they do not contain functional groups that poison 29,019A-F -10-conven-tional Ziegler catalysts. Preferably such organic moieties do not contain active hydrogen, i.e., those suffici,en-tly active to react with the Zerewi-tinoff reagen-t.
In preparing the reaction product or complex of the present invention, the transition metal compo-nen-t and oxygen-containing component are mixed together in a sui-table inert solvent or diluent -followed by the - addi-tion of the alkylating agen-t in a quantity and under suitable conditions so as to effect a color change in the reaction mixture. Suitable conditions include temperatures of from about -50C to 110C, preferably from 0C to 30C. At lower temperatures, longer times may be re~uired to effect a color change.
The reaction time is also affected by the concentration of the reactants, e.g. low concentrations require longer times at any given temperature than do higher concentrations. The solvents which can be employed include those suitable for preparing the catalysts of this invention with the hydrocarbon sol-vents being most suitable.
The color change which occurs upon addition of the essentially non-reducing alkylating agent varies depending upon the particular components employed, i.e.
the particular oxygen-containing compound and/or the particular alkylating agent.
The magnesium halide can be preformed from the organomagnesium compound and the halide source or it can be prepared in situ in which instance the catalyst is prepared by mixing in a suitable solvent (1) the 29,019A-F
organomagnesium component, B-l, (23 the halide source, B-2 and (3) the reaction product or complex formed by mixing,(a) a mixtuxe of said -transition metal component (A-1.1) and said oxygen-containing componen-t (A-1.2)and (b) said alkylating agent (A-2).
The foregoing catalyst components are com-bined in proportions sufficient to provide atomic ratios as previously mentioned.
In cases wherein neither the organomagnesium component nor the halide source contains aluminum or contains an insufficient quantity of aluminum, it is necessary to include in the total catalyst an aluminum compound such as an alkyl aluminum compound, e.g. a trialkyl aluminum, an alkyl aluminum halide or an aluminum halide. If polymerization temperatures below 180C are employed, the atomic ratios of Al:Ti may be from 0.1:1 to 200:1, preferably from 1:1 to 100:1.
However, when polymerization -temperatures above 180C
are employed, the aluminum compound is used in propor-tions such that the Mg:Al ratio is more than 0.3:1,preferably from 0.5:1 to 10:1, and Al:Ti ratio is less than 120:1, preferably less than 50:1. It is understood, however, that the use of very low amounts of aluminum necessitates the use of high purity solvents or diluents in the polymerization zone. Further, other components present in the zone should be essentially free of impurities which react with aluminum alkyls. Otherwise, additional quantities of an organometallic compound as previously described, preferably an organoaluminum compound, must be used to react with such impurities.
Moreover, it is understood that in -the catalyst the aluminum compound should be in the form of trialkyl 29,019A-F -12-2~L~
~13-aluminum or alkyl aluminum halide provided that the alkyl aluminum halide be substantially free of alkyl alumin~m dihalide. In the above mentioned aluminum compounds, the alkyl groups independently have from 1 to 20, preferably from 1 to 10, carbon atoms.
When additional quantities of aluminum compound are employed, it can be added to the aforementioned catalyst during the preparation -thereof or the aluminum deficient catalyst can be mixed with the appropriate aluminum compound prior to entry into the polymeriza-tion reactor o~, alternatively, the aluminum deficient catalyst and the aluminum compound can be added to the polymerization reactor as separate streams or additions.
The foregoing catalytic reaction is prefer-ably carried out in the presence of an inert diluen-t.
The concentrations of catalyst components are prefer-ably such that when the essential components of the catalytic reaction product are combined, the resultant slurry is from 0.005 to 1.0 molar (moles/liter) with respect to magnesium. By way of an example of suitable inert organic diluents can be mentioned liquified ethane, propane, isobutane, n-butane, n-hexane, the various isomeric hexanes, isooctane, paraffinic mixtures of alkanes having from 8 to 12 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, 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 200C. Also included as suitable inert diluents are benzene, toluene, ethylbenzene, cumene, decalin and the like.
29,019A-F -13-Mixing of the catalyst components to provide the desired catalytic reaction product is advantageously carried out under an inert atmosphere such as nitrogen, argon or other inert gas at temperatures in the range 5 from -100 to 200C, preferably from about 0 to 100C.
The period of mixing is not considered to be critical as it is found that a sufficient catalyst composi-tion most of-ten occurs within about 1 minute or less. In the preparation of the catalytic reaction product, it is not necessary to separate hydrocarbon soluble componen-ts from hydrocarbon insoluble components of the reaction product.
In order to maximize catalyst efficiency, the catalyst is prepared by mixing the components of the catalyst in an inert liquid diluent in the following order: organomagnesium compound, halide source, the aluminum compound if required, and the reaction product or complex formed from said transition metal compound, oxygen-containing compound and alkylating agent. This is not to imply, however, that other orders of addition would not result in catalysts having very high efficiencies.
In the polymerization process employing the aforementioned catalytic reaction product, polymer-ization is effected by adding a catalytic amount of theabove catalyst composition to a polymerization zone containing at least one ~-olefin monomer, or vice versa. The polymerization zone is maintained at temperatures in the range from about 0 to 300C, preferably at solution polymerization temperatures, e.g., from about 130 to 250C, for a residence time of a few seconds to several days, preferably 15 29,019A-F -14-%~ -seconds to 2 hours. It is generally desirable to carry out the polymerization in the absence of moisture and oxygen,and a catalytic amount of the catalytic reaction product is generally wi-thin the range from 0.0001 to o.l millimoles tltanium per liter of diluent. It is understood, however, that the most advantageous catalyst concen-tration will depend upon polymerization conditions such as temperature, pressure, solvent and presence of catalyst poisons and that the foregoing range is given to obtain maximum catalyst yields in weight of polymer per unit weight of titanium. Generally, in the poly-merization process, a carrier which may be an inert organic diluent or solvent or excess monomer is employed.
In order to realize the full benefit of the high efficiency catalyst of the present invention, care must be taken to avoid oversaturation of the solvent with polymer. If such saturation occurs before the catalyst becomes depleted, the full efficiency of the catalys-t is not realized. For best results, it is preferred that the amount of polymer in the carrier not exceed about 50 weight percent based on the total weight of the reaction mixture.
It is understood that inert diluents employed in the polymerization recipe are suitably as defined hereinbefore.
The polymerization pressures preferably employed are relatively low, e.g., from 0.45-7.09 MPa (50 to 1000 psig), especially from 0.80-5.00 MPa (100 to 700 psig). However, polymerization within the scope of the present invention can occur at pressures from atmospheric up to pressures determined by the capa-bilities of the polymerization equipment. During 29,019A-F -15-2~
polymerization it is desirable to stir the polymerization recipe to obtain better temperature control and to mainta1n uniform polymerization mixtures througou-t the polymerization zone.
In order to optimize catalyst yields in the polymerization of ethylene, it is preferable to main-tain an ethylene concentration in -the solven-t in the range of from 1 to 10 weight percent, most advan-tageously from 1.2 to 2 weight percent. To achieve this, when an excess of ethylene is fed into the system, a portion of the ethylene can be vented.
~ Iydrogen can be employeA in the practice of this invention to control the molecular weight of the resultant polymer. For the purpose of this invention, it is beneficial to employ hydrogen in concentrations ranging from 0.001 to 1 mole per mole of monomer. The larger amounts of hydrogen within this range are found to produce generally lower molecular weight polymers.
It is understood that hydrogen can be added with a monomer stream to the polymerization vessel or sepa-rately 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 monomer or mixture of monomers is con-tacted with the catalytic reaction product in anyconventional manner, preferably by bringing the cata-lytic reaction product and monomer together with intimate agitation provided by suitable stirring or other means. Agitation can be continued during poly-merization, or in some instances, the polymerizationcan be allowed to remain unstirred while the polymer-ization takes place. In the case of more rapid 29,019A-F -16-reactions with more active catalysts, means can be provided for refluxing monomer and solven-t, if any of the labter is present, in order to remove the heat of reaction. In any event, adequate means should be provided for dissipa-ting the exothermic heat of poly-merization. If desired, the monomer can be brought in the vapor phase into contact with the catalytic reac-tion product, in -the presence or absence of liquid ma-terial.
The polymerization can be effected in the 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 media 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. Thus, 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 of the types convention-ally employed for deactivating Ziegler catalysts. The resultant polymer is found to contain insignificant amounts of catalyst residue.
The following examples are given to illustrate the invention. All percentages are by weight and all parts are by molar or atomic ratio unless otherwise indicated.
29,019A-F -17-L9~
EXAMPLES 1-10 AND COMPARATIVE EXPERIMENTS A, B AND C
A. Preparation of the Titanium Complexes , All titanium-alcohol die-thyl zinc complexes were prepared by simple admixture of the neat tetraiso-propyl titanate (TiPT) with the neat n-propanol (n-PrOH), followed by addition of a 15% solution of diethyl zinc (DEZ) in Isopar~ E (an isoparaEfinic hydrocarbon fraction having a boiling range of 116C-134C). After development of a dark, usually greenish color (generally within ~30 minutes), the mixture was diluted to give an overall titanium concentration of 0.025 molar. The complexes were then used in catalyst preparations.
B. Preparation of the Catalyst In a narrow mouth catalyst bottle under an inert atmosphere was mixed the following components in the following order:
97.80 ml Isopar~ E
O.80 ml of 0.94 M ethylaluminum dichloride (EADC) 0.80 ml of 0.745 M di-n-hexyl magnesium (as obtained commercially from Lithium Corporation of America) 0.60 ml of 0.025 M titanium complex 100.00 ml Various titanium-n-propanol-diethyl zinc complexes ~ere employed as shown in examples 1-12 of Table I. In addition, one catalyst was prepared con-taining only tetraisopropyl titanate (comparative experimen-t A) and one catalyst contained a tetraiso-propyl titaniate diethyl zinc complex (comparative experiment B), taught in U.S. Patents 4,250,286 and 4,269,733-29,019A-F -18-C. Polvmerization Into a stirred one-gallon batch reactor was added 2~liters of Isopar~ E, 0.028 MPa (4 psig) of hydrogen, 1.22 ~Pa (175 psig) of ethylene, and 10 ml (0.0015 mmoles Ti) of the previously described ca-talysts.
Ethylene pressure was kept constant a-t 1.40 MPa (200 psig) (the solven-t vapor pressure being 0.25 MPa (21 psig)) and the reactor temperature was controlled at 150C. Because of the high initial activities of these catalysts, an initial exotherm is produced, the size of which is dependent on catalyst activity (the higher the exotherm, the higher the initial catalyst activity).
This exotherm can be controlled to some extent by cooling the reactor with large volumes of air blown past the reactor. Total reaction time was 30 minutes.
Catalyst efficiencies and exotherms are listed in Table I.
It is obvious from the data in Table I that the addition of small quantities of an alcohol followed by diethyl zinc leads to a large and unèxpected increase in catalyst activity as evidenced by improved exotherms and catalyst efficiencies. Not all ratios of Ti :ROH:DEZ
improves catalyst efficiency, however, as large amoun-ts (5 or greater mole parts) leads to poorer efficiencies.
Also, a point is reached on DEZ where additional DEZ
will not improve catalyst efficiency and may even lower the observed efficiency. These runs show that the addition of 1 or 2 alcohols along with 2 or more DEZ
gives the optimum efficiency.
A. Preparation of the Titanium Complexes Additional complexes were prepared as in examples 1-10 above, however this time n-butanol or 29,019A-F -19-ethanol were employed. After development of the dark color (green for butanol and blue for ethanol), the solutio~s were diluted to 0.025 Molar in titanium concentration.
B. Preparation of the Catalyst Catalysts were prepared in a manner inden-tical to that outlined in examples 1-10 above using the titanium-alcohol-diethyl zinc complex shown in Table I.
C. Polymerization Polymerization conditions were identical to those outlined in examples 1-10 above. Catalyst exo-therms and efficiencies are listed in Table I.
By comparing examples 11 and 5 and examples 12, 13 and 4, it is readily apparent that the type of alcohol used (i.e., the size of the alkyl group) has little effect on the catalyst exotherm and efficiency.
A. Preparation of the Titanium Complexes Complexes were prepared as previously described, except that n-butanol, acetone and water were used as the oxygen-contai~ing compounds. The H2O and acetone mixtures were diluted to 0.025 Molar while the n-butanol was diluted to 0.0336 Molar, both in titanium.
B. Preparation of the Catalysts Catalysts were prepared in similar fashion to examples 1-10 above using the following compounds.
29,019A-F -20-98.20-x ml of Isopar~ E
0.80 ml of 0.94 M EADC
1.00 ml of 0.60 M n-butyl sec-butyl Mg (obtained from Lithium Corpora-tion of America) x ml of y M titanium compound 100.00 ml where x and y as well as the titanium compound can be found in the following table:
EXAMPLE x,ml y~ Compound 1014 0.60 0.025 1 TIPT-1 H2O-3 DEZ
0.60 0.0336 1 TiPT-1 BuOH-3 DEZ
16 0.45 0.0336 1 TiPT-1 BuOH-3 DEZ
17 0.60 0.025 1 TiPT 1 acetone-3 DEZ
C. Pol~merization All polymerizations were conducted at 150C
using 0.13 MPa (19 psig) of hydrogen and 1.12 MPa (160 psig) of ethylene. The length of these runs was 20 minutes. Run results can be found in Table II.
These run results once again show that the oxygen compound used has little effect on catalyst efficiency, although it did effect the exotherm in the case of acetone. In example 15, a lower efficiency based on titanium resulted from increased titanium levels in the catalyst even though the initial activity of the catalyst appeared higher than the others during the run.
COMPARATIVE EXPERIMENTS D, E AND F
A. PreParation of the Titanium Complexes A tetraisopropyltitanate-diethyl zinc complex was prepared by mixing the neat TiPT with the 15% DEZ
29,019A-F -21-(1:1 molar ratio). To one aliquot of this solution was added 1 mole part BuOH. To another ali~uot was added 1 mole pa,rt H2O. All solutions were then diluted to 0.025 M in Ti concentration. These solutlons were then used to prepare ca-talysts.
B. Preparation of the Catalyst Catalys-ts were prepaxed in a manner similar to that previously described in examples 1-10. The procedure used was:
97.79 ml o 2,2,4-trimethylpentane 0.80 ml of 0.94 M EADC
0.60 ml of 0.025 M ti-tanium complex 1.11 ml of 0.54 M n-butyl-sec-butyl Mg 100.00 ml The oxygen-containing component employed to form the titanium complex is shown in Table II.
C. Polymerization Polymerization was conducted as previously described using 2,2,4-trimethylpentane as the reaction solvent and using 0.06 MPa (9 psig) of hydrogen and 0.91 MPa (130 psig) of ethylene for a total pressure of 1.36 MPa (180 psig) (including the 0.39 MPa ~41 psig) solvent vapor pressure). Results of these runs are given in Table II.
Comparative experiments E and F show a decrease in catalyst efficiency as compared to experiment D even though an oxygen-containing compound and diethyl zinc have been added. This is due to the order of mixing.
If the diethyl zinc is added to the titanium species, a 29,019A-F -22--23~
change of color occurs. If the oxygen-containing species is then added, an additional color change may occur ~nd the resulting titanium complex shows a reduced eEficiency over catalysts made by the preferred me-thod.
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(2.2) a metallic halide correspond-ing to the empirical formula MR~ aXa wherein M is a metal of Group IIIA or IVA of Mendel~
eev's Periodic Table o Elements, X is a monovalent hydrocarbyl radical, X is halogen, y is a number corresponding to the, valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound is added which is represented by the empirical formula AlRy,Xy,l wherein R and X are as defined above and y' and y"
each have a value of from zero to three with the sum of y' and y" being three;
and said components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from 1:1 to 200:1; Zn:Tm of from 0.1:1 to 10:1; O:Tm of from 0.1:1 to 4 1; Al:Tm of from 0.1:1 to 200:1 and an excess X:Al of from 0.0005:1 to 5:1.
Another aspect of the presen~ invention is a process for polymerizing ethylene and other ~-olefins under Ziegler polymerization conditions in the presence of a catalyst comprising a magnesium halide, a titanium compound, and a zinc compound characterized in that the catalyst is prepared by first forming a reaction product or complex (A) of a mixture of a titanium compound of the formula Ti(OR)4 where R is Cl-C10 alkyl and an alcohol in quantities to provide an atomic ratio of OoTi of 0.1:1 to 4:1 with an organo zinc compound of the formula ZnRx wherein R is Cl-C10 29,019A-F -3b-~3c-(A) of a mixture of a titanium com~ound of ~he formula Ti(OR~4 where R ls Cl-C10 alkyl and an alcohol in quantities to provide an atomic ratio of O:Ti of 0.1:1 to 4:1 with an organo zinc compound of the formula ZnR2 wherein R is Cl-C10 alkyl; and thereafter admi~cing (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR"2-xMR"y wherein M is aluminum or zinc, each R"
is independently a hydrocarbyl or hydro-carbyloxy group having from 1 to 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (2.1) an active non-metallic halide, , said non-metallic halide corres-ponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst, and X
. is halogen or (2.2) a metallic halide corresponding to ~he empirical formula MRy aXa wherein ~ is a metal of Group IIIA
or IVA of Mendeleev's Periodic Table of Elements, R is a mono-valent hydrocarbyl radical, X is halogen, y is a number corres-ponding to the valence of M and a is a number of 1 to y; and 29,019A-F -3c-(C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound is added which is represented by the empirical formula AlRy~Xyl~ wherein R
and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and said components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from 1:1 to 200:1; Zn:Tm of from 0.1:1 to 10:1; O:Tm of from 0.1:1 to 4:1; AloTm of from 0.1:1 to 200:1 and an excess X:Al of from 000005:1 to 501.
The components are employed in quantities which provide the composition with atomic ratios of the elements as follows.
29,010A-~ -4-2~D
Mg:Tm is from l:1 -to 200:1, preferably ~rom 2:1 to 100:1 and ~lost preerably from 5:1 -to 75:1.
, Al:Tm is from 0.1:1 to 200:1, preferably from 0.5:1 to 100:1 and most preferably from 1:1 to 75:1.
Excess X:Al is from 0.0005:1 to 5:1, preferably from 0.002:1 to 2:1 and most preferably from 0.01:1 to 1.4:1.
Excess X is the amount of halide above that amount which is theoretically required to convert the organomagnesium component to magnesium dihalide.
The present invention is most advantageously practiced in a polymerization process wherein an ~-olefin is polymerized, generally in the presence of hydrogen as a molecular weight control agent, in a polymerization zone containing an inert diluent and the catalytic reaction product as hereinbefore described. Especially advantageous is the copolymerization of ethylene and higher ~-olefins using the catalytic reaction product of this invention. The foregoing polymerization process is most beneficially carried out undex inert atmosphere and relatively low pressures, although very high pressures are optionally employed.
Olefins which are suitably homopolymeri~ed or copolymerized in the practice of this invention are generally the aliphatic ~-monoolefins or non-conjugated ~-diolefins having from 2 to 18 carbon atoms. Illustra-tively, such ~-olefins can include ethylene, propylene, butene-1, pentene-1, 3-methylbutene~ methylpentene-1, hexene-1, octene-l, dodecene-1, octadecene-1, 1,7 octadiene, 1,4-hexadiene, and mixtures thereof. It is understood 29,019A-F -5-2~) -that ~-olefins may be copolymerized with other ~-olefins and/or with small amounts, i.e., up to abou-t 25 weight perc~nt,based on the polymer, of other ethylenically unsaturated monomers such as styrene, ~-methylstyrene S and similar ethylenically unsaturated monomers which do not destroy conventional Ziegler catalysts. Mos-t benefits are realized in the polymerization of aliphatic ~-monoolefins, particularly ethylene and mixtures of ethylene with up to 50, especially from 0.1 to 40, weight percent of propylene, butene-1, hexene-1, octene-l, 4-methylpentene-1, 1,7-octadiene, 1,4-hexadiene or similar ~-olefin or non-conjugated ~-diolefins based on total monomer.
Suitable zinc compounds which can be employed as the essentially non-reducing alkylating agent are those represented by the empirical formulae R2Zn or RZnX wherein each R is independently a hydrocarbyl group having from l to 20, preferably from 1 to 10, carbon atoms and X is a halogen, preferably chlorine or bromine. Particularly suitable zinc compounds include, for example, diethyl zinc, dimethyl zinc, ethyl zinc chloride, diphenyl zinc and mixtures thereof.
~ y the term essentially non-reducing it is meant that simple mixing of the alkylating agent with the titanium species at normal conditions does not lead to a reduction in the oxidation state of the titanium compound.
Suitable non-metallic oxygen-containing compounds which can be employed herein include, for example, molecular oxygen, alcohols, ketones, alde-hydes, carboxylic acids, esters of carboxylic acids, 29,019A-F -6---7~
peroxides, and water. Those compounds which are so]uble in hydrocarbon solvent are especially preferred.
r Particularly suitable alcohols include, for example, n-butanol, sec-butanol, iso-propanol, n-pxopanol, and mixtures -thereof.
Particularaly suitable ketones which can be employed herein include, for example, acetone, methyl-ethyl ketone, methyl isobutyl ketone, and mixtures thereof.
Particularly suitable carboxylic acids which can be employed herein include, for example, formic acid, acetic acid, stearic acid, and mixtures thereof.
Particularly suitable ethers which can be employed include, for example, diethyl ether, ethyl vinyl ether, and mixtures thereof.
Particularly suitable aldehydes which can be employed herein include, for example, formalehyde, acetaldehyde, propionaldehyde, and mixtures thereof.
Particularly suitable peroxides which can be employed herein include, for example, hydrogen peroxide, t-butylperoxide, and mixtures thereof.
Suitable transition metal compounds which can be employed in the present invention include those represented by the empirical formulae Tm(OR)yXx y , Tm(OR)x 2 or TmOXx 2 wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is indepen-dently a hydrocarbyl group, preferably alkyl or aryl, 29,019A-F -7-312~
having from 1 to 20, preferably from 1 to 10, carbon atoms; each X is independently a halogen, preferably chlorin~ or bromine; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm.
Particularly suitable transition metal com-pounds include for example tetraethoxy titanium, tetra-isopropoxy titanium, tetra-n-bu-toxy titanium, di-n-butoxy titanium dichloride, tetraphenoxy titanium, tetra-n-propoxy titanium, tetra-(2-ethylhexoxy) titanium, tri-n-butoxy vanadium oxide, oxyvanadium trichloride, tri-isopropoxy vanadium oxide, zirconium tetra-n-butoxide, zirconium tetra-n-propoxide, zirconium tetra-isopropoxide, and mixtures thereof.
Suitable organomagnesium components which can be ~mployed in the present invention include those represented by the empirical formula MgR"2-xMR"y wherein each R" is independently hydrocarbyl or hydrocarbyloxy, M is aluminum, zinc or mixtures thereof and x is zero to 10, preferably zero to 5, most preferably from zero to 2.5; and y denotes the number of hydrocarbyl and/or hydrocarbyloxy groups which corresponds to the valence of M. As used herein, hydrocarbyl and hydrocarbyloxy are monovalent hydrocarbon radicals. Preferably, hydrocarbyl is alkyl, cycloalkyl, aryl, aralkyl, alkenyl and similar hydrocarbon radicals having 1 to 20 carbon atoms, with alkyl having 1 to 10 carbon atoms being especially preferred. Likewise, preferably, hydro-carbyloxy is alkoxy, cycloalkyloxy, aryloxy, aralkyloxy, alkenyloxy and similar oxyhydrocarbon radicals having 1 to 20 carbon atoms, with alkoxy having 1 to 10 carbon atoms b~ing preferred. Hydrocarbyl is preferred over hydrocarbyloxy.
29,019A-F -8-2~1D
`~ g Preferably the organomagnesium compound is a hydrocarbon soluble dihydrocarbylmagnesium such as the magnes~um dialkyls and the magnesium diaryls. Exemplary suitable ma~nesium dial]~yls include particularly n-butyl-sec-buty] magnesium, di.isopropyl magnesium, di-n-hexyl magnesium, isopropyl~n-butyl magnesium, ethyl-n-hexyl magnesium, ethyl-n-butyl magnesium, di-n-octyl magnesium and others wherein the alkyl has from 1 to 20 carbon atoms. Exemplary suitable magnesium diaryls include diphenylmagnesium, dibenzyl-magnesium, and ditolylmagnesium. Suitable organo-magnesium compounds include alkyl and aryl magnesium alkoxides and aryloxides and aryl and alkyl magnesium halides with the halogen-free organomagnesium compounds being more desirable.
Among the halide sources which can be employed herein are the active non-metallic halides and me-tallic halides.
Suitable non-metallic halides are represented by the empirical formula R'X wherein R' is hydrogen or an active monovalent organic radical and X is a halogen.
Particularly suitable non-metallic halides include, for example, hydrogen halides and active organic halides such as t-alkyl halides, allyl halides, benzyl halides and other active hydrocarbyl halides wherein hydro-carbyl is as defined hereinbefore. By an active organic halide is meant a hydrocarbyl halide that contains a labile halogen at least as active, i.e. as easily lost to another compound, as the halogen of sec-butyl chloride, preferably as active as t-butyl chloride. In addition to the organic monohalides, it is understood that organic dihalides, trihalides and other polyhalides 29,019A-F -9-that are ac-tive as defined hereinbefore are also suit-ably employed. Examples of preferred active non-metalli,c halides include hydrogen chloride, hydrogen bromide, t-butyl chloride, t-amyl bromide, allyl chloride, benzyl chloride, crotyl chloride, methylvinyl carbinyl chloride, ~phenylethyl bromide, and diphenyl methyl chloride. Most preferred are hydrogen chloride, t-butyl chloride, allyl chloride and benzyl chloride.
Suitable metallic halides which can be employed herein include those represented by the empirical formula MRy aXa wherein M is a metal of Groups IIIA or IVA, of Mendeleev's Periodic Table of Elements, R is a monovalent organic radical, X is a halogen, y has a value corresponding to the valence of M and a has a value from 1 to y. A suitable metallic halide is SnCl4, although the preferred metallic halides are aluminum halides of the empirical formula AlR3 aXa wherein each R is independently hydrocarbyl as herein-before defined such as alkyl, X is a halogen and a is a number from 1 to 3. Most preferred are alkylaluminum halides such as ethylaluminum sesquichloride, diethyl aluminum chloride, ethylaluminum dichloride, and diethylaluminum bromide, with e-thylaluminum dichloride being especially preferred. Alternatively, a metal halide such as aluminum trichloride or a combination of aluminum trichloride with an alkyl aluminum halide or a trialkyl aluminum compound may be suitably employed.
It is understood that the organic moieties of the aforementioned organomagnesium, e.g. R", and the organic moieties of the halide source, e.g. R and R', are suitably any other organic radical provided that they do not contain functional groups that poison 29,019A-F -10-conven-tional Ziegler catalysts. Preferably such organic moieties do not contain active hydrogen, i.e., those suffici,en-tly active to react with the Zerewi-tinoff reagen-t.
In preparing the reaction product or complex of the present invention, the transition metal compo-nen-t and oxygen-containing component are mixed together in a sui-table inert solvent or diluent -followed by the - addi-tion of the alkylating agen-t in a quantity and under suitable conditions so as to effect a color change in the reaction mixture. Suitable conditions include temperatures of from about -50C to 110C, preferably from 0C to 30C. At lower temperatures, longer times may be re~uired to effect a color change.
The reaction time is also affected by the concentration of the reactants, e.g. low concentrations require longer times at any given temperature than do higher concentrations. The solvents which can be employed include those suitable for preparing the catalysts of this invention with the hydrocarbon sol-vents being most suitable.
The color change which occurs upon addition of the essentially non-reducing alkylating agent varies depending upon the particular components employed, i.e.
the particular oxygen-containing compound and/or the particular alkylating agent.
The magnesium halide can be preformed from the organomagnesium compound and the halide source or it can be prepared in situ in which instance the catalyst is prepared by mixing in a suitable solvent (1) the 29,019A-F
organomagnesium component, B-l, (23 the halide source, B-2 and (3) the reaction product or complex formed by mixing,(a) a mixtuxe of said -transition metal component (A-1.1) and said oxygen-containing componen-t (A-1.2)and (b) said alkylating agent (A-2).
The foregoing catalyst components are com-bined in proportions sufficient to provide atomic ratios as previously mentioned.
In cases wherein neither the organomagnesium component nor the halide source contains aluminum or contains an insufficient quantity of aluminum, it is necessary to include in the total catalyst an aluminum compound such as an alkyl aluminum compound, e.g. a trialkyl aluminum, an alkyl aluminum halide or an aluminum halide. If polymerization temperatures below 180C are employed, the atomic ratios of Al:Ti may be from 0.1:1 to 200:1, preferably from 1:1 to 100:1.
However, when polymerization -temperatures above 180C
are employed, the aluminum compound is used in propor-tions such that the Mg:Al ratio is more than 0.3:1,preferably from 0.5:1 to 10:1, and Al:Ti ratio is less than 120:1, preferably less than 50:1. It is understood, however, that the use of very low amounts of aluminum necessitates the use of high purity solvents or diluents in the polymerization zone. Further, other components present in the zone should be essentially free of impurities which react with aluminum alkyls. Otherwise, additional quantities of an organometallic compound as previously described, preferably an organoaluminum compound, must be used to react with such impurities.
Moreover, it is understood that in -the catalyst the aluminum compound should be in the form of trialkyl 29,019A-F -12-2~L~
~13-aluminum or alkyl aluminum halide provided that the alkyl aluminum halide be substantially free of alkyl alumin~m dihalide. In the above mentioned aluminum compounds, the alkyl groups independently have from 1 to 20, preferably from 1 to 10, carbon atoms.
When additional quantities of aluminum compound are employed, it can be added to the aforementioned catalyst during the preparation -thereof or the aluminum deficient catalyst can be mixed with the appropriate aluminum compound prior to entry into the polymeriza-tion reactor o~, alternatively, the aluminum deficient catalyst and the aluminum compound can be added to the polymerization reactor as separate streams or additions.
The foregoing catalytic reaction is prefer-ably carried out in the presence of an inert diluen-t.
The concentrations of catalyst components are prefer-ably such that when the essential components of the catalytic reaction product are combined, the resultant slurry is from 0.005 to 1.0 molar (moles/liter) with respect to magnesium. By way of an example of suitable inert organic diluents can be mentioned liquified ethane, propane, isobutane, n-butane, n-hexane, the various isomeric hexanes, isooctane, paraffinic mixtures of alkanes having from 8 to 12 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, 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 200C. Also included as suitable inert diluents are benzene, toluene, ethylbenzene, cumene, decalin and the like.
29,019A-F -13-Mixing of the catalyst components to provide the desired catalytic reaction product is advantageously carried out under an inert atmosphere such as nitrogen, argon or other inert gas at temperatures in the range 5 from -100 to 200C, preferably from about 0 to 100C.
The period of mixing is not considered to be critical as it is found that a sufficient catalyst composi-tion most of-ten occurs within about 1 minute or less. In the preparation of the catalytic reaction product, it is not necessary to separate hydrocarbon soluble componen-ts from hydrocarbon insoluble components of the reaction product.
In order to maximize catalyst efficiency, the catalyst is prepared by mixing the components of the catalyst in an inert liquid diluent in the following order: organomagnesium compound, halide source, the aluminum compound if required, and the reaction product or complex formed from said transition metal compound, oxygen-containing compound and alkylating agent. This is not to imply, however, that other orders of addition would not result in catalysts having very high efficiencies.
In the polymerization process employing the aforementioned catalytic reaction product, polymer-ization is effected by adding a catalytic amount of theabove catalyst composition to a polymerization zone containing at least one ~-olefin monomer, or vice versa. The polymerization zone is maintained at temperatures in the range from about 0 to 300C, preferably at solution polymerization temperatures, e.g., from about 130 to 250C, for a residence time of a few seconds to several days, preferably 15 29,019A-F -14-%~ -seconds to 2 hours. It is generally desirable to carry out the polymerization in the absence of moisture and oxygen,and a catalytic amount of the catalytic reaction product is generally wi-thin the range from 0.0001 to o.l millimoles tltanium per liter of diluent. It is understood, however, that the most advantageous catalyst concen-tration will depend upon polymerization conditions such as temperature, pressure, solvent and presence of catalyst poisons and that the foregoing range is given to obtain maximum catalyst yields in weight of polymer per unit weight of titanium. Generally, in the poly-merization process, a carrier which may be an inert organic diluent or solvent or excess monomer is employed.
In order to realize the full benefit of the high efficiency catalyst of the present invention, care must be taken to avoid oversaturation of the solvent with polymer. If such saturation occurs before the catalyst becomes depleted, the full efficiency of the catalys-t is not realized. For best results, it is preferred that the amount of polymer in the carrier not exceed about 50 weight percent based on the total weight of the reaction mixture.
It is understood that inert diluents employed in the polymerization recipe are suitably as defined hereinbefore.
The polymerization pressures preferably employed are relatively low, e.g., from 0.45-7.09 MPa (50 to 1000 psig), especially from 0.80-5.00 MPa (100 to 700 psig). However, polymerization within the scope of the present invention can occur at pressures from atmospheric up to pressures determined by the capa-bilities of the polymerization equipment. During 29,019A-F -15-2~
polymerization it is desirable to stir the polymerization recipe to obtain better temperature control and to mainta1n uniform polymerization mixtures througou-t the polymerization zone.
In order to optimize catalyst yields in the polymerization of ethylene, it is preferable to main-tain an ethylene concentration in -the solven-t in the range of from 1 to 10 weight percent, most advan-tageously from 1.2 to 2 weight percent. To achieve this, when an excess of ethylene is fed into the system, a portion of the ethylene can be vented.
~ Iydrogen can be employeA in the practice of this invention to control the molecular weight of the resultant polymer. For the purpose of this invention, it is beneficial to employ hydrogen in concentrations ranging from 0.001 to 1 mole per mole of monomer. The larger amounts of hydrogen within this range are found to produce generally lower molecular weight polymers.
It is understood that hydrogen can be added with a monomer stream to the polymerization vessel or sepa-rately 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 monomer or mixture of monomers is con-tacted with the catalytic reaction product in anyconventional manner, preferably by bringing the cata-lytic reaction product and monomer together with intimate agitation provided by suitable stirring or other means. Agitation can be continued during poly-merization, or in some instances, the polymerizationcan be allowed to remain unstirred while the polymer-ization takes place. In the case of more rapid 29,019A-F -16-reactions with more active catalysts, means can be provided for refluxing monomer and solven-t, if any of the labter is present, in order to remove the heat of reaction. In any event, adequate means should be provided for dissipa-ting the exothermic heat of poly-merization. If desired, the monomer can be brought in the vapor phase into contact with the catalytic reac-tion product, in -the presence or absence of liquid ma-terial.
The polymerization can be effected in the 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 media 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. Thus, 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 of the types convention-ally employed for deactivating Ziegler catalysts. The resultant polymer is found to contain insignificant amounts of catalyst residue.
The following examples are given to illustrate the invention. All percentages are by weight and all parts are by molar or atomic ratio unless otherwise indicated.
29,019A-F -17-L9~
EXAMPLES 1-10 AND COMPARATIVE EXPERIMENTS A, B AND C
A. Preparation of the Titanium Complexes , All titanium-alcohol die-thyl zinc complexes were prepared by simple admixture of the neat tetraiso-propyl titanate (TiPT) with the neat n-propanol (n-PrOH), followed by addition of a 15% solution of diethyl zinc (DEZ) in Isopar~ E (an isoparaEfinic hydrocarbon fraction having a boiling range of 116C-134C). After development of a dark, usually greenish color (generally within ~30 minutes), the mixture was diluted to give an overall titanium concentration of 0.025 molar. The complexes were then used in catalyst preparations.
B. Preparation of the Catalyst In a narrow mouth catalyst bottle under an inert atmosphere was mixed the following components in the following order:
97.80 ml Isopar~ E
O.80 ml of 0.94 M ethylaluminum dichloride (EADC) 0.80 ml of 0.745 M di-n-hexyl magnesium (as obtained commercially from Lithium Corporation of America) 0.60 ml of 0.025 M titanium complex 100.00 ml Various titanium-n-propanol-diethyl zinc complexes ~ere employed as shown in examples 1-12 of Table I. In addition, one catalyst was prepared con-taining only tetraisopropyl titanate (comparative experimen-t A) and one catalyst contained a tetraiso-propyl titaniate diethyl zinc complex (comparative experiment B), taught in U.S. Patents 4,250,286 and 4,269,733-29,019A-F -18-C. Polvmerization Into a stirred one-gallon batch reactor was added 2~liters of Isopar~ E, 0.028 MPa (4 psig) of hydrogen, 1.22 ~Pa (175 psig) of ethylene, and 10 ml (0.0015 mmoles Ti) of the previously described ca-talysts.
Ethylene pressure was kept constant a-t 1.40 MPa (200 psig) (the solven-t vapor pressure being 0.25 MPa (21 psig)) and the reactor temperature was controlled at 150C. Because of the high initial activities of these catalysts, an initial exotherm is produced, the size of which is dependent on catalyst activity (the higher the exotherm, the higher the initial catalyst activity).
This exotherm can be controlled to some extent by cooling the reactor with large volumes of air blown past the reactor. Total reaction time was 30 minutes.
Catalyst efficiencies and exotherms are listed in Table I.
It is obvious from the data in Table I that the addition of small quantities of an alcohol followed by diethyl zinc leads to a large and unèxpected increase in catalyst activity as evidenced by improved exotherms and catalyst efficiencies. Not all ratios of Ti :ROH:DEZ
improves catalyst efficiency, however, as large amoun-ts (5 or greater mole parts) leads to poorer efficiencies.
Also, a point is reached on DEZ where additional DEZ
will not improve catalyst efficiency and may even lower the observed efficiency. These runs show that the addition of 1 or 2 alcohols along with 2 or more DEZ
gives the optimum efficiency.
A. Preparation of the Titanium Complexes Additional complexes were prepared as in examples 1-10 above, however this time n-butanol or 29,019A-F -19-ethanol were employed. After development of the dark color (green for butanol and blue for ethanol), the solutio~s were diluted to 0.025 Molar in titanium concentration.
B. Preparation of the Catalyst Catalysts were prepared in a manner inden-tical to that outlined in examples 1-10 above using the titanium-alcohol-diethyl zinc complex shown in Table I.
C. Polymerization Polymerization conditions were identical to those outlined in examples 1-10 above. Catalyst exo-therms and efficiencies are listed in Table I.
By comparing examples 11 and 5 and examples 12, 13 and 4, it is readily apparent that the type of alcohol used (i.e., the size of the alkyl group) has little effect on the catalyst exotherm and efficiency.
A. Preparation of the Titanium Complexes Complexes were prepared as previously described, except that n-butanol, acetone and water were used as the oxygen-contai~ing compounds. The H2O and acetone mixtures were diluted to 0.025 Molar while the n-butanol was diluted to 0.0336 Molar, both in titanium.
B. Preparation of the Catalysts Catalysts were prepared in similar fashion to examples 1-10 above using the following compounds.
29,019A-F -20-98.20-x ml of Isopar~ E
0.80 ml of 0.94 M EADC
1.00 ml of 0.60 M n-butyl sec-butyl Mg (obtained from Lithium Corpora-tion of America) x ml of y M titanium compound 100.00 ml where x and y as well as the titanium compound can be found in the following table:
EXAMPLE x,ml y~ Compound 1014 0.60 0.025 1 TIPT-1 H2O-3 DEZ
0.60 0.0336 1 TiPT-1 BuOH-3 DEZ
16 0.45 0.0336 1 TiPT-1 BuOH-3 DEZ
17 0.60 0.025 1 TiPT 1 acetone-3 DEZ
C. Pol~merization All polymerizations were conducted at 150C
using 0.13 MPa (19 psig) of hydrogen and 1.12 MPa (160 psig) of ethylene. The length of these runs was 20 minutes. Run results can be found in Table II.
These run results once again show that the oxygen compound used has little effect on catalyst efficiency, although it did effect the exotherm in the case of acetone. In example 15, a lower efficiency based on titanium resulted from increased titanium levels in the catalyst even though the initial activity of the catalyst appeared higher than the others during the run.
COMPARATIVE EXPERIMENTS D, E AND F
A. PreParation of the Titanium Complexes A tetraisopropyltitanate-diethyl zinc complex was prepared by mixing the neat TiPT with the 15% DEZ
29,019A-F -21-(1:1 molar ratio). To one aliquot of this solution was added 1 mole part BuOH. To another ali~uot was added 1 mole pa,rt H2O. All solutions were then diluted to 0.025 M in Ti concentration. These solutlons were then used to prepare ca-talysts.
B. Preparation of the Catalyst Catalys-ts were prepaxed in a manner similar to that previously described in examples 1-10. The procedure used was:
97.79 ml o 2,2,4-trimethylpentane 0.80 ml of 0.94 M EADC
0.60 ml of 0.025 M ti-tanium complex 1.11 ml of 0.54 M n-butyl-sec-butyl Mg 100.00 ml The oxygen-containing component employed to form the titanium complex is shown in Table II.
C. Polymerization Polymerization was conducted as previously described using 2,2,4-trimethylpentane as the reaction solvent and using 0.06 MPa (9 psig) of hydrogen and 0.91 MPa (130 psig) of ethylene for a total pressure of 1.36 MPa (180 psig) (including the 0.39 MPa ~41 psig) solvent vapor pressure). Results of these runs are given in Table II.
Comparative experiments E and F show a decrease in catalyst efficiency as compared to experiment D even though an oxygen-containing compound and diethyl zinc have been added. This is due to the order of mixing.
If the diethyl zinc is added to the titanium species, a 29,019A-F -22--23~
change of color occurs. If the oxygen-containing species is then added, an additional color change may occur ~nd the resulting titanium complex shows a reduced eEficiency over catalysts made by the preferred me-thod.
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Claims (10)
1. A catalyst for the polymerization of .alpha.-olefins under Ziegler polymerization conditions and comprising a magnesium halide, a transition metal compound and a zinc compound characterized by first forming:
(A) a reaction product or complex formed from the admixture of (1) a reaction product or complex formed by mixing (1.1) at least one transition metal compound represented by the empirical formulae Tm(OR)yXx-y , TmOXx-2 or Tm(OR)x-2O wherein Tm is a transition metal selected from groups IVB, VB
or VIB; each R is independently a hydrocarbyl group, having from 1 to 20 carbon atoms; each X is inde-pendently a halogen; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm; and (1.2) at least one oxygen-containing compound; and (2) at least one non-reducing alkylating agent represented by the empirical formulae ZnR2 or RZnX wherein X is a halogen, preferably chlorine or bromine and each R is independently an alkyl group having from 1 to 20 carbon atoms;
and thereafter admixing (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR"2?xMR"y wherein M is aluminum or zinc, each R"
is independently a hydrocarbyl or hydro-carbyloxy group having from 1 to 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (2.1) an active non-metallic halide, said non-metallic halide corres-ponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst, and X
is halogen or (2.2) a metallic halide corresponding to the empirical formula MRy-aXa wherein M is a metal of Group IIIA
or IVA of Mendeleev's Periodic Table of Elements, R is a mono-valent hydrocarbyl radical, X is halogen, y is a number corres-ponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quanti-ties of aluminum, an aluminum compound is added which is represented by the empirical formula AlRy'Xy" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and said components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from 1:1 to 200:1; Zn:Tm of from 0.1:1 to 10:1; 0:Tm of from 0.1:1 to 4:1; Al:Tm of from 0.1:1 to 200:1 and an excess X:Al of from 0.0005:1 to 5:1.
(A) a reaction product or complex formed from the admixture of (1) a reaction product or complex formed by mixing (1.1) at least one transition metal compound represented by the empirical formulae Tm(OR)yXx-y , TmOXx-2 or Tm(OR)x-2O wherein Tm is a transition metal selected from groups IVB, VB
or VIB; each R is independently a hydrocarbyl group, having from 1 to 20 carbon atoms; each X is inde-pendently a halogen; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm; and (1.2) at least one oxygen-containing compound; and (2) at least one non-reducing alkylating agent represented by the empirical formulae ZnR2 or RZnX wherein X is a halogen, preferably chlorine or bromine and each R is independently an alkyl group having from 1 to 20 carbon atoms;
and thereafter admixing (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR"2?xMR"y wherein M is aluminum or zinc, each R"
is independently a hydrocarbyl or hydro-carbyloxy group having from 1 to 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (2.1) an active non-metallic halide, said non-metallic halide corres-ponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst, and X
is halogen or (2.2) a metallic halide corresponding to the empirical formula MRy-aXa wherein M is a metal of Group IIIA
or IVA of Mendeleev's Periodic Table of Elements, R is a mono-valent hydrocarbyl radical, X is halogen, y is a number corres-ponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quanti-ties of aluminum, an aluminum compound is added which is represented by the empirical formula AlRy'Xy" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and said components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from 1:1 to 200:1; Zn:Tm of from 0.1:1 to 10:1; 0:Tm of from 0.1:1 to 4:1; Al:Tm of from 0.1:1 to 200:1 and an excess X:Al of from 0.0005:1 to 5:1.
2. The catalyst of Claim 1 wherein component A-1.1 is a titanium compound wherein each R is inde-pendently a C1-C10 hydrocarbyl group, and X is chlorine or bromine; component A-1.2 is an alcohol; component A-2 has the formula ZnR2 wherein each R is independently C1-C10 hydrocarbyl group; the Zn:Ti atomic ratio is 0.25:1 to 5:1, and the O:Ti atomic ratio is 0.25:1 to 3:1.
3. The catalyst of Claim 2 wherein component A-1.1 is titanium tetraethoxide, titanium tetra-n--propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra(2-ethylhexoxide) or mixtures thereof; component A-1.2 is n-butanol, sec-butanol, n-propanol, isopropanol, water, acetone, or mixtures thereof; and component A-2 is dimethyl zinc, diethyl zinc, diphenyl zinc or mixtures thereof.
4. The catalyst of Claim 2 wherein component B-1, M is aluminum and R" is a hydrocarbyl group having from 1 to 10 carbon atoms and x has a value of from zero to 5; in component B-2.1, R' is hydrogen or a tertiary butyl group and X is chlorine; in component B-2.2, M is a metal from Groups IIIA or IVA, y-a is zero, 1 or 2, and X is chlorine; in component C, the aluminum compound is a trialkyl aluminum compound wherein the alkyl groups independently have from 1 to 10 carbon atoms; and the components are employed in quantities to provide atomic ratios of Mg:Ti of 2:1 to 100:1; Zn:Ti of 0.25:1 to 5:1; O:Ti of 0.25:1 to 3:1;
Al:Ti of 0.5:1 to 100:1 and excess X:Al of 0.002:1 to 2:1.
Al:Ti of 0.5:1 to 100:1 and excess X:Al of 0.002:1 to 2:1.
5. The catalyst of Claim 2 wherein component A-1.1 is titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-isopropoxide, titanium tetra-n-butoxide, titanium tetra-(2-ethylhexoxide) or a mixture thereof;
component A-1.2 is n-butanol, sec-butanol, n-propanol, isopropanol, or a mixture thereof; component A-2 is dimethyl zinc, diethyl zinc, diphenyl zinc or a mixture thereof; component B-1 is a dialkyl magnesium compound wherein the alkyl groups independently have from 1 to 10 carbon atoms; component B-2 is substantially anhydrous hydrogen chloride, ethyl aluminum dichloride or tin tetrachloride; and component C, if required, is a trialkyl aluminum compound wherein the alkyl groups independently have from 1 to 10 carbon atoms.
component A-1.2 is n-butanol, sec-butanol, n-propanol, isopropanol, or a mixture thereof; component A-2 is dimethyl zinc, diethyl zinc, diphenyl zinc or a mixture thereof; component B-1 is a dialkyl magnesium compound wherein the alkyl groups independently have from 1 to 10 carbon atoms; component B-2 is substantially anhydrous hydrogen chloride, ethyl aluminum dichloride or tin tetrachloride; and component C, if required, is a trialkyl aluminum compound wherein the alkyl groups independently have from 1 to 10 carbon atoms.
6. A catalytic reaction product of Claim 5 wherein the components are added in the order (B-1), (B-2), (C) if employed and (A).
7. A catalytic reaction product of Claim 5 wherein the components are added in the order (B-1), (B-2), (A) and (C) if employed, and provided that the halide source, (B-2), is not a tin compound.
8. A process for polymerizing one or more .alpha.-olefins which process comprises conducting the poly-under Ziegler polymerization conditions in the presence of a catalyst of Claim 2.
9. The process of Claim 8 wherein ethylene and at least one higher C3-C10 .alpha.-olefin are polymerized under solution polymerization conditions.
10. A process for polymerizing ethylene and other .alpha.-olefins under Ziegler polymerization conditions in the presence of a catalyst comprising a magnesium halide, a titanium compound, and a zinc compound characterized in that the catalyst is prepared by first forming a reaction product or complex (A) of a mixture of a titanium compound of the formula Ti(OR)4 where R is C1-C10 alkyl and an alcohol in quantities to provide an atomic ratio of O:Ti of 0.1:1 to 4:1 with an organo zinc compound of the formula ZnR2 wherein R is C1-C10 alkyl; and thereafter admixing (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR''2?xMR''y wherein M is aluminum or zinc, each R"
is independently a hydrocarbyl or hydro-carbyloxy group having from 1 to 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (2.1) an active non-metallic halide, said non-metallic halide corres-ponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst, and X
is halogen or (2.2) a metallic halide corresponding to the empirical formula MRy-aXa wherein M is a metal of Group IIIA
or IVA of Mendeleev's Periodic Table of Elements, R is a mono-valent hydrocarbyl radical, X is halogen, y is a number corres-ponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quanti-ties of aluminum, an aluminum compound is added which is represented by the empirical formula AlRy'Xy" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and said components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from 1:1 to 200:1; Zn:Tm of from 0.1:1 to 10:1; O:Tm of from 0.1:1 to 4:1; Al:Tm of from 0.1:1 to 200:1 and an excess X:Al of from 0.0005:1 to 5:1.
is independently a hydrocarbyl or hydro-carbyloxy group having from 1 to 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (2.1) an active non-metallic halide, said non-metallic halide corres-ponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst, and X
is halogen or (2.2) a metallic halide corresponding to the empirical formula MRy-aXa wherein M is a metal of Group IIIA
or IVA of Mendeleev's Periodic Table of Elements, R is a mono-valent hydrocarbyl radical, X is halogen, y is a number corres-ponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quanti-ties of aluminum, an aluminum compound is added which is represented by the empirical formula AlRy'Xy" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and said components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from 1:1 to 200:1; Zn:Tm of from 0.1:1 to 10:1; O:Tm of from 0.1:1 to 4:1; Al:Tm of from 0.1:1 to 200:1 and an excess X:Al of from 0.0005:1 to 5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000420064A CA1190210A (en) | 1983-01-24 | 1983-01-24 | Ultra high efficiency catalyst for polymerizing olefins prepared from organotitanium and alkylzinc compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000420064A CA1190210A (en) | 1983-01-24 | 1983-01-24 | Ultra high efficiency catalyst for polymerizing olefins prepared from organotitanium and alkylzinc compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1190210A true CA1190210A (en) | 1985-07-09 |
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ID=4124413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000420064A Expired CA1190210A (en) | 1983-01-24 | 1983-01-24 | Ultra high efficiency catalyst for polymerizing olefins prepared from organotitanium and alkylzinc compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1190210A (en) |
-
1983
- 1983-01-24 CA CA000420064A patent/CA1190210A/en not_active Expired
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