CA1056546A - High efficiency, high temperature catalyst for polymerizing olefins - Google Patents
High efficiency, high temperature catalyst for polymerizing olefinsInfo
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- CA1056546A CA1056546A CA253,338A CA253338A CA1056546A CA 1056546 A CA1056546 A CA 1056546A CA 253338 A CA253338 A CA 253338A CA 1056546 A CA1056546 A CA 1056546A
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- 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
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Abstract
ABSTRACT
Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins at temperatures above 140°C are provided by reacting a transition metal compound such as tetra(isopropoxy)titanium, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum, e.g., di-n-butylmagnesium-x tri-ethylaluminum and a hydrogen halide or an active hydro-carbyl halide such as t-butyl chloride. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics.
Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins at temperatures above 140°C are provided by reacting a transition metal compound such as tetra(isopropoxy)titanium, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum, e.g., di-n-butylmagnesium-x tri-ethylaluminum and a hydrogen halide or an active hydro-carbyl halide such as t-butyl chloride. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics.
Description
This invention provides a process for the poly-merization of ~-olefins utilizing a catalyst which is sufficiently ~ctive, even at solution polymerization tem-peratures to produce such high quantities of polymer per unit of catalyst that it is no longer necessary to remove catalyst residue in order to obtain a polymer o the desired purity.
More particularly, the invention provides a process or the polymerization of an ~-olefin und~r con-ditions characteristic of Zie~ler polymerization in thepresence of a catalytic amount of a catalytic reaction product of (A) compound of a transition metal ~TM), (B) an organomagnesium component selected from (1) an organo-magnesium compound or (2) a complex of an organomagnesium compound and an organometallic compound in an amount sufficient to solubilize the organomagnesium co~pound in hydrocarbon and (C) a non-metallic halide corresponding to the formula R'X wherein R' is hydrogen or a hydrocarbyl group containing a labile halogen atom as easily lost to another compound as the chloride atom of sec-butyl chloride, and X is halogen; said reaction product being produced in a manner such that the organomagnesium component reacts with the non-metallic halide to form a hydrocarbon insoluble portion, and further provided that aluminum, in th~ form of a hydrocarbyl-aluminum compound represented by the formula R3 aAlX wherein R is hydrocarbyl, X is halide and a is a number from 0 to 1.0, is present in the catalytic reaction product in an amount sufficient to provide a reaction product that is catalytic for the polymerization of an ~-olefin; the proportions of the components of 17,712-F
B
~05~;S4t;
catalytic reaction p.roduct~eing such that the atomic ratio of Mg:TM is within the range from 20:1 to 2000:1, the atomic ratio of X:TM is within the range from 40:1 to 2000:1, the atomic ratio of Mg:X is within the range from 0.1:1 to 1:1, the atomic ratio of Mg:Al is more than 0.3:1, and the atomic ratio of Al:TM is less than 120:1 and the process is carried out at a polymerization tem-perature above 150C.
In view of the reduced activity of conventional Ziegler catalysts at solution polymerization temperatures, it is indeed surprising that the catalytic reaction pro-duct of this invention is a high efficiency catalyst capable of producing more than a million weight parts of olefin polymer per weight part of transition metal 17,712-F -la-:1(3S65~i at polymeri~ation temperatures greater than 150C, e.g., from 185 to 220C and higher. Accordingly, olefin polymers produced in accordance with the foregoing pro-cess generally contain lower amounts of catalyst residues than polymers produced in the presence of conventional catalysts even after subjecting such polymers to catalyst removal treatments. Further, these catalytic reaction products enable a higher degree of control over the polymerization in order that a more uniform product can be made. Additionally, polymers produced in the practice of the present invention often have very narrow molecular weight distributions and are therefore highly useful in molding applications such as injection molding, film application and rotational molding.
The present invention i5 most advantageously practiced in a polymerization process wherein an a-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 reaction product as hereinbefore described~ The polymerization process is most beneficially carried out under inert atmosphere and relatively low temperature and pressure, although very high pressures can be employed.
Olefins which are suitably polymerized or co-polymerized in-the practice of this invention are gen-erally the aliphatic a-monoolefins having from 2 to 18 carbon atoms such as, for example, ethylene, propylene, butene-l, pentene-l, 3 methylbutene-l, hexene-l, octene-l, dodecene-l, and octadecene-l. The a-olefins may be 1/,712-F 2 ~C~56S46 copolymerized with other ~-olefins and/or with small amounts, i.e., up to 10 weight percent based on the polymer, of other ethylenically unsaturated monomers such as butadiene, isoprene, pentadiene-1,3, styrene, a-methylstyrene and similar ethylenically unsaturated monomers which do not destroy conventional Zieyler cata-lysts. Most beneits are realized in the polymerization of aliphatic a-monoolefins, particularly ethylene and mixtures of ethylene and up to 10, especially from 0.1 to 5, weight percent of propylene, butene-l or similar higher a-olefin based on total monomer.
Advantageously, the novel catalyst composi-tion of the present invention is the reaction product of (A) a compound of a transition metal (hereinafter called "TM") of Groups 4b, 5b, 6b, 7b and 8 of Mendeleev's Periodic Table of Elements as shown in The Chemical Rubber Company's Handbook of Chemistry and Physics, 48th edition, and (B) an intermediate raaction product of (a) a hydro-carbon soluble organomagnesium compound or a hydrocarbon soluble complex of an organomagnesium compound and an organometallic compound having the formula MRy wherein M is a metal of Groups 2b, 3a including boron, la, 4a including silicon; R is a monovalent hydrocarbon radical, i.e., hydrocarbyl, such as alkyl, cycloalkyl, alkenyl, aryl, arylalkyl and alkylaryl, or other monovalent organic radical such as, for example, alkoxy, aryloxy, and alkoxyalkyl; and y is a number corresponding to the valence of M, and (b) an active non-metallic halide corresponding to the formula R'X wherein R' is hydrogen 17,712-F ~3~
or hydrocarbyl such as, for example, alkyl and aryl and that are at least as active as sec butyl and X is halogen, preferably chloride, bromide, or iodide. The organic moieties of the aforementioned catalyst components, e.g., R and R', are suitably any other organic radical provided that they do not contain unctional groups that poison conventional Ziegler catalysts. Preferably such organic moieties do not contain active hydrogen, i.e., those sufficiently active to react with the Zerewitinoff re-agent. The catalyst composition preferably has an atomic ratio of Mg:TM in the range from 30:1 to 200:1, most preferably from 30:1 to 60:1; an atomic ratio of Mg:X
in the range from 0.2 1 to 0.7:1, most preferably from 0.4:1 to 0.6:1; and an atomic ratio of X:TM in the range from 50:1 to 400:1, most preferably from 60:1 to 120:1.
Of the suitable transition metal compounds, those of titanium, vanadium, zirconium are more advan-tageously employed, with those of titanium being most advantageous. Beneficial compounds are the halides, oxyhalides, alcoholates, amides, acetylacetonates, alkyls, aryls, alkenyls, and alkadienyls. The alcoholates of titanium, so-called titanates, are the most beneficial.
Of the titanates, preferred ones are alkoxides or aryloxides, especially alkoxides having from 1 to 12 carbon atoms or a phenoxide, of trivalent or tetra-valent titanium. Such titanates are preferably derived from halides of trivalent or tetravalent titanium includ-ing alkyl titanium halides wherein one or more halogen atoms are replaced by an alkoxy or aryloxy group. Exemplary 17,712-F ~4~
~OS6546 preferred -titanates include tetrabutoxytitanium, tetra-(isopropoxy)titanium, diethoxytitanium bromide, dibutoxy-titanium dichloride, n-butyltriisopropoxytitanium, ethyl dibutoxytitanium chloride, monoethoxytitanium trichloride, and tetraphenoxytitanium. Of the prefer~ed titanates, the tetravalent ones wherein all halogen atoms are re-placed by alkoxide are most preferred, with tetra(iso-propoxy)titanium and tetrabutoxytitanium being especially preferred.
Examples of other transition metal compounds which are advantageously employed are titanium tetra-chloride, titanium trichloride, vanadium trichloride, vanadium tetrachloride, vanadium oxychloride, zirconium tetrachloride, titanocene dichloride, zirconium tetra-alcoholates such as tetrabutoxyzirconium, and vanadium acetylacetonate.
The preferred organomagnesium complex is a hydrocarbon soluble complex illustrated by the formula MgR~ xMRy wherein R is hydrocarbyl, M is aluminum, zinc or mixtures thereof and x is 0.001 to lO, especially from 0.15 to 2.5 and y denotes the number of hydrocar-byl groups which corresponds to the valence of M. This complex is prepared by reacting particulate magnesium such as magnesium turnings or magnesium particles with about a stoichiometric amount of hydrocarbon halide, illustrated as RX. The resulting hydrocarbon insolu-ble MgR2 is then solubilized by adding the organometallic compound such as AlR3 or mixtures thereof with ZnR2.
When employing a mixture of AlR3 and ZnR2 to solubilize 17,712-~ -5-~056S46 MgR2, the atomi~ ratio of Zn to Al is from 3000:1 to 0.01:1, preferably from 350:1 to 1:1. The amount of organometallic compound which is added to the MgR2 to ~orm the organomagnesium complex should be enough to solubilize a significant amount of MgR2, e.g., at least 5 weight per-cent o~ MgR2 is solubilized. It is pre~erred to solubilize at least 50 weight percent of the MgR2 and especially pre-~erred to solubilize all of MgR2. In order to obtain maximum catalyst efficiency at polymerization temperatures above 180C, it is desirable to minimize the amount of aluminum in the complex as well as in the total catalyst.
In catalyst systems employing aluminum, it is desirable that the Al:TM atomic ratio be less than 120:1, preferably less than 40:1. Accordingly, for such catalysts, it is desir-able to have a Mg:Al atomic ratio more than 0.3:1, prefer-ably from 0.5:1 to 10:1 and most preferably 0.6:1 to 7:1.
In suitable complexes, organometallic compounds (other than AlR3, ZnR2 or mixtures thereof) which also solubilize the organomagnesium compound in hydrocarbon are employed in beneficial amounts, usually an amount su~ficient to produce an atomic ratio of 0.01:1 to 10:1 of metal of the organo-metallic compound to magnesium. Examples of such other organometallic compounds include boron trialkyls such as boron triethyl, alkyl silanes such as dimethyl silane and tetraethyl silane.
Alternative to the aforementioned hydrocarbon soluble complexes, it is also advantageous to employ organomagnesium compounds as the organomagnesium compo-nent. Such compounds, although conventionally insoluble in hydrocarbon, are suitably employed. These compounds can be rendered soluble in hydrocarbon by ways kno~n in 17,712-~ -6-~56546 the art. The hydrocarbon solubilized organomagnesium compounds which do not contain catalyst poisons are the most desirable if an organomagnesium compound is to be used as the organomagnesium component~
Preferably the organomaynesium compound is dihydrocarbylmagnesium such as the magnesium dialkyls and the magnesium diaryls. Exemplary suitable magnesium dialkyls include dibutylmagnesium, dipropylmagnesium~
diethylmagnesium, dihexylmagnesium, propylbutylmagnesium and others wherein alkyl has from 1 to 20 carbon atoms.
~xemplary suitable magnesium diaryls include diphenyl-magnesium, dibenzylmagnesium, and ditolylmagnesium, with the di~lkylmagnesiums such as dibutylmagnesium, being especially preferred. Suitable organomagnesium compounds include alkyl and aryl magnesium alkoxides and aryloxides and aryl and alkyl magnesium halides with the halogen-free organomagnesium compounds being more desirable.
In cases wherein the organomagnesium component does not contain aluminum, it is sometimes desirable 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 such that high~y active trialkyl aluminum or dialkyl aluminum halide is available in small proportions as indicated herein-before.
The active non-metallic halides of the formula set forth hereinbefore include hydrogen halides and active organic halides such as t-alkyl halides, allyl halides, benzyl halides and other active hydrocarbyl halides wherein 17,712-F ~7~
ilL~565~6 hydrocarbyl is a monovalent hydrocarbon radical. By an active organic halide is meant a hydrocarbyl halide that contains 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.
In addition to the organic monohalides, it is understood that organic dihalides, trihalides and other polyhalides that are active as defined hereinbefore are also suitably employed.
Examples of preferred active 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.
The organomagnesium component is preferably reacted in hydrocarbon with the active non-metallic halide by adding with stirring the halide to the hydrocarbon con-taining the organomagnesium component. Alternatively, this desired intermediate reaction product may be formed by adding with stirring the organomagnesium component to the active halide or by simultaneously adding and mixing the halide and the organomagnesium component over a period of ~S time. The reaction between the organomagnesium component and the active halide causes the formation of a finely divided insoluble material. This intermediate reaction product now contains hydrocarbon insoluble portions as well as soluble portions. The amount of the halide added 11,712-F 8 ~StiS46 to the organomagnesium component is sufficiGnt to provide an atomic ratio of Mg:X as set forth hereinbefore. How-ever, in instances wherein aluminum is present or is to be subsequently employed in the preparation o~ the catalytic reaction product, the amount o halide should not be in such amounts as to produce significant amounts of monoalkyl aluminum dihalide or similar catalyst deactivating agents.
The aforementioned intermediate reaction product is then advantageously mixed with an amount of the transi-tion metal compound, preferably by adding the transition metal compound to the intermediate reaction product, sufficient to provide a catalytic reaction product having an atomic ratio of X:TM and Mg:TM as indicated herein-before.
While the catalytic reaction product prepared in the foregoing manner is especially preferred in the practice of this invention, a ~eneficial catalytic re-action product can be prepared by mixing the active nonmetallic halide with the transition metal compound to form an intermediate reaction product thereof and subsequently reacting this intermediate product with the organomagnesium complexO Also sui~able, but less preferred, catalytic reaction products can be made by first mixing the organomagnesium complex with the tran-sition metal compound and then adding the active non~
metallic halide or by adding and mixing all three com-ponents simultaneously.
In the preparation of the foregoing catalytic reaction products, it is preferred to carry out such 17,71~-F ~9~
1~56546 `
preparation in the presence of an inert diluent. The concentrations of catalyst components are preferably such that when the active non-metallic halide, and the magnesium complex are combined, the resultant slurry is from 0.005 to 0.1 molar (moles/liter) with respect to magnesium. By way of an example of suitable inert organic diluents can be mentioned liquefied ethane, propane, isobutane, n-bu~ane, n-hexane, khe various isomeric hexanes, isooctane, paraf~inic mi~tures of alkanes having from 8 to 9 carbon atoms, cyclohexane, m~thylcyclopentane, dimethylcyclohexane, dodecane, in-dustrial solvents composed of satura~ed or aromatic hydrocarbons such as kerosene and naphthas especially when freed of any olefin compounds and other impurities, and especially those having boiling points in the range from -50 to 200C. Also included as suitable inert diluents are, for example, benzene, toluene, ethylben-zene, cumene and decalin.
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 from -50 to 150C, preferably from 0 to 50C. The period of mixing is not considered to be critical as it is found that a sufficient catalys~ composition most often occurs within 1 minute or less. In the preparation of the catalytic reaction product, it is not necessary to sepa-rate hydrocarbon soluble components from hydrocarbon insoluble components of the reaction product. Further 1 ,712-F -10-~05~546 it is not r~quired to add a cocatalyst or an activator such as an alkyl aluminum compound to the catalytic reaction product in order to obtain a high ef~iciency catalyst. In fact, it is generally undesirable to add any aluminum compound in excess o~ the amount~ prescribed hereinbefore in order to retain high catalyst efficiency at high polymerization temperatures.
In the polymerization process employing the aforementioned catalytic reaction product, polymerization is effected by adding a catalytic amount of the above catalyst composition to a polymerization zone containing ~-olefin monomer, or vice versa. The polymerization zone is maintained at temperatures in the range from 0 to 300C, preferably at solution polymerization tem-peratures, e.g., from 150 to 250C for a residence time of 10 minutes to several hours, preferably 15 minutes to 1 hour. 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 within the range from 0.0001 to .01 milligram--atoms transition metal per liter of diluent. The most advantageous catalyst concentration will depend upon polymerization conditions such as tem~erature, pressure, solvent and presence o~ catalyst poisons and that the foregoing range is given to obtain maximum catalyst yields. Generally in the polymerization process, a carrier which may be an inert organic diluent or solvent or excess monomer is generally employed. In order to realize the full benefit of the high efficiency catalyst 1l,712-F -11-l~S6S~
of the present invention care must be taken to avoid over saturation of the solvent with polymer. If such saturation occurs ~efore the catalyst becomes depleted, the full efficiency of the catalyst is not realized.
For best results, it is preferred that the amount of polymer in the carrier not exceed 50 weight percent based on the total weight of the reaction mixture.
The polymerization pressures preferably employed are relatively low, e.g., from 100 to 500 psig (70 to 350 kg~sq cm gauge). However, polymerization within the scope of the present invention can occur at pressures from atmospheric up to pressures determined by the ca~
pabilities of the polymerization equipment. During polymerization it is desirable to stir the polymerization recipe to obtain better temperature control and to main tain uniform polymerization mixtures throughout the polymerization zone.
In order to optimize catalyst yields in the polymerization of ethylene, it is preferable to maintain an ethylene concentration in the solvent in the range from 1 to 10 weight percent, most advantageously 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.
Hydrogen is often employed in the practice of this invention to lower molecular weight of the re-sultant 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 17,712-F -12-~S~;S4~;
lar~er amounts of hydrogen within this range are found to produce generally lower molecular weight polymers.
Hydrogen can be added with a monomer strearn to the poly-merization vessel or separately added to the vessel be-fore, during or after addition of the monomer to the polymerization vessel, but during or before the addition of the catalyst.
The monomer or mixture o~ monomers is contacted with the catalytic reaction product in any conventional manner, preferably by bringing the catalytic reaction product and monomer to~ether with intimate agitation provided by suitable stirring or other means. ~gitation ; can be continued during polymerization, or in some in-stances, the polymerization can be allowed to remain unstirred while polymerization takes place. 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 poly-merization. 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 the batch mannerr 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 equili-3~ brium overflow reactor or a series of the same.
17,712-F -13-1~56S~6 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 cata-lyst 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 ~ound to contain insignificant amounts of catalyst residue and to possess a very narrow molecular weight distribution.
The fallowing examples are given to i.llustrate the invention. A11 parts and percentages are by weight unless otherwise indicated.
In the following examples the catalyst prepara-tions are carried out in the absence of oxygen or wa~er in a nitrogen filled gloved box. The catalyst components are used as diluted solutions in either n-heptane or Isopar E (a mixture of saturated isoparaffins having 8 to 9 carbon atoms). The polymerization reactions are carried out in a five liter stainless steel stirred batch reactor at 150C unless otherwise stated. In such poly-merization reactions two liters of dry oxygen-free Isopar E are added to the reactor and heated to 150C. The reactor is vent~d to about 25 psig (1.75 kg/sq. cm. gauge) and 15-to 20 psi ~1.05 to 1.4 kg./sq. cm.) of hvdrogen is added for polymer molecular weight control. Then, 120 psi (8.4 kg./sq. cm.) of ethylene is added to the reactor and the ethylene pressure is set to maintain the reactor 17,712-F -14-105654~;
pressure at 155 to 165 psig (10.9 to 11.6 kg./sq. cm.).
The catalyst is then pressured into the reactor using nitrogen and the reactor temperature is maintained for the desired polymerization time. The polymerization reactor contents are dumped into a stainless steel beaker and allowed to cool. The resulting slurry is filtered and the polymer dried and weighed. The ethylene consumption during polymerization is recorded with a DP cell which shows the rate of polymerization and the amount of polymer produced.
Catalyst efficiencies are reported as grams of polyethyl-ene catalyst per gram of titanium, g.PE/g.Ti.
Example 1 A catalyst is prepared by adding with stirring 0.946 ml of 0.519 M di(n-butyl)magnesium 2 triethylalumi-num to a solution of 15 ml of 0.123 M anhydrous hydrogen chloride in Isopar E . A white precipitate results immediately upon addition of the magnesium complex.
To the resultant slurry are added 1.18 ml of 0.01 M
tetra(isopropoxy)titanium and 82.9 ml of Isopar E .
A 12.7-ml aliquot (0.0015 mmoles Ti) of this catalyst is added to the polymerization reactor producing an increase in temperature to 167C. After 30 minutes, 230 grams of linear polyethylene is formed to give a catalyst efficiency of 3.2 x 10 g.PE/g.Ti.
Example 2 A catalyst is prepared by adding 93 ml of Isopar E , 2.5 ml of 1.15 M t-butylchloride in Isopar E , 3.05 ml of 0.295 M di(n-butyl)magnesium 2 triethylaluminum 17,712-F -15-l~S6~
to a 4 oz. bottle. To the resultant slurry is added 1.5 ml of O.al M tetra(isopropoxy)titanium. Ten milli-liters of this catalyst (0O0015 mmoles Ti) is added to the polymerization reactor and after 30 minutes the reactor contents are dumped. The yield of polymer is 204 grams indicating a catalyst eficiency of 2.8 x 106 g.PE/g.Ti.
Example 3 _ To 247 weiyht parts of Isopar ER is added 133 weight parts of 0.516 M di(n-butyl)magnesium-2 aluminum tri~thyl complex~ An 11.75 weight part portion of hy-drogen chloride gas is added to the foregoing solution of the complex with agitation~ The resultant slurry is cooled to ambient temperature (~25C) and 322 ml of neat tetra(isopropoxy)titanium is added. The result-ing catalyst is diluted with Isopar ER to give 500 weight parts of total catalyst. This catalyst is added continu-ously to a 6900 gallon (26 cu meters) reactor along with 40,000 wt parts/hr of ethylene and Isopar E~. The amounts of catalyst and Isopar ER are varied to maintain a reactor temperature of at least 185C. Hydrogen is added to the reactor to control molecular weight of the polymer such that the polymer has a Melt Index of 2.5 to 12 decigrams per minute as determined by ASTM D-1238-65T
(Condition E). The catalyst efficiency of the foregoing polymerization is greater than 1 X 106 g.PE/g.TiO
Example 4 To establish the improved stability of the present catalyst at high temperature, three runs are 17,712-F -16-lOS6S46 carried out employing catalysts which differ only as to source of halide and concentration of aluminum.
In accordance with the present invention, a catalyst is prepared by adding to 30.16 Kg. of Isopar ER the following components:
311.85 g. of HCl gas 5.556 Kg. o~ 0~548M DBMg~2ATE* in Isopar ER
29.6 mls. (28.27g.) of neat tetra(isopropoxy)-titanium *di(n-butyl)magnesium-2 aluminum triethyl The resulting catalyst has an atomic ratio as follows:
Cl/Mg/Al/Ti = 9O/31O5/59.5/1.
Following the general polymerization procedure in a 250 gallon (945 liter) stirred reaction vessel except employ-ing a polymerization temperature of 185C, the foregoing catalyst exhibits a catalyst efficiency of 1.07 x 106 g.PE/g.Ti.
For purposes of comparison, a catalyst is pre-pared by adding to 25.54 kg. of Isopar ER the following components:
- 6.01 Kg. of 15 p~rcent ethylaluminum dichloride in Isopar E
6.69 Kg. of 0.548M DBMg-2ATE* in Isopar ER
31.5 mls. (30.08 g.) neat tetra~isopropoxy)-titanium.
*ai (n~butyl)magnesium-2 aluminum triethyl The resulting catalyst has an atomic ratio as follows:
Cl/Mg/Al/Ti = 134/40/147/1 Again following the foregoing general polymerization procedure except for polymerization temperature two runs using this catalyst are carried out at polymerization 17,712-F -17-i~S65~6 temperatures of 150C and 170C. In these runs, the catalyst exhibits catalyst efficiencies of 1.16 x 106 g.PE/g.Ti and 0.43 x 106 g.PE/g.Ti, respectivelyO In - a similar run wherein a polymerization temperature of 185C is employed, no measurable amount o polyethylene is produ~ed.
_ ample 5 As evidence of preferred order of addikion of components in catalyst preparation, three runs are carried out under similar conditions except that the order of addition of components in preparation of the catalyst differs from one run to another. The compo-nents of the catalyst are as follows:
.0657 g. of HCl in 15 mls. of Isopar ER
,1726 g. of 0.51M DBMg-2ATE* in Isopar ER
.0039 g. of neat tetra(isopropoxy)titanium.
*di(n-butyl)magnesium-2 aluminum triethyl Atomic ratio of the components is Cl/Mg/A1/Ti = 130/40/80/1.
Polymerization is carried out according to thP procedure of Example 4 using a polymerization temperature of 150C.
The r~sults are recorded in Table I.
7,712-F -18-:~OS6546 TABLE I
Catalyst Run Efficiency,(2) No. Order of Addition (1) g.PE/g.Ti 1 HCl/DBMg-2ATE*/Ti(OiPr)4 2.0 x 10
More particularly, the invention provides a process or the polymerization of an ~-olefin und~r con-ditions characteristic of Zie~ler polymerization in thepresence of a catalytic amount of a catalytic reaction product of (A) compound of a transition metal ~TM), (B) an organomagnesium component selected from (1) an organo-magnesium compound or (2) a complex of an organomagnesium compound and an organometallic compound in an amount sufficient to solubilize the organomagnesium co~pound in hydrocarbon and (C) a non-metallic halide corresponding to the formula R'X wherein R' is hydrogen or a hydrocarbyl group containing a labile halogen atom as easily lost to another compound as the chloride atom of sec-butyl chloride, and X is halogen; said reaction product being produced in a manner such that the organomagnesium component reacts with the non-metallic halide to form a hydrocarbon insoluble portion, and further provided that aluminum, in th~ form of a hydrocarbyl-aluminum compound represented by the formula R3 aAlX wherein R is hydrocarbyl, X is halide and a is a number from 0 to 1.0, is present in the catalytic reaction product in an amount sufficient to provide a reaction product that is catalytic for the polymerization of an ~-olefin; the proportions of the components of 17,712-F
B
~05~;S4t;
catalytic reaction p.roduct~eing such that the atomic ratio of Mg:TM is within the range from 20:1 to 2000:1, the atomic ratio of X:TM is within the range from 40:1 to 2000:1, the atomic ratio of Mg:X is within the range from 0.1:1 to 1:1, the atomic ratio of Mg:Al is more than 0.3:1, and the atomic ratio of Al:TM is less than 120:1 and the process is carried out at a polymerization tem-perature above 150C.
In view of the reduced activity of conventional Ziegler catalysts at solution polymerization temperatures, it is indeed surprising that the catalytic reaction pro-duct of this invention is a high efficiency catalyst capable of producing more than a million weight parts of olefin polymer per weight part of transition metal 17,712-F -la-:1(3S65~i at polymeri~ation temperatures greater than 150C, e.g., from 185 to 220C and higher. Accordingly, olefin polymers produced in accordance with the foregoing pro-cess generally contain lower amounts of catalyst residues than polymers produced in the presence of conventional catalysts even after subjecting such polymers to catalyst removal treatments. Further, these catalytic reaction products enable a higher degree of control over the polymerization in order that a more uniform product can be made. Additionally, polymers produced in the practice of the present invention often have very narrow molecular weight distributions and are therefore highly useful in molding applications such as injection molding, film application and rotational molding.
The present invention i5 most advantageously practiced in a polymerization process wherein an a-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 reaction product as hereinbefore described~ The polymerization process is most beneficially carried out under inert atmosphere and relatively low temperature and pressure, although very high pressures can be employed.
Olefins which are suitably polymerized or co-polymerized in-the practice of this invention are gen-erally the aliphatic a-monoolefins having from 2 to 18 carbon atoms such as, for example, ethylene, propylene, butene-l, pentene-l, 3 methylbutene-l, hexene-l, octene-l, dodecene-l, and octadecene-l. The a-olefins may be 1/,712-F 2 ~C~56S46 copolymerized with other ~-olefins and/or with small amounts, i.e., up to 10 weight percent based on the polymer, of other ethylenically unsaturated monomers such as butadiene, isoprene, pentadiene-1,3, styrene, a-methylstyrene and similar ethylenically unsaturated monomers which do not destroy conventional Zieyler cata-lysts. Most beneits are realized in the polymerization of aliphatic a-monoolefins, particularly ethylene and mixtures of ethylene and up to 10, especially from 0.1 to 5, weight percent of propylene, butene-l or similar higher a-olefin based on total monomer.
Advantageously, the novel catalyst composi-tion of the present invention is the reaction product of (A) a compound of a transition metal (hereinafter called "TM") of Groups 4b, 5b, 6b, 7b and 8 of Mendeleev's Periodic Table of Elements as shown in The Chemical Rubber Company's Handbook of Chemistry and Physics, 48th edition, and (B) an intermediate raaction product of (a) a hydro-carbon soluble organomagnesium compound or a hydrocarbon soluble complex of an organomagnesium compound and an organometallic compound having the formula MRy wherein M is a metal of Groups 2b, 3a including boron, la, 4a including silicon; R is a monovalent hydrocarbon radical, i.e., hydrocarbyl, such as alkyl, cycloalkyl, alkenyl, aryl, arylalkyl and alkylaryl, or other monovalent organic radical such as, for example, alkoxy, aryloxy, and alkoxyalkyl; and y is a number corresponding to the valence of M, and (b) an active non-metallic halide corresponding to the formula R'X wherein R' is hydrogen 17,712-F ~3~
or hydrocarbyl such as, for example, alkyl and aryl and that are at least as active as sec butyl and X is halogen, preferably chloride, bromide, or iodide. The organic moieties of the aforementioned catalyst components, e.g., R and R', are suitably any other organic radical provided that they do not contain unctional groups that poison conventional Ziegler catalysts. Preferably such organic moieties do not contain active hydrogen, i.e., those sufficiently active to react with the Zerewitinoff re-agent. The catalyst composition preferably has an atomic ratio of Mg:TM in the range from 30:1 to 200:1, most preferably from 30:1 to 60:1; an atomic ratio of Mg:X
in the range from 0.2 1 to 0.7:1, most preferably from 0.4:1 to 0.6:1; and an atomic ratio of X:TM in the range from 50:1 to 400:1, most preferably from 60:1 to 120:1.
Of the suitable transition metal compounds, those of titanium, vanadium, zirconium are more advan-tageously employed, with those of titanium being most advantageous. Beneficial compounds are the halides, oxyhalides, alcoholates, amides, acetylacetonates, alkyls, aryls, alkenyls, and alkadienyls. The alcoholates of titanium, so-called titanates, are the most beneficial.
Of the titanates, preferred ones are alkoxides or aryloxides, especially alkoxides having from 1 to 12 carbon atoms or a phenoxide, of trivalent or tetra-valent titanium. Such titanates are preferably derived from halides of trivalent or tetravalent titanium includ-ing alkyl titanium halides wherein one or more halogen atoms are replaced by an alkoxy or aryloxy group. Exemplary 17,712-F ~4~
~OS6546 preferred -titanates include tetrabutoxytitanium, tetra-(isopropoxy)titanium, diethoxytitanium bromide, dibutoxy-titanium dichloride, n-butyltriisopropoxytitanium, ethyl dibutoxytitanium chloride, monoethoxytitanium trichloride, and tetraphenoxytitanium. Of the prefer~ed titanates, the tetravalent ones wherein all halogen atoms are re-placed by alkoxide are most preferred, with tetra(iso-propoxy)titanium and tetrabutoxytitanium being especially preferred.
Examples of other transition metal compounds which are advantageously employed are titanium tetra-chloride, titanium trichloride, vanadium trichloride, vanadium tetrachloride, vanadium oxychloride, zirconium tetrachloride, titanocene dichloride, zirconium tetra-alcoholates such as tetrabutoxyzirconium, and vanadium acetylacetonate.
The preferred organomagnesium complex is a hydrocarbon soluble complex illustrated by the formula MgR~ xMRy wherein R is hydrocarbyl, M is aluminum, zinc or mixtures thereof and x is 0.001 to lO, especially from 0.15 to 2.5 and y denotes the number of hydrocar-byl groups which corresponds to the valence of M. This complex is prepared by reacting particulate magnesium such as magnesium turnings or magnesium particles with about a stoichiometric amount of hydrocarbon halide, illustrated as RX. The resulting hydrocarbon insolu-ble MgR2 is then solubilized by adding the organometallic compound such as AlR3 or mixtures thereof with ZnR2.
When employing a mixture of AlR3 and ZnR2 to solubilize 17,712-~ -5-~056S46 MgR2, the atomi~ ratio of Zn to Al is from 3000:1 to 0.01:1, preferably from 350:1 to 1:1. The amount of organometallic compound which is added to the MgR2 to ~orm the organomagnesium complex should be enough to solubilize a significant amount of MgR2, e.g., at least 5 weight per-cent o~ MgR2 is solubilized. It is pre~erred to solubilize at least 50 weight percent of the MgR2 and especially pre-~erred to solubilize all of MgR2. In order to obtain maximum catalyst efficiency at polymerization temperatures above 180C, it is desirable to minimize the amount of aluminum in the complex as well as in the total catalyst.
In catalyst systems employing aluminum, it is desirable that the Al:TM atomic ratio be less than 120:1, preferably less than 40:1. Accordingly, for such catalysts, it is desir-able to have a Mg:Al atomic ratio more than 0.3:1, prefer-ably from 0.5:1 to 10:1 and most preferably 0.6:1 to 7:1.
In suitable complexes, organometallic compounds (other than AlR3, ZnR2 or mixtures thereof) which also solubilize the organomagnesium compound in hydrocarbon are employed in beneficial amounts, usually an amount su~ficient to produce an atomic ratio of 0.01:1 to 10:1 of metal of the organo-metallic compound to magnesium. Examples of such other organometallic compounds include boron trialkyls such as boron triethyl, alkyl silanes such as dimethyl silane and tetraethyl silane.
Alternative to the aforementioned hydrocarbon soluble complexes, it is also advantageous to employ organomagnesium compounds as the organomagnesium compo-nent. Such compounds, although conventionally insoluble in hydrocarbon, are suitably employed. These compounds can be rendered soluble in hydrocarbon by ways kno~n in 17,712-~ -6-~56546 the art. The hydrocarbon solubilized organomagnesium compounds which do not contain catalyst poisons are the most desirable if an organomagnesium compound is to be used as the organomagnesium component~
Preferably the organomaynesium compound is dihydrocarbylmagnesium such as the magnesium dialkyls and the magnesium diaryls. Exemplary suitable magnesium dialkyls include dibutylmagnesium, dipropylmagnesium~
diethylmagnesium, dihexylmagnesium, propylbutylmagnesium and others wherein alkyl has from 1 to 20 carbon atoms.
~xemplary suitable magnesium diaryls include diphenyl-magnesium, dibenzylmagnesium, and ditolylmagnesium, with the di~lkylmagnesiums such as dibutylmagnesium, being especially preferred. Suitable organomagnesium compounds include alkyl and aryl magnesium alkoxides and aryloxides and aryl and alkyl magnesium halides with the halogen-free organomagnesium compounds being more desirable.
In cases wherein the organomagnesium component does not contain aluminum, it is sometimes desirable 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 such that high~y active trialkyl aluminum or dialkyl aluminum halide is available in small proportions as indicated herein-before.
The active non-metallic halides of the formula set forth hereinbefore include hydrogen halides and active organic halides such as t-alkyl halides, allyl halides, benzyl halides and other active hydrocarbyl halides wherein 17,712-F ~7~
ilL~565~6 hydrocarbyl is a monovalent hydrocarbon radical. By an active organic halide is meant a hydrocarbyl halide that contains 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.
In addition to the organic monohalides, it is understood that organic dihalides, trihalides and other polyhalides that are active as defined hereinbefore are also suitably employed.
Examples of preferred active 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.
The organomagnesium component is preferably reacted in hydrocarbon with the active non-metallic halide by adding with stirring the halide to the hydrocarbon con-taining the organomagnesium component. Alternatively, this desired intermediate reaction product may be formed by adding with stirring the organomagnesium component to the active halide or by simultaneously adding and mixing the halide and the organomagnesium component over a period of ~S time. The reaction between the organomagnesium component and the active halide causes the formation of a finely divided insoluble material. This intermediate reaction product now contains hydrocarbon insoluble portions as well as soluble portions. The amount of the halide added 11,712-F 8 ~StiS46 to the organomagnesium component is sufficiGnt to provide an atomic ratio of Mg:X as set forth hereinbefore. How-ever, in instances wherein aluminum is present or is to be subsequently employed in the preparation o~ the catalytic reaction product, the amount o halide should not be in such amounts as to produce significant amounts of monoalkyl aluminum dihalide or similar catalyst deactivating agents.
The aforementioned intermediate reaction product is then advantageously mixed with an amount of the transi-tion metal compound, preferably by adding the transition metal compound to the intermediate reaction product, sufficient to provide a catalytic reaction product having an atomic ratio of X:TM and Mg:TM as indicated herein-before.
While the catalytic reaction product prepared in the foregoing manner is especially preferred in the practice of this invention, a ~eneficial catalytic re-action product can be prepared by mixing the active nonmetallic halide with the transition metal compound to form an intermediate reaction product thereof and subsequently reacting this intermediate product with the organomagnesium complexO Also sui~able, but less preferred, catalytic reaction products can be made by first mixing the organomagnesium complex with the tran-sition metal compound and then adding the active non~
metallic halide or by adding and mixing all three com-ponents simultaneously.
In the preparation of the foregoing catalytic reaction products, it is preferred to carry out such 17,71~-F ~9~
1~56546 `
preparation in the presence of an inert diluent. The concentrations of catalyst components are preferably such that when the active non-metallic halide, and the magnesium complex are combined, the resultant slurry is from 0.005 to 0.1 molar (moles/liter) with respect to magnesium. By way of an example of suitable inert organic diluents can be mentioned liquefied ethane, propane, isobutane, n-bu~ane, n-hexane, khe various isomeric hexanes, isooctane, paraf~inic mi~tures of alkanes having from 8 to 9 carbon atoms, cyclohexane, m~thylcyclopentane, dimethylcyclohexane, dodecane, in-dustrial solvents composed of satura~ed or aromatic hydrocarbons such as kerosene and naphthas especially when freed of any olefin compounds and other impurities, and especially those having boiling points in the range from -50 to 200C. Also included as suitable inert diluents are, for example, benzene, toluene, ethylben-zene, cumene and decalin.
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 from -50 to 150C, preferably from 0 to 50C. The period of mixing is not considered to be critical as it is found that a sufficient catalys~ composition most often occurs within 1 minute or less. In the preparation of the catalytic reaction product, it is not necessary to sepa-rate hydrocarbon soluble components from hydrocarbon insoluble components of the reaction product. Further 1 ,712-F -10-~05~546 it is not r~quired to add a cocatalyst or an activator such as an alkyl aluminum compound to the catalytic reaction product in order to obtain a high ef~iciency catalyst. In fact, it is generally undesirable to add any aluminum compound in excess o~ the amount~ prescribed hereinbefore in order to retain high catalyst efficiency at high polymerization temperatures.
In the polymerization process employing the aforementioned catalytic reaction product, polymerization is effected by adding a catalytic amount of the above catalyst composition to a polymerization zone containing ~-olefin monomer, or vice versa. The polymerization zone is maintained at temperatures in the range from 0 to 300C, preferably at solution polymerization tem-peratures, e.g., from 150 to 250C for a residence time of 10 minutes to several hours, preferably 15 minutes to 1 hour. 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 within the range from 0.0001 to .01 milligram--atoms transition metal per liter of diluent. The most advantageous catalyst concentration will depend upon polymerization conditions such as tem~erature, pressure, solvent and presence o~ catalyst poisons and that the foregoing range is given to obtain maximum catalyst yields. Generally in the polymerization process, a carrier which may be an inert organic diluent or solvent or excess monomer is generally employed. In order to realize the full benefit of the high efficiency catalyst 1l,712-F -11-l~S6S~
of the present invention care must be taken to avoid over saturation of the solvent with polymer. If such saturation occurs ~efore the catalyst becomes depleted, the full efficiency of the catalyst is not realized.
For best results, it is preferred that the amount of polymer in the carrier not exceed 50 weight percent based on the total weight of the reaction mixture.
The polymerization pressures preferably employed are relatively low, e.g., from 100 to 500 psig (70 to 350 kg~sq cm gauge). However, polymerization within the scope of the present invention can occur at pressures from atmospheric up to pressures determined by the ca~
pabilities of the polymerization equipment. During polymerization it is desirable to stir the polymerization recipe to obtain better temperature control and to main tain uniform polymerization mixtures throughout the polymerization zone.
In order to optimize catalyst yields in the polymerization of ethylene, it is preferable to maintain an ethylene concentration in the solvent in the range from 1 to 10 weight percent, most advantageously 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.
Hydrogen is often employed in the practice of this invention to lower molecular weight of the re-sultant 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 17,712-F -12-~S~;S4~;
lar~er amounts of hydrogen within this range are found to produce generally lower molecular weight polymers.
Hydrogen can be added with a monomer strearn to the poly-merization vessel or separately added to the vessel be-fore, during or after addition of the monomer to the polymerization vessel, but during or before the addition of the catalyst.
The monomer or mixture o~ monomers is contacted with the catalytic reaction product in any conventional manner, preferably by bringing the catalytic reaction product and monomer to~ether with intimate agitation provided by suitable stirring or other means. ~gitation ; can be continued during polymerization, or in some in-stances, the polymerization can be allowed to remain unstirred while polymerization takes place. 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 poly-merization. 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 the batch mannerr 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 equili-3~ brium overflow reactor or a series of the same.
17,712-F -13-1~56S~6 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 cata-lyst 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 ~ound to contain insignificant amounts of catalyst residue and to possess a very narrow molecular weight distribution.
The fallowing examples are given to i.llustrate the invention. A11 parts and percentages are by weight unless otherwise indicated.
In the following examples the catalyst prepara-tions are carried out in the absence of oxygen or wa~er in a nitrogen filled gloved box. The catalyst components are used as diluted solutions in either n-heptane or Isopar E (a mixture of saturated isoparaffins having 8 to 9 carbon atoms). The polymerization reactions are carried out in a five liter stainless steel stirred batch reactor at 150C unless otherwise stated. In such poly-merization reactions two liters of dry oxygen-free Isopar E are added to the reactor and heated to 150C. The reactor is vent~d to about 25 psig (1.75 kg/sq. cm. gauge) and 15-to 20 psi ~1.05 to 1.4 kg./sq. cm.) of hvdrogen is added for polymer molecular weight control. Then, 120 psi (8.4 kg./sq. cm.) of ethylene is added to the reactor and the ethylene pressure is set to maintain the reactor 17,712-F -14-105654~;
pressure at 155 to 165 psig (10.9 to 11.6 kg./sq. cm.).
The catalyst is then pressured into the reactor using nitrogen and the reactor temperature is maintained for the desired polymerization time. The polymerization reactor contents are dumped into a stainless steel beaker and allowed to cool. The resulting slurry is filtered and the polymer dried and weighed. The ethylene consumption during polymerization is recorded with a DP cell which shows the rate of polymerization and the amount of polymer produced.
Catalyst efficiencies are reported as grams of polyethyl-ene catalyst per gram of titanium, g.PE/g.Ti.
Example 1 A catalyst is prepared by adding with stirring 0.946 ml of 0.519 M di(n-butyl)magnesium 2 triethylalumi-num to a solution of 15 ml of 0.123 M anhydrous hydrogen chloride in Isopar E . A white precipitate results immediately upon addition of the magnesium complex.
To the resultant slurry are added 1.18 ml of 0.01 M
tetra(isopropoxy)titanium and 82.9 ml of Isopar E .
A 12.7-ml aliquot (0.0015 mmoles Ti) of this catalyst is added to the polymerization reactor producing an increase in temperature to 167C. After 30 minutes, 230 grams of linear polyethylene is formed to give a catalyst efficiency of 3.2 x 10 g.PE/g.Ti.
Example 2 A catalyst is prepared by adding 93 ml of Isopar E , 2.5 ml of 1.15 M t-butylchloride in Isopar E , 3.05 ml of 0.295 M di(n-butyl)magnesium 2 triethylaluminum 17,712-F -15-l~S6~
to a 4 oz. bottle. To the resultant slurry is added 1.5 ml of O.al M tetra(isopropoxy)titanium. Ten milli-liters of this catalyst (0O0015 mmoles Ti) is added to the polymerization reactor and after 30 minutes the reactor contents are dumped. The yield of polymer is 204 grams indicating a catalyst eficiency of 2.8 x 106 g.PE/g.Ti.
Example 3 _ To 247 weiyht parts of Isopar ER is added 133 weight parts of 0.516 M di(n-butyl)magnesium-2 aluminum tri~thyl complex~ An 11.75 weight part portion of hy-drogen chloride gas is added to the foregoing solution of the complex with agitation~ The resultant slurry is cooled to ambient temperature (~25C) and 322 ml of neat tetra(isopropoxy)titanium is added. The result-ing catalyst is diluted with Isopar ER to give 500 weight parts of total catalyst. This catalyst is added continu-ously to a 6900 gallon (26 cu meters) reactor along with 40,000 wt parts/hr of ethylene and Isopar E~. The amounts of catalyst and Isopar ER are varied to maintain a reactor temperature of at least 185C. Hydrogen is added to the reactor to control molecular weight of the polymer such that the polymer has a Melt Index of 2.5 to 12 decigrams per minute as determined by ASTM D-1238-65T
(Condition E). The catalyst efficiency of the foregoing polymerization is greater than 1 X 106 g.PE/g.TiO
Example 4 To establish the improved stability of the present catalyst at high temperature, three runs are 17,712-F -16-lOS6S46 carried out employing catalysts which differ only as to source of halide and concentration of aluminum.
In accordance with the present invention, a catalyst is prepared by adding to 30.16 Kg. of Isopar ER the following components:
311.85 g. of HCl gas 5.556 Kg. o~ 0~548M DBMg~2ATE* in Isopar ER
29.6 mls. (28.27g.) of neat tetra(isopropoxy)-titanium *di(n-butyl)magnesium-2 aluminum triethyl The resulting catalyst has an atomic ratio as follows:
Cl/Mg/Al/Ti = 9O/31O5/59.5/1.
Following the general polymerization procedure in a 250 gallon (945 liter) stirred reaction vessel except employ-ing a polymerization temperature of 185C, the foregoing catalyst exhibits a catalyst efficiency of 1.07 x 106 g.PE/g.Ti.
For purposes of comparison, a catalyst is pre-pared by adding to 25.54 kg. of Isopar ER the following components:
- 6.01 Kg. of 15 p~rcent ethylaluminum dichloride in Isopar E
6.69 Kg. of 0.548M DBMg-2ATE* in Isopar ER
31.5 mls. (30.08 g.) neat tetra~isopropoxy)-titanium.
*ai (n~butyl)magnesium-2 aluminum triethyl The resulting catalyst has an atomic ratio as follows:
Cl/Mg/Al/Ti = 134/40/147/1 Again following the foregoing general polymerization procedure except for polymerization temperature two runs using this catalyst are carried out at polymerization 17,712-F -17-i~S65~6 temperatures of 150C and 170C. In these runs, the catalyst exhibits catalyst efficiencies of 1.16 x 106 g.PE/g.Ti and 0.43 x 106 g.PE/g.Ti, respectivelyO In - a similar run wherein a polymerization temperature of 185C is employed, no measurable amount o polyethylene is produ~ed.
_ ample 5 As evidence of preferred order of addikion of components in catalyst preparation, three runs are carried out under similar conditions except that the order of addition of components in preparation of the catalyst differs from one run to another. The compo-nents of the catalyst are as follows:
.0657 g. of HCl in 15 mls. of Isopar ER
,1726 g. of 0.51M DBMg-2ATE* in Isopar ER
.0039 g. of neat tetra(isopropoxy)titanium.
*di(n-butyl)magnesium-2 aluminum triethyl Atomic ratio of the components is Cl/Mg/A1/Ti = 130/40/80/1.
Polymerization is carried out according to thP procedure of Example 4 using a polymerization temperature of 150C.
The r~sults are recorded in Table I.
7,712-F -18-:~OS6546 TABLE I
Catalyst Run Efficiency,(2) No. Order of Addition (1) g.PE/g.Ti 1 HCl/DBMg-2ATE*/Ti(OiPr)4 2.0 x 10
2 HCl/Ti(OiPr)4/DBMg~2ATE* 0~98 x 106
3 DBMg-2ATE*/Ti(OiPr)4/HC1 0.68 x 10 (1) Components added to the catalyst reaction vessel in left to right order. In Run No. 3, the mix-ture of DBM~2ATE* ~ Ti(OiPr)4 is added to HCl in Isopar E 1.
(2) Catalyst efficiency in grams of polyethylene per gram of titaniuma * di (n-butyl)magnesium-2 aluminum triethyl Example 6 To illustrate the relation between Al:Ti and Al:Mg ratios and catalyst efficiencies as temperature increases, several runs are carried out using different proportions of the following catalyst components:
anhydrous HC1 DBMg-x ATE*
tetra(isopropoxy)titanium *di(n-butyl)magnesium-x al~inum triethyl wherein x is a value between 1/6 and 2 obtained by combining different amounts of DBMg-l/6 ATE and DBMg~2ATE.
in Isopar ERo The ratios of the foregoing catalyst components are shown in Table II.
Following the polymerization procedure of EX-ample 4 at a polymerization temperature as indicated in Table II, ethylene is polymerized in the presence of the several catalysts and the results are shown in Table II.
17,712-F -19-~S~i~46 TABLE II
Catalyst Run Atomic Ratio, Polymerization Efficiency, No. Cl/Mg/Al/Ti Temperature,C g.PE/g.Ti 1 134/40/58/1 185 1.8 x 106 2 90/40/58/1 185 }.0 x 106 3 90/40/40/1 189 1.0 x 106
(2) Catalyst efficiency in grams of polyethylene per gram of titaniuma * di (n-butyl)magnesium-2 aluminum triethyl Example 6 To illustrate the relation between Al:Ti and Al:Mg ratios and catalyst efficiencies as temperature increases, several runs are carried out using different proportions of the following catalyst components:
anhydrous HC1 DBMg-x ATE*
tetra(isopropoxy)titanium *di(n-butyl)magnesium-x al~inum triethyl wherein x is a value between 1/6 and 2 obtained by combining different amounts of DBMg-l/6 ATE and DBMg~2ATE.
in Isopar ERo The ratios of the foregoing catalyst components are shown in Table II.
Following the polymerization procedure of EX-ample 4 at a polymerization temperature as indicated in Table II, ethylene is polymerized in the presence of the several catalysts and the results are shown in Table II.
17,712-F -19-~S~i~46 TABLE II
Catalyst Run Atomic Ratio, Polymerization Efficiency, No. Cl/Mg/Al/Ti Temperature,C g.PE/g.Ti 1 134/40/58/1 185 1.8 x 106 2 90/40/58/1 185 }.0 x 106 3 90/40/40/1 189 1.0 x 106
4 90/40/~0/1 lg6 1.0 x 106 90/40/13.3/1 199 1.6 x 106 6 90/40/8/1 199 1.5 x 106 7 90/40/8/1 205 1.4 x 106 8 84O5/~0/6.25/1 212 1.1 x 106 As evidenced by the foregoing data of Example 4 and Table II, as polymerization temperature increases, the ratio of Al~Mg and Al:Ti should be reduced in order to ob-tain high catalyst efficiencies.
17,712-F -20-
17,712-F -20-
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. The polymerization of an a-olefin under conditions characteristic of Ziegler polymerization in the presence of a catalytic amount of a catalytic reaction product of (A) compound of a transition metal (TM), (B) an organomagnesium component selected from (1) an organo-magnesium compound or (2) a complex of an organomagnesium compound and an organometallic compound in an amount sufficient to solubilize the organomagnesium compound in hydrocarbon and (C) a non-metallic halide corresponding to the formula R'X wherein R' is hydrogen or a hydrocarbyl group containing a labile halogen atom as easily lost to another compound as the chloride atom of sec-butyl chloride, and X is halogen; said reaction product being produced in a manner such that the organomagnesium component reacts with the non-metallic halide to form a hydrocarbon insoluble portion, and further provided that aluminum, in the form of a hydrocarbyl-aluminum compound represented by the formula R3-aAlXa wherein R is hydrocarbyl, X is halide and a is a number from 0 to 1.0, is present in the catalytic reaction product in an amount sufficient to provide a reaction product that is catalytic for the polymerization of an .alpha.-olefin; the proportions of the components of catalytic reaction product being such that the atomic ratio of Mg:TM is within the range from 20:1 to 2000:1, the atomic ratio of X:TM is within the range from 40:1 to 2000:1, the atomic ratio of Mg:X is within the range from 0.1:1 to 1:1, the atomic ratio of Mg:Al is more than 0.3:1, and the atomic ratio of Al:TM is less than 120:1 and the process is carried out at a polymerization temperature above 150°C.
2. The process of Claim 1 wherein the organo-magnesium compound is a dihydrocarbyl magnesium
3. The process of Claim 1 wherein the organo-magnesium component is a complex of dialkyl magnesium and a trialkyl aluminum represented by the formula MgR2?XAlR3 wherein R is alkyl and X is from 0.001 to 3.3.
4. The process of Claim 3 wherein the atomic ratio of Mg:TM is from 30:1 to 60:1, the atomic ratio of Mg:X is from 0.2:1 to 0.7:1 and the atomic ratio of Mg:Al is from 0.6:1 to 7:1 for the total catalytic reaction product.
5. The process of Claim 4 wherein the transi-tion metal compound is a hydrocarbyloxide of tetravalent or trivalent titanium.
6. The process of Claim 5 wherein the catalytic reaction product is the reaction product of the alkoxide of titanium with an intermediate reaction product of the organomagnesium component and the non-metallic halide.
7. The process of Claim 1 wherein the transi-tion metal compound is a tetra(alkoxy)titanium, the organo-magnesium compound is a dihydrocarbyl magnesium, the organometallic compound is a trihydrocarbyl aluminum, the non-metallic halide is a hydrogen halide or a t-alkyl halide, the Mg:X ratio is from 0.2:1 to 0.7:1, the Mg:Al ratio is from 0.6:1 to 7:1, the Al:Ti ratio is less than 40:1, and the polymerization temperature is at least 185°C.
8. The process of Claim 7 wherein the transition metal compound is a tetra(alkoxy)titanium, the organo-magnesium compound is a dialkyl magnesium, the non-metallic halide is hydrogen chloride, the .alpha.-olefin is ethylene or a mixture of ethylene and up to 10 weight percent of higher .alpha.-olefin and the process is carried out at a polymerization temperature from 185°C to 250°C.
9. The process of Claim 8 wherein the non--metallic halide is hydrogen chloride, the tetra(alkoxy)-titanium is tetra(isopropoxy)titanium or tetra(butoxy)-titanium, the dialkyl magnesium is dibutyl magnesium, the .alpha.-olefin is ethylene or a mixture of ethylene and up to 5 weight percent of propylene or butene-1, the Mg:X
ratio is from 0.4:1 to 0.6:1 and the process is carried out at a polymerization temperature from 185°C to 220°C.
ratio is from 0.4:1 to 0.6:1 and the process is carried out at a polymerization temperature from 185°C to 220°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58129475A | 1975-05-27 | 1975-05-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1056546A true CA1056546A (en) | 1979-06-12 |
Family
ID=24324626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,338A Expired CA1056546A (en) | 1975-05-27 | 1976-05-26 | High efficiency, high temperature catalyst for polymerizing olefins |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS51144397A (en) |
| AU (1) | AU502872B2 (en) |
| BE (1) | BE842254A (en) |
| BR (1) | BR7603336A (en) |
| CA (1) | CA1056546A (en) |
| DE (1) | DE2623332C2 (en) |
| ES (1) | ES448189A1 (en) |
| FR (1) | FR2312289A1 (en) |
| GB (1) | GB1500873A (en) |
| IT (1) | IT1061612B (en) |
| NL (1) | NL163525C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031056A (en) * | 1994-07-01 | 2000-02-29 | Dsm N.V. | Catalyst system for the polymerization of ethylene |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4135046A (en) | 1977-02-28 | 1979-01-16 | Arco Polymers, Inc. | High efficiency catalysts for olefin polymerization |
| US4390677A (en) | 1978-03-31 | 1983-06-28 | Karol Frederick J | Article molded from ethylene hydrocarbon copolymer |
| US4198315A (en) | 1978-09-05 | 1980-04-15 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| CA1132125A (en) * | 1978-09-05 | 1982-09-21 | Donald F. Birkelbach | High efficiency catalyst for polymerizing olefins |
| US4243785A (en) | 1978-09-05 | 1981-01-06 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| ZA801724B (en) * | 1979-04-01 | 1981-03-25 | Stamicarbon | Catalytic titanium compound,process for the manufacture thereof,and process for the polymerization of lakenes-1 with application of such a titanium component |
| US4323665A (en) | 1979-04-09 | 1982-04-06 | The Dow Chemical Co. | High efficiency catalyst for polymerizing olefins |
| US4224186A (en) | 1979-04-09 | 1980-09-23 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| US4276191A (en) | 1979-06-04 | 1981-06-30 | Standard Oil Company (Indiana) | Catalyst and process for polymerization of alpha-olefins |
| JPS55164206A (en) | 1979-06-11 | 1980-12-20 | Mitsui Petrochem Ind Ltd | Preparation of wax |
| US4244838A (en) | 1979-06-25 | 1981-01-13 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| US4246383A (en) | 1979-06-25 | 1981-01-20 | The Dow Chemical Company | Process for polymerizing olefins in the presence of a catalyst prepared from an organomagnesium component which does not reduce TiCl4 |
| JPS56161406A (en) * | 1980-05-17 | 1981-12-11 | Mitsubishi Petrochem Co Ltd | Polymerization of ethylene |
| US4238355A (en) | 1979-09-10 | 1980-12-09 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| CA1129400A (en) * | 1979-09-28 | 1982-08-10 | Masayasu Furusato | PROCESS FOR POLYMERIZING .alpha.-OLEFINS |
| US4308369A (en) | 1979-09-28 | 1981-12-29 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| US4269733A (en) | 1979-09-28 | 1981-05-26 | The Dow Chemical Company | Ultra high efficiency catalyst for polymerizing olefins |
| US4263422A (en) | 1979-12-31 | 1981-04-21 | The Dow Chemical Company | Polymerization of olefins with dual, independently supported catalysts |
| US4285834A (en) | 1979-12-31 | 1981-08-25 | The Dow Chemical Company | Dual, independently supported catalyst mixtures |
| US4496660A (en) * | 1980-10-01 | 1985-01-29 | The Dow Chemical Company | Catalyst prepared from organo-magnesium compound; oxygen- or nitrogen-containing compound; halide source; transition metal compound and reducing agent |
| EP0053632B1 (en) * | 1980-12-05 | 1986-04-23 | The Dow Chemical Company | Catalyst composition and polymerization of alpha-olefins employing such a catalyst composition |
| US4399053A (en) | 1980-12-24 | 1983-08-16 | The Dow Chemical Company | High efficiency catalyst containing titanium, zirconium and zinc for polymerizing olefins |
| US4380616A (en) | 1981-05-14 | 1983-04-19 | The Dow Chemical Company | Polymerization of olefins in the presence of chromium-containing catalysts |
| US4362654A (en) | 1981-05-14 | 1982-12-07 | The Dow Chemical Company | Chromium-containing catalysts for polymerizing olefins |
| US4409126A (en) | 1981-10-22 | 1983-10-11 | The Dow Chemical Company | Ultra high efficiency catalyst for polymerizing olefins |
| US4381253A (en) | 1981-10-22 | 1983-04-26 | The Dow Chemical Company | Ultra high efficiency catalyst for polymerizing olefins |
| US4380508A (en) | 1981-10-22 | 1983-04-19 | The Dow Chemical Company | Ultra high efficiency catalyst for polymerizing olefins |
| US4434282A (en) | 1982-10-04 | 1984-02-28 | The Dow Chemical Company | Process for polymerizing olefins |
| EP0114902A1 (en) * | 1983-01-26 | 1984-08-08 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins prepared from organotitanium and magnesium components |
| NL8301822A (en) * | 1983-05-21 | 1984-12-17 | Stamicarbon | ETHENE POLYMERIZATION CATALYST AND (CO) POLYMERIZATION OF ETHENE WITH THAT CATALYST. |
| US4496661A (en) * | 1983-10-24 | 1985-01-29 | The Dow Chemical Company | High efficiency catalyst for polymerizing olefins |
| JPH0780968B2 (en) * | 1987-09-09 | 1995-08-30 | 住友化学工業株式会社 | Process for producing olefin polymer |
| US5045612A (en) * | 1990-04-18 | 1991-09-03 | The Dow Chemical Company | Catalyst and process for polymerizing olefins |
| US5114897A (en) * | 1990-04-18 | 1992-05-19 | The Dow Chemical Company | Catalyst and process for polymerizing olefins |
| BR112014000863B1 (en) | 2011-08-26 | 2020-02-18 | Dow Global Technologies Llc | PROCESS TO FORM A BIAXIALLY ORIENTED FILM, BIAXIALLY ORIENTED FILM AND LAMINATE FILM STRUCTURE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE785673A (en) * | 1971-06-30 | 1973-01-02 | Naphtachimie Sa | POLYMERIZATION CATALYZERS OF OLEFINS PREPARED FROM DECOMPOSED ORGANOMAGNESIANS |
-
1976
- 1976-05-24 NL NL7605544A patent/NL163525C/en not_active IP Right Cessation
- 1976-05-24 ES ES448189A patent/ES448189A1/en not_active Expired
- 1976-05-25 AU AU14263/76A patent/AU502872B2/en not_active Expired
- 1976-05-25 DE DE19762623332 patent/DE2623332C2/en not_active Expired
- 1976-05-26 IT IT4967376A patent/IT1061612B/en active
- 1976-05-26 BE BE167359A patent/BE842254A/en not_active IP Right Cessation
- 1976-05-26 JP JP6103176A patent/JPS51144397A/en active Granted
- 1976-05-26 CA CA253,338A patent/CA1056546A/en not_active Expired
- 1976-05-26 BR BR7603336A patent/BR7603336A/en unknown
- 1976-05-26 GB GB2193076A patent/GB1500873A/en not_active Expired
- 1976-05-26 FR FR7616109A patent/FR2312289A1/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6031056A (en) * | 1994-07-01 | 2000-02-29 | Dsm N.V. | Catalyst system for the polymerization of ethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS551283B2 (en) | 1980-01-12 |
| FR2312289A1 (en) | 1976-12-24 |
| JPS51144397A (en) | 1976-12-11 |
| NL163525B (en) | 1980-04-15 |
| NL7605544A (en) | 1976-11-30 |
| IT1061612B (en) | 1983-04-30 |
| DE2623332A1 (en) | 1976-12-09 |
| FR2312289B1 (en) | 1981-12-11 |
| BE842254A (en) | 1976-11-26 |
| GB1500873A (en) | 1978-02-15 |
| DE2623332C2 (en) | 1986-08-07 |
| ES448189A1 (en) | 1977-07-01 |
| NL163525C (en) | 1980-09-15 |
| BR7603336A (en) | 1976-12-07 |
| AU502872B2 (en) | 1979-08-09 |
| AU1426376A (en) | 1977-12-01 |
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