JPS648002B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel catalyst compositions useful for initiating and promoting the polymerization of alpha-olefins and to polymerization methods using such catalyst compositions. The present invention comprises (A) a complex of trivalent titanium with an electron donor and (B) (1) an organomagnesium compound or (2) an organomagnesium compound in an amount sufficient to dissolve the organomagnesium compound in a hydrocarbon. an organomagnesium component selected from a complex with an organometallic compound of (C)(1) of the formula R' is a halogen) or an active nonmetallic halide of the formula (2 ₎ MR _ya group, X is a halogen, y is a number corresponding to the valence of M, and a is a number from 1 to y). provide a reaction product; provided that the ratio of the aforementioned components of the catalytic reaction product is such that the atomic ratio of Mg:Ti is from 1:1 to
2000:1, and the atomic ratio of Al:Ti is 0.1:1 ~
2000:1, and the atomic ratio of Mg:X is
The condition is that the ratio is 0.01:1 to 1:1. The present invention also provides a method for polymerizing at least one alpha-olefin under conditions typical of Ziegler polymerization, in which the aforementioned reaction product is preferably used as the only catalyst. Olefin polymers produced according to the method of the present invention contain only small amounts of catalyst residues and are highly homogeneous. The invention is most conveniently carried out in a polymerization process in which alpha-olefins are polymerized in a polymerization zone containing a non-active diluent and a catalytic reaction product, generally in the presence of hydrogen as a molecular weight modifier. Particularly advantageous is the copolymerization of ethylene with higher α-olefins using the catalytic reaction products of the invention. The polymerization process is most advantageously carried out in an inert environment and under relatively low temperatures and pressures, although very high pressures are occasionally used. The olefins which are conveniently monopolymerized or copolymerized in the practice of this invention are generally aliphatic α-monoolefins having 2 to 18 carbon atoms or α-
-It is a diolefin. Such α-olefins include, for example, ethylene, propylene, butene-
1, pentene-1, 3-methylbutene-1, hexene-1, octene-1, dodecene-1, octadecene-1, butadiene, isoprene and 1,
Contains 7-octadiene. α-olefins may contain other olefins and/or small amounts, e.g. up to 25% by weight based on the polymer, of other ethylenically based monomers such as styrene, α-methylstyrene and similar ethylenically unsaturated monomers that do not destroy customary Ziegler catalysts. It is possible to copolymerize with unsaturated monomers. Based on aliphatic α-monoolefins, especially ethylene and ethylene and total monomers
propylene up to 50%, especially from 0.5 to 40% by weight,
The greatest benefits are obtained in the polymerization of butene-1,1,7-octadiene or mixtures with similar higher α-olefins. Electron donor compounds which can be suitably used include, for example, aliphatic alcohols such as isopropyl alcohol, ethanol, n-propyl alcohol, butanol and other alcohols having 2 to 10 carbon atoms; ethers with, ketones with 3 to 20 carbon atoms;
Includes amines with 1 to 20 carbon atoms; aldehydes or olefins with 2 to 20 carbon atoms and water. Preferably, the trivalent titanium complex has the empirical formula:
TiZ ₃ (L) _x where Z is a halide and L is water or an organic electron donor, such as an alcohol,
electron-donating compounds such as ethers, ketones, amines or olefins, and x is an integer from 1 to 6). Typically, the organic electron donor has 1 to 12 carbon atoms and donates a lone pair of electrons to the complex. In the most preferred complexes Z is chloride or bromide, most preferably chloride and L is an alcohol, especially an aliphatic alcohol having 2 to 8 carbon atoms and most preferably isopropyl alcohol, n-propyl Alcohols having 3 to 6 carbon atoms such as n-butyl alcohol and isobutyl alcohol. The exact structure of the complex is unknown but is believed to contain a trivalent bond to the halide ion and 1 to 6, preferably 2 to 4 coordinate bonds to the electron donating compound. . Titanium halide complexes are most conveniently made by heating trivalent titanium halides dispersed in an electron donating compound under nitrogen or a similar neutral atmosphere. Complex formation is usually indicated visually by a distinct change in color. For example, dark purple α
When TiCl ₃ is heated in anhydrous isopropyl alcohol under a nitrogen atmosphere, complex formation is indicated by the formation of a bright blue solution. For desirable complexes, the complex is usually a solid. In the preparation of the complex, in addition to α- _TiCl3 , Δ,
Titanium trichloride in the gamma and beta crystalline forms is advantageously used. Also suitable are, for example, titanium tribromide and titanium trifluoride. Of the foregoing, titanium trichloride in the γ- and α-forms is preferred. Particularly preferred catalytic reaction products are those in which the trivalent titanium complex TiZ ₃ (L) _x is a complex of titanium trichloride and isopropyl alcohol, and x is from 2 to
4, and when the organomagnesium compound is dibutylmagnesium. The preferred organomagnesium component has the formula MgR″ ₂ .
mAlR ₃・nZnR′′′′ ₂ (wherein R″, R, and R
′′′′ are individually hydrocarbyl, and m is
0.001 to 10, especially 0.15 to 2.5, and n is 0, or m is 0, and n is 0.001 to 10, especially
0.15 to 2.5, or m and n are both 0
and m+n is from 0.001 to 10, especially from 0.15 to 2.5). Hydrocarbyl as used herein is a monovalent hydrocarbyl. Desirably hydrocarbyl is alkyl, cycloalkyl, aryl, aralkyl, alkenyl and similar hydrocarbon groups having from 1 to 8 carbon atoms, with alkyl having from 1 to 4 carbon atoms being particularly preferred. The complex is prepared by reacting granular magnesium, such as magnesium shavings, or magnesium granules, with a stoichiometric amount of hydrocarbyl halide, denoted R″X.
MgR″ ₂ is made soluble by the addition of an organometallic compound such as AlR ₃ or its mixture with ZnR′′′′ _2. An organometallic compound that is added to MgR″ ₂ to form an organomagnesium complex. The amount of
A significant amount of MgR″ ₂ , e.g. at least 5% by weight
The amount should be sufficient to solubilize the _MgR''2 . It is desirable that at least 50% by weight of the _MgR''2 be solubilized and it is especially desirable that all the _MgR''2 be solubilized. The organomagnesium component is preferably a complex of dialkylmagnesium and trialkylaluminum, and Mg in the organomagnesium component:
The atomic ratio of Al is in the range of 0.3:1 to 1000:1. AlR and _ZnR to solubilize MgR″ ₂
′′′ _′ When using a mixture of
The ratio is 1:1. To obtain the highest catalyst efficiency at polymerization temperatures above 180°C, it is desirable to minimize the amount of aluminum in the complex as well as in the total catalyst. It is therefore desirable to have a Mg:Al atomic ratio of 0.3 to 1 or higher, and preferably 0.5:1 to 10:1, for catalysts having an Al:Ti atomic ratio of less than 120:1. In suitable complexes, the organometallic compound (other than AlR ₃ , ZnR′′′′ ₂ or mixtures thereof) which solubilizes the organomagnesium compound in the hydrocarbon is present in an advantageous amount, usually the metal to magnesium of the organometallic compound. Atomic ratio of 0.01:1~
Use in sufficient amount to yield a 10:1 ratio. Examples of such other organometallic compounds include trialkylborons such as triethylboron, alkylsilanes such as dimethylsilane and tetraethylsilane, alkyltin and alkyl phosphate compounds. As an alternative to the solubilized magnesium complexes mentioned above, the use of organomagnesium compounds as organomagnesium component is also advantageous. Although such compounds are often insoluble in hydrocarbons, they are preferably used. These compounds can be made soluble in hydrocarbons by the addition of ethers, amines, etc., but such solubilizers often reduce the activity of the catalyst. Recently, it has been taught, for example, in US Pat. No. 3,646,231, that such compounds could be made hydrocarbon soluble without the use of such catalyst poisons. More recently, hydrocarbon-solubilized organomagnesium compounds are most desirable if the organomagnesium compound is used as the organomagnesium component. Desirably the organomagnesium compound is a dihydrocarbylmagnesium such as magnesium dialkyl and magnesium diaryl. Examples of suitable magnesium dialkyls include dibutylmagnesium, especially di-n-butylmagnesium and n-butyl sec-butylmagnesium, dipropylmagnesium, diethylmagnesium, dihexylmagnesium, propylbutylmagnesium and those in which the alkyl has 1 to 20 carbon atoms. Including other things that you have. Examples of suitable magnesium diaryls include diphenylmagnesium, dibenzylmagnesium, and ditolylmagnesium, with dialkylmagnesiums such as dibutylmagnesium being particularly preferred. Suitable organomagnesium compounds include alkyl and arylmagnesium alkoxides, aryloxides, and aryl and alkylmagnesium halides, and more preferably organomagnesium compounds that do not contain halogens. Preferred halide sources include active non-metallic halides of the formulas shown above, including hydrogen halides and tertiary alkyl halides, allyl halides, benzyl halides and other active hydrocarbyl halides where hydrocarbyl is as defined above. By active organic halide is meant a hydrocarbyl halide containing at least an active, ie unstable, halogen such as the halogen of sec-butyl chloride, which is easily lost to other compounds. It goes without saying that in addition to organic monohalides, organic dihalides, trihalides and other active polyhalides as defined in the preamble are preferably used. Preferred active nonmetallic halides include, for example, hydrogen chloride, hydrogen bromide, tertiary butyl chloride, tertiary amyl bromide, allyl chloride, benzyl chloride, crotyl chloride, methylvinylcarvinyl chloride, α-phenylethyl bromide, and Contains diphenylmethyl chloride. The most desirable is hydrogen chloride,
These are tert-butyl chloride, allyl chloride and benzyl chloride. Suitable metal halides indicated by the formula in the preamble are metals 3a or 4a of the Mendeleev Table of the Elements.
Organometallic halides and metal halides that are in the group. The preferred metal halide has the formula
AlR _3-a X _a (wherein R is hydrocarbyl such as alkyl, X is halogen and a is 1-
3) aluminum halide. More preferred are alkylaluminum halides such as ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, and diethylaluminum bromide, with ethylaluminum dichloride being particularly preferred. Alternatively, aluminum trichloride or a combination of aluminum trichloride and an alkyl aluminum halide or a trialkyl aluminum compound can also be suitably used. The organic part of the organomagnesium component, e.g.
R'', R, and R''''' and the organic moieties of the halide source, such as R and R', may be any other organic group as long as they do not contain functional groups that would poison customary Ziegler catalysts Preferably, such organic moieties are free of active hydrogen, i.e., hydrogen that reacts sufficiently actively with the Tzelevitinoff reagent. To maximize catalytic efficiency, the catalyst comprises the catalyst components in the following particularly desirable order: Prepared by mixing in a diluent: organomagnesium, titanium complex, and halide source. A somewhat inferior order of addition is the organomagnesium component first added to the neutral liquid diluent, then the halide source, and then the titanium. Adding the complex. Suitable but least favorable addition orders are (1) mixing the halide source first with the titanium complex and then adding the organomagnesium, or (2) adding and mixing the three components simultaneously. The above-mentioned catalyst component has an atomic ratio of Mg:Ti of 1:1 to 2000:1, preferably 10:1 to 2000:1.
100:1, most preferably in the range of 20:1 to 80:1; Mg:X atomic ratio of 0.01:1 to 1:1, preferably 0.2:1 to 0.7:1, most preferably 0.4:1
Combine in sufficient proportions to give a range of ~0.6:1. If neither the organomagnesium component nor the halide source contains aluminum, it is desirable to include an aluminum compound in the total catalyst, such as an aluminum trialkyl, an alkyl aluminum halide, or an aluminum halide. If it's 180℃
When using a polymerization temperature lower than Al:
The atomic ratio of Ti is preferably 0.1:1 to 2000:1, preferably 1:1 to 200:1. However, when using polymerization temperatures higher than 180°C, the Mg:Al ratio is greater than 0.3:1, preferably between 0.5:1 and 10:1;
The aluminum compound is then used in such a proportion that the Al:Ti ratio is less than 120:1, preferably less than 75:1. However, when very little aluminum is used, it is necessary to use high purity solvents or diluents in the polymerization zone. Additionally, the other components present in the zone must be essentially free of impurities that would react with the aluminum alkyl. Otherwise, additional organoaluminum must be used to react with such impurities. Moreover, in the catalyst the aluminum compound should be in the form of a trialkylaluminum or an alkyl aluminum halide, as long as the alkyl aluminum halide is substantially free of alkyl aluminum dihalides. The basis for specifying the atomic ratio in the above-mentioned catalytic reaction product is generally as follows. Mg:Ti ratio (1:1 to 80:1) At levels of Mg:Ti ratio below 10:1, the catalyst efficiency decreases significantly, while the high At one level, a poorly colored product may be produced. At Mg:Ti levels higher than 80:1, excess amounts of expensive magnesium alkyls are used and residues from the magnesium salts produced are known to cause corrosion problems in processing equipment. Al:Ti Ratio (1:1 to 200:1) At low levels of Al:Ti, the catalyst becomes inefficient at producing polymer or fails to produce polymer at all. Aluminum alkyls are very effective scavengers for oxygen and water that inhibit polymerization;
However, this is not the only effect of aluminum alkyls. At high levels of Al:Ti, aluminum alkyl is wasted. Also, high residual levels of aluminum alkyl can react with certain polymer additives to produce poorly colored products. Mg:Al (0.5:1 to 10:1) At a Mg:Al ratio of 0.5:1, the amount of aluminum in the total catalyst formulation is relatively high and aluminum alkyl is wasted. Also, high residual levels of aluminum alkyls can react with some polymer additives to produce poorly colored products.At a Mg:Al ratio of 10:1, the catalyst produces polymer The process reaches a point where it becomes inefficient or no polymer can be produced at all. Mg:X (0.2:1 to 0.7:1) Outside the specific range, the catalyst efficiency decreases significantly. The aforementioned catalytic reaction products are preferably carried out in the presence of a non-effect diluent. The concentration of the catalyst components is desirably such that the resulting slurry is between 0.005 and 0.1 moles (mol/) of magnesium when the three major components of the catalytic reaction product are combined. Suitable non-effect diluents are, for example, liquefied ethane, propane, isobutane, n-butane,
n-hexane, various isomeric hexane, isooctane, paraffinic mixtures of alkanes with 8-9 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, industrial solvents such as kerosene, naphtha, etc. It includes saturated or aromatic hydrocarbons, especially those free of any olefinic compounds and other impurities, and especially those with a boiling point in the range -50° to 200°C. Also included as suitable non-effect diluents are, for example, benzene, toluene, ethylbenzene, cumene and decalin. Mixing of the catalyst components to give the desired catalytic reaction product is carried out at -100° to 200°C under a non-toxic atmosphere such as nitrogen, argon or other non-toxic gas.
It is conveniently carried out at temperatures preferably in the range 0° to 100°C. Mixing time is not believed to be critical as sufficient catalyst composition has been found to occur most often within about 1 minute or less. In preparing the catalytic reaction product, it is not necessary to separate the hydrocarbon-soluble components from the hydrocarbon-insoluble components of the reaction product. Polymerization is carried out by adding a catalytic amount of the catalyst composition to the polymerization zone containing the alpha-olefin monomer, or vice versa. The polymerization zone is 0° to 300°C, preferably solution polymerization temperature, e.g.
Temperatures ranging from 130 DEG to 250 DEG C. are maintained for residence times of about 1 minute to several days, preferably 15 minutes to 2 hours. It is generally desirable to carry out the polymerization in the absence of moisture and oxygen and the catalytic amount of catalytic reaction product is generally in the range of 0.0001 to 0.1 mmol titanium per diluent. The most convenient catalyst concentration will depend on the polymerization conditions such as temperature, pressure, solvent and the presence of catalyst poisons and the range mentioned above will be in order to obtain the highest catalyst yield by weight of polymer per unit weight of titanium. Given. In the polymerization process, carriers utilizing inert organic diluents or solvents or excess monomer are generally used.
To realize the maximum benefits of the high efficiency catalysts of this invention, care must be taken to avoid oversaturation of the solvent with the polymer. If such saturation occurs before catalyst depletion, full efficiency of the catalyst is not achieved. For best results, the amount of polymer in the carrier should be 50% based on the total weight of the reaction mixture.
It is desirable that the weight percentage does not increase. The polymerization pressure is preferably a relatively low pressure, e.g. 50-1000 psig (3.5-70 Kg/ ^cm2 gauge), especially
Use 100-600 psig (7-42 Kg/cm ² gauge).
However, polymerizations within the scope of the present invention can be carried out at atmospheric pressure up to a pressure determined by the capacity of the polymerization apparatus. During the polymerization, it is desirable to stir the polymerization mixture to obtain better temperature control and maintain a homogeneous polymerization mixture and total polymerization zone. In order to optimize the yield of ethylene polymerization, it is desirable to maintain the ethylene concentration in the solvent in the range 1 to 10% by weight, most advantageously 1.2 to 2% by weight.
To achieve this, if excess ethylene is fed into the system, some of the ethylene may be discharged. Hydrogen is often used in the practice of this invention to reduce the molecular weight of the resulting polymer. It is advantageous to use hydrogen in concentrations ranging from 0.001 to 1 mol per mol of monomer. It has been found that amounts of hydrogen greater than within this range generally result in lower molecular weight polymers. Hydrogen can be added to the polymerization vessel with the monomer stream or separately to the polymerization vessel before, during, or after adding the monomer to the polymerization vessel, but during or before addition of the catalyst. The monomer or monomer mixture is contacted with the catalytic reaction product by any conventional method, but preferably the catalytic reaction mixture and monomer are brought together by intimate agitation provided by suitable stirring or other means. bring into contact. Stirring can be continued during the polymerization, or in some cases it can be left off while the polymerization is occurring.
In the case of more rapid reactions with more active catalysts, means can be provided for refluxing the monomer and solvent, if the latter is present at all, and thus removing the heat of reaction. In any event, suitable means should be provided to dissipate the heat generated by polymerization. If desired, the monomer can be contacted with the catalytic reactant in the vapor phase in the presence or absence of a liquid material. The polymerization can be carried out batchwise or continuously, for example by passing the reaction mixture through a stretched reaction tube in external contact with a suitable coolant to maintain the desired reaction temperature, or by equilibrium effluent. It can be carried out by passing the reaction mixture through a type reactor or a series thereof. The polymer is easily recovered from the polymerization mixture by driving off unreacted monomer and any solvent used. There is no need to remove any further impurities. Thus, a significant advantage of the present invention lies in the omission of the catalyst residue removal step. However, in some cases it may be desirable to add small amounts of catalyst quenchers of the type commonly used for the quenching of Ziegler catalysts. The resulting polymer was found to contain insignificant amounts of catalyst residue and to have a very narrow molecular weight distribution. The following examples further illustrate the invention. All parts and percentages are by weight unless otherwise noted. In the following examples, the catalyst preparation is carried out in a 120 ml serum bottle filled with nitrogen in the absence of oxygen or water. The catalyst components are used as dilute solutions in n-heptane or Isopar E (a mixture of saturated isoparaffins having 8 to 9 carbon atoms). The polymerization reactions are carried out at 150° C. in a No. 5 stainless steel stirred batch reactor unless otherwise specified. In such a polymerization reaction, two portions of dry, oxygen-free Isopal E are added to the reactor and heated to 150°C.
The reactor was degassed to approximately 25 psig (1.75 Kg/cm ² gauge) and 15-20 psi (1.05-20 psig) for molecular weight control.
Add 1.4Kg/cm ² ) of hydrogen. Then 120psi (8.4
Kg/cm ² ) of ethylene is added to the reactor and the ethylene pressure is adjusted to maintain the reactor pressure at 160 psig (11.2 Kg/cm ² gauge). The catalyst is then forced into the reactor using nitrogen and the temperature of the reactor is maintained for the desired reaction time. The contents of the polymerization reactor are discharged all at once into a stainless steel beaker and cooled.
The resulting slurry is drained and the polymer is dried and weighed. Ethylene consumption during polymerization is recorded in a DP cell, which indicates the rate of polymerization and the amount of polymer produced. Catalyst efficiency is 1g of titanium
The number of grams of polyethylene per unit, i.e. g. PE/g.
Report in Ti. In addition, α-TiCl ₃ used in the examples is
Commercially available from Stauffer Chemical, and a series of dibutylmagnesium triethylaluminum complexes are available from Taxas Alkyls or
Commercially available from Ethyl Corporation. Example 1 0.43 ml of Isopar E with stirring
A catalyst is prepared by adding 0.688M di(n-butylmagnesium.1/6 triethylaluminum to 48.5 ml of Isopar E. 0.66 ml of titanium complex is added to this solution, which is equal to the Ti in Isopar E.
The standard is 0.0076M. This complex is prepared by heating 20 g of α-TiCl ₃ in 800 ml of isopropanol at a temperature of 80° C. until a bright blue solution is formed.
The resulting slurry was dissolved in cyclohexane.
Add 0.41 ml of 0.92M ethylaluminum dichloride. A quantity of 10 ml (0.0010 mmol Ti) of the obtained reaction product is added to the polymerization reactor. After 37 minutes, 248 g of linear polyethylene was formed, giving a catalyst efficiency of 5.7×10 ⁶ g. PE/g. Give Ti. Example 2 A catalyst is prepared by adding 81.61 ml of Isopal E and 1.49 ml of 0.516M di(n-butyl)magnesium/2-triethylaluminum in Isopal E to a serum bottle. To the resulting solution was added, in order, 1.9 ml of the slurry of the titanium complex described in Example 1;
This is 0.0081M for Ti in Isopal E, and 0.113M for 15 ml in Isopal E.
Add HCl. 10ml (0.0015 mmol) of this catalyst
Add Ti) to the polymerization reactor and collect the reactor contents after 30 minutes. The yield of polymer was 158 g, and the catalyst efficiency was 2.2×10 ⁶ g. PE/g. Indicates Ti. Example 3 Several catalysts are made and polymerization experiments are performed according to the general operating procedure described in the preamble. Unless otherwise specified, the total catalyst concentration in the polymerization reactor is 0.001 mmol based on Ti and the polymerization temperature is 150°C.
It is. The catalysts and results of these polymerization experiments are reported in the following table.

【table】

[Table] Example 4 Polymerization experiments were carried out generally according to the general operating procedure using a catalyst prepared according to Example 1 and having an atomic ratio of Mg/Ti/Al of 60/1/75, but with the following: The only difference is that the quantity is changed in place of the solvent, 1,7-octadiene is substituted, and in the absence of hydrogen, 150 psig (10.5 Kg/cm ² gauge) of ethylene is used. Octadiene in 2 solvents from 0.1 to 20.0ml
, the catalyst efficiency is 2.32 per gram of Ti.
×10 ⁶ to 0.38 × 10 ⁶ polymer. Increasing octadiene also broadens the molecular weight distribution of the polymer and improves the environmental stress cracking resistance of the polymer. Example 5 Polymerization experiments are carried out according to the general operating procedure, again using the catalyst prepared according to Example 1, with the exception that
The difference is that 45 g of butene-1 is used in Isopar E. The catalyst (component corresponding to 0.0045 mmol of Ti) is added to the reaction vessel and after 33 minutes 303 g of polymer are obtained, representing a catalytic efficiency of 1.4×10 ⁶ g of polymer per gram of Ti. The polymer has a very narrow molecular weight distribution and low peak molecular weight. If the polymerization temperature is lowered to 80° C., a polymer with a broad molecular weight distribution and high molecular weight is obtained and the recovered polymer exhibits rubbery properties. Example 6 Polymerization experiments are carried out using the catalyst prepared as in Example 1 and according to the general operating procedure, with the exception that
The difference is that 100 psig (7 Kg/cm ² gauge) of propylene is introduced into the reactor followed by 200 psig (14 Kg/cm ² gauge) of ethylene and the polymerization is carried out at 75°C. After 50 minutes, 188 g of rubbery ethylene/propylene copolymer was obtained, representing a catalyst efficiency of 0.44×10 ⁶ g copolymer per gram of Ti. If the propylene pressure is reduced to 120 psig (8.4 g/cm ² gauge), the ethylene pressure will be
162 psig (11.34 Kg/cm ² gauge) and the polymerization was carried out at 100°C, the catalyst efficiency was
^The resulting copolymer is extremely tough and has good transparency. Example 7 Polymerization experiments are carried out using the catalyst prepared as in Example 1 and according to the general operating procedure, except that 50 ml of 1-hexene is introduced into the reactor followed by 160 psig of ethylene and the polymerization is carried out using the catalyst prepared as in Example 1. The difference is that it is carried out at 150℃. After 30 minutes, 165 g of ethylene/1-hexene copolymer were obtained, which means a catalyst efficiency of 1.5×10 ⁶ g copolymer per gram of Ti. Example 8 Polymerization experiments are carried out using the catalyst prepared as in Example 1 and according to the general operating procedure, except that 50 ml of 1-octene is introduced into the reactor followed by 160 psig of ethylene and the polymerization is carried out using the catalyst prepared as in Example 1. The difference is that it is carried out at 150℃. After 30 minutes, 150 g of ethylene/1-octene copolymer were obtained, which means a catalyst efficiency of 1.4×10 ⁶ copolymer per gram of Ti. Example 9 A catalyst was made as follows. Isopal E medium
Gaseous hydrogen chloride was added to a 0.20M dibutylmagnesium solution until the Cl:Mg ratio was 2. 3.0ml of this mixture and 45ml of Isopal E
To this, 0.045 mm of titanium complex in the solvent was added. The Ti complex in this example contains 12 g of α-
It was prepared by heating TiCl ₃ and 19 ml of n-hexanol in 180 ml of solvent to a temperature of 120° C. until all the solids were dissolved. To the resulting blue-green slurry was added 0.12 ml of a 0.15M solution of triethylaluminum in solvent. The Mg/Ti/Al ratio of this catalyst was 40/3/12. A 10 ml quantity (0.009 mmM Ti) of the resulting reaction product was added to the polymerization reactor according to the general operating procedure. However, the ethylene pressure was 370 psig and the polymerization temperature was set at 195°C. After 20 minutes, 240
g of polyethylene was obtained, which means a catalyst efficiency of 0.55×10 ⁶ g per gram of Ti. Example 10 A polymerization experiment is carried out according to Example 9, except that Ti
The complex was mixed with α-TiCl ₃ and 20 ml of n in Isopar E.
- differs in that it is made from decanol. After 20 minutes, an amount of 252 g of ethylene polymer was obtained, which means a catalyst efficiency of 0.58×10 ⁶ g polymer per 1 g of Ti. Example 11 A catalyst is prepared in the same manner as in Example 9, but
However, the difference is that the Ti complex is derived from α-TiCl ₃ and n-octanol. A catalyst slurry containing HCl, dibutylmagnesium, and titanium-octanol complex was prepared using 0.6 ml of a 0.15 M solution of ethylaluminum dichloride in Isopal E.
and a 0.15M solution of triethylaluminum 1.8
React with ml.

[Brief explanation of the drawing]

FIG. 1 is a flow chart showing one method for producing the catalyst of the present invention.

Claims (1)

[Claims] 1 (A) Empirical formula TiCl ₃ (L) _x (wherein L is a carbon atom 2
~10 aliphatic alcohols, and x
is an integer from 1 to 6), and (B) (1) an organomagnesium compound or (2) an organomagnesium compound and an amount sufficient to solubilize the organomagnesium compound in a hydrocarbon. An organomagnesium component selected from a complex with an organometallic compound [provided that the organomagnesium compound and the complex have the formula MgR″ ₂ ,
and of the formula MgR″ ₂ ·mAlR ₃ ·nZn ² ′′′′ ₂ , where R″, R, and R′′″ are individually alkyl of 1 to 4 carbon atoms, and m is 0.001 to 10, and n is 0, or both m and n are not 0, and m+n
is 0.001 to 10)] and (C) (1) of the formula R'X, where R' is hydrogen or alkyl, and X is a halogen; provided that the unstable halogen is at least as active as the halogen of sec-butyl chloride) or (2)
Catalytic reaction formation with a halide source selected from metal halides having the formula AlR _3-a X _a , where R is alkyl, X is halogen, and a is a number from 1 to 3. wherein the proportion of said components in the catalytic reaction product is such that the atomic ratio of Mg:Ti is from 1:1 to 80:1, and (B), (C), or a mixture thereof The atomic ratio of Al:Ti is 1:1 to 200:1, and the atomic ratio of Mg:X is 0.2:1 to 200:1.
Catalytic reaction product provided that the ratio is 0.7:1. 2. Claim 1, wherein the organomagnesium component is a complex of dialkylmagnesium and trialkylaluminum, and the atomic ratio of Mg:Al in the organomagnesium component is in the range of 0.5:1 to 10:1. Products as described. 3. The atomic ratio of Mg:Ti is between 20:1 and 80:1, the atomic ratio of Mg:X is between 0.2:1 and 0.7:1, and for the total catalytic reaction products
3. A product according to claim 2, wherein the atomic ratio of Mg:Al is between 0.5:1 and 10:1. 4. The atomic ratio of Mg:Ti is from 10:1 to 80:1, the atomic ratio of Mg:X is from 0.4:1 to 0.6:1, and the Mg:Al in the total catalytic reaction product is
A product according to claim 1, wherein the atomic ratio of is from 0.5:1 to 10:1. 5 L is an aliphatic alcohol of 3 to 6 carbon atoms, the active nonmetal halide is hydrogen chloride or tertiary alkyl chloride, and the metal halide is an alkyl aluminum chloride. The product described in. 6 L is isopropyl alcohol and x is 2
-4 and R'' is butyl.