JPH0380798B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to intermetallic compounds of transition metal alkoxides and methods for producing the same. More particularly, the present invention provides catalyst precursors for interreacting with halide activators to provide catalyst components suitable for alpha-olefin polymerization. Polyethylene, produced by solution or slurry processes at low pressure or in autoclaves or tubular reactors at high pressure, has been the subject of commercial production for many years. Recent interest has focused on the linearity and short side chains afforded by alkene comonomers, characterized by the narrow molecular weight distribution, improved strength properties,
High melt viscosity, high softening point, improved ESCR
The focus has been on linear low-density polyethylene resins, which offer (environmental stress cracking resistance) and improved low-temperature brittleness. These and related properties provide advantages to users in applications such as blown films, wire and cable coatings, cast films, coextrusion, and injection and rotational molding. The linear olefin polymers were prepared using catalysts of the general type disclosed by Ziegler, i.e. catalysts consisting of a transition metal compound (usually a titanium halide) mixed with an organometallic compound (e.g. an alkyl aluminum). It has been produced representatively. The transition metal component can be activated by reaction with a halogenated promoter, such as an alkyl aluminum halide. Some improved catalysts of this type incorporate a magnesium component, usually by interreacting the magnesium or its compound with a transition metal component or an organometallic component, e.g. by milling or by chemical reaction or Manufactured by coalescence. There is also interest in using this type of coordination catalyst to produce medium to high density resins with modified properties. In particular, resins with broad molecular weight distribution and high melt index are desired. The present invention involves reacting an alkoxide of a transition metal selected from the group consisting of titanium and zirconium with a hydrate of a salt of aluminum, cobalt, iron, magnesium, or nickel to produce an alkoxide of a multimeric transition metal oxide. Magnesium,
A method for producing an intermetallic compound, which comprises contacting the intermetallic compound with a reducing metal selected from the group consisting of calcium, zinc, aluminum, and mixtures thereof. In the present invention, the intermetallic compound is a compound containing a transition metal and a reducing metal, that is, a metal with reducing power in one molecule, and is useful as a precursor of an olefin polymerization catalyst. A multimeric transition metal oxide alkoxide (hereinafter referred to as a polymerized transition metal oxide alkoxide) is one in which two or more transition metal atoms are multimolecularly bonded via an oxygen atom and has an alkoxide group. This reaction product can be activated to serve as an olefin polymerization catalyst component. Polymeric transition metal oxide alkoxides can be prepared separately by controlled hydrolysis of the alkoxides, and polymeric oxoalkoxides can be prepared by in situ reaction, e.g., by hydrolysis in a reaction medium containing a reducing metal. It can be obtained by For example, titanium or zirconium tetrabutoxide can be reacted with magnesium metal in a hydrocarbon solvent and in the presence of a controlled source of water, preferably a hydrated metal salt (e.g., magnesium halide-hexahydrate). . Transition metal alkoxides, especially titanium alkoxides, are known for their binding properties in organic solvents and their sensitivity to hydrolysis. It has been reported that hydrolysis reactions proceeding from oligomeric, usually trimeric, titanium alkoxides generally produce polymeric titanium oxide alkoxides of the formula: Ti(OR) ₄ +nH ₂ O→TiOn(OR) _4-2o +2nROH Particularly at elevated temperatures, a condensation reaction also occurs, resulting in the following structure containing a first-order metal-oxygen-metal bridge. . This then takes part in or constitutes a precursor for the hydrolysis reaction. These polymerized titanium alkoxides or oxoalkoxides (sometimes referred to as u-oxoalkoxides) can be represented by the following formula. [Ti _3(x+1) O _4x (OR) _4(x+3) ] In the formula, x=0, 1, 2, 3,... This structure reflects the coordination expansion of the metal beyond its primary valence combined with the alkoxide's ability to bridge two or more metal atoms. Irrespective of the particular form that the alkoxide is expected to take, in reality, oligomers of the alkoxide undergo a cyclic form upon controlled hydrolysis, from a dimer to a linear chain up to infinite chain length. It is sufficient to recognize that a series of polymeric oxide alkoxides are formed ranging from polymers to polymers. On the other hand, more complete hydrolysis results in the precipitation of insoluble products, and ultimately complete hydrolysis produces orthotitanic acid. For ease of description, these materials will be referred to as polymeric oxide alkoxides of the respective transition metals representing partial hydrolysis products. The hydrolysis reaction can be carried out separately and the product can be separated and stored for later use. However,
This is particularly inconvenient from the point of view of further hydrolysis. Therefore, the preferred practice is to generate these substances in the reaction medium. The same hydrolysis reaction was demonstrated to occur in situ. The hydrolysis reaction itself can be controlled by the amount of water fed to the transition metal alkoxide and the rate of its addition. Water must be supplied incrementally or in stages or continuously. Bulk addition will not produce the desired reaction and will cause excessive hydrolysis and insoluble precipitate. Although dropwise addition is suitable for the use of reaction water, it may be more convenient to provide the reaction water as water of crystallization (sometimes referred to as cationic, anionic, lattice or zeolitic water). I understand. Thus, conventional hydrated gold salts are commonly used when the presence of the salt itself is not detrimental to the system. Either the binding provided by the coordination regions of water in the hydrated salt is suitable for controlling the release and/or availability of water, or water-related substances to the system necessary to carry out the reaction participate in this reaction. or control this reaction. The total amount of water used, as mentioned above, has a direct relationship to the form of the polymerized oxide alkoxide produced, and therefore the amount is selected in relation to catalyst performance. (It is believed without limitation that the configuration of the partially hydrolyzed transition metal alkoxide partially determines or contributes to the catalytic nature or outcome of the activated catalyst component.) In general, the transition It has been found that a small amount of water, on the order of 0.5 mole per mole of metal, is sufficient. Quantities of up to 1.5 mol are suitable, and quantities as high as 20 mol can be operated as long as precipitation of the hydrolysis product from the hydrocarbon solvent medium is avoided. This is generally accomplished by reducing the addition rate and stopping the addition as soon as precipitation occurs. Although this reaction is believed to be substantially equimolar, it is appropriate to use a small excess of water if, as is customary, there is a slight excess of water. The stereoisomer, chain length, etc. of the hydrolyzed product may change slightly due to the elevated temperature required for the subsequent reaction with the reducing metal, and similarly, in the in situ method, due to the effect of mass action. It will be understood that this will affect the equilibrium. Similarly, alkanol by-products also affect equilibrium, reaction rate, etc. This hydrolysis reaction proceeds under ambient pressure and temperature conditions and does not require special conditions. Hydrocarbon solvents can be used, but are not required. these substances for a period of time, usually
Simply contacting for 10-30 minutes up to 2 hours is sufficient. The resulting material is stable under normal storage conditions and can be brought to the appropriate desired concentration simply by dilution with a hydrocarbon solvent. This polymerized transition metal oxide alkoxide is reacted with a reducing metal having a higher oxidation potential than the transition metal. Preferably polymerized titanium oxide alkoxides are used together with magnesium, calcium, potassium, aluminum or zinc as reducing metals. Combinations of transition metal alkoxides, reducing metals, and hydrated metal salts are usefully selected with reference to potentials that minimize side reactions, as is known in the art; and are generally selected with reference to potentials that minimize side reactions; To ensure favorable activity levels, magnesium values are fed into the system by appropriate selection of reducing metal/hydrated metal salts. In a preferred embodiment (the following is labeled with explanatory numerals for convenience), titanium-tetra-n
- Reacting butoxide (TBT) with magnesium shavings and a hydrated metal salt (most preferably magnesium chloride hexahydrate) in a reaction vessel at autogenous pressure at a temperature of 50-150<0>C. Although TBT may constitute the reaction medium, hydrocarbon solvents may also be used. The Ti/Mg molar ratio can vary between 1:0.1 and 1:1, but for the most homogeneous reaction system it should be 1:1.
A stoichiometric relationship of Ti:Mg° is preferred, and the amount of hydrated metal salt fed during the reaction is preferably about 1 mole of water per mole of Mg°. This hydrocarbon soluble catalyst precursor contains Ti in combination with Mg values in one or more configurational complexes believed to constitute primarily the oxygenated species.
It mainly consists of valuables. There is some evidence of mixed oxidation states of titanium values, possibly in a pseudo-equilibrium relationship, at least under dynamic reaction conditions.
This suggests a correlation between the constituent species of Ti〓, Ti〓, and Ti〓. Preferred precursors include without limitation (Ti
-o-Mg) bridge structure. The intermetallic compound is produced in the presence or absence of a reducing agent or activator, such as an organometallic compound of a Group A, Group A, Group A or Group B metal, in a supported or unsupported system. It is of particular interest as a catalyst precursor for the isomerization, dimerization, oligomerization or polymerization of alkenes, alkynes or substituted alkenes in the presence of In a preferred use of such precursors, these precursors are reacted with chloride activators such as alkyl aluminum halides and, in combination with organometallic compounds, are particularly suitable for the production of polyethylene by polymerization of ethylene and comonomers. Catalyst system. The transition metal component is an alkoxide, usually with a substantial -OR substituent, R containing up to 10 carbon atoms, preferably 2 to 5 carbon atoms;
most preferably a titanium or zirconium alkoxide (n-alkyl such as n-butyl). The selected components are normally liquid under ambient conditions and convenient reaction temperatures, and are also hydrocarbon soluble for ease of use. Although it is preferred to use transition metal compounds containing only alkoxide substituents to facilitate the associated hydrolysis reactions, the substituents do not interfere with the reaction in the sense of significantly modifying the performance in use. It can also be intended. Generally, chloride-free n-alkoxys are used. In particular, the transition metal component is provided in its highest oxidation state to provide the desired conformational structure. Most suitably, as mentioned above, the alkoxide is a titanium or zirconium alkoxide. Suitable titanium compounds include titanium tetraethoxide; as well as n-propoxy, isopropoxy, n-butoxy, isobutoxy,
-class butoxy, tertiary butoxy, n-pentoxy,
There are related compounds that contain one or more alkoxy groups, including tertiary pentoxy, tertiary amyloxy, n-hexyloxy, n-heptyloxy, nonyloxy, and the like. Some evidence suggests that the rate of hydrolysis of these normal derivatives decreases with increasing chain length, and that the rate of hydrolysis depends on the complexity of the molecule, i.e., tertiary, secondary, etc.
This suggests that it decreases as the number increases to normal. These considerations can therefore be taken into account in selecting preferred derivatives.
In general, titanium tetrabutoxide has been found to be excellent in carrying out the invention, and related tetraalkoxides are preferred as well. It will be appreciated that mixed alkoxides are perfectly suitable and may be used where conveniently available. Multiple titanium alkoxides sometimes containing other metal components can also be used. The reducing metal is provided as a necessary component of the reaction system at least partially in the zero oxidation state. Convenient resources are shavings, ribbons or powder. As commercially supplied, these materials are in a state of passivated surface oxidation, and grinding or polishing to provide at least some fresh surface is preferred, at least to control the reaction rate. The reducible metal may conveniently be provided in the form of a slurry in the transition metal component and/or hydrocarbon diluent, or it may be added directly to the reactor. In the case of in-situ production (or also in the case of independent production of polymeric transition metal alkoxides):
A water source or water-related species is provided so that the required amount of water is released or diffused or made available during the reaction in a slow and controlled manner, as the case may be. As mentioned above, the coordination region provided by the hydrated metal salt has been found to be suitable for this purpose, but other water sources in the same proportions can also be used. Thus, calcined silica gels without other active ingredients but containing controlled amounts of bound water may also be used. Generally, preferred water sources are hydrous complexes in which water is coordinated to a substrate material in a well-known manner. Suitable materials include hydrated metal salts, especially inorganic salts such as chlorides, nitrates, sulfates, carbonates, carboxylates of aluminum, nickel, cobalt, iron, magnesium. The interaction of these components is conveniently carried out in a closed reactor, preferably in combination with a reflux function for the heated volatile components produced in the reactor. Autogenous pressure is used because the reaction proceeds smoothly under ambient conditions by heating to initiate and hold the reaction. In such reactions, stirring is preferred only to prevent caking or coating of the surfaces of the reaction vessel, to provide intimate mixing of the components, and to maintain a homogeneous reaction system. Hydrocarbon solvents such as hexane, heptane, octane, decalin, mineral spirits, etc. are also commonly used to facilitate intermixing of the components, heat transfer, and maintenance of a homogeneous reaction system. Saturated hydrocarbons with a boiling point in the range 60-190°C are preferred. Liquid transition metal components may also serve, at least in part, as reaction media. This is especially true if no solvent addition is carried out. The reaction may include a step in which the additional volatile components form an azeotrope with the solvent or, when the components are used neat (without solvent), the additional volatile components may be added to the reflux source. However, in each case it is preferred that the reaction be carried out over a suitable reaction time, with at least an intermediate step of returning volatile materials to the reaction zone. Thus, when the titanium component is titanium-tetra n-butoxide, butanol is generated and forms an azeotrope with the hydrocarbon solvent.
The choice of solvent and/or alkoxide with respect to the possible reduction of the reaction temperature is therefore a consideration well known by those skilled in the art. The reaction temperature is a matter of choice within a wide range depending on the rate of reaction to be conveniently carried out. The reaction system (composed of liquid transition metal components, dissolved hydrated metal salts, reducible metal particles, and, if desired, solvent) was observed to demonstrate visible gas evolution at approximately 60-70°C. Served. This is about
It is suggested that the onset temperature or activation energy at 50° C. and that this temperature therefore constitutes the required minimum temperature of the polymeric oxide alkoxide and the reducing metal. This reaction is exothermic during the consumption of the reducing metal and therefore can be easily transferred to the next step at reflux temperature. Since the alkanol generated is consumed in large quantities (as a separate species) in the course of the continued reaction, the temperature of the actual reaction system will vary, and the completion of the reaction will be delayed by visible metal consumption and/or by 30 to 4 minutes. This is confirmed by the attainment of the reflux temperature of the pure solvent within a time of the order of hours or more. Such temperatures can reach 140-190°C. Higher temperatures than this can of course be used, but there is no particular advantage. 50-150℃ preferably 70
It is most convenient to operate in the range ~140°C.
In the absence of a solvent, the upper limit is simply established by the reflux temperature of the alkanol generated during the reaction. The reaction of the components is most clearly seen from the exothermic, noticeable color change accompanied by the onset of gas evolution. When observation shows that the solution is not opaque or turbid, the evolution of gases ranging from bubbling to violent boiling is most pronounced at the surface of the metal, and the generally light-colored solution immediately turns gray; It then rapidly darkens to a blue, sometimes purple, usually blue-black color with green tones. Gas analysis shows no HCI and essentially _H2 . After the rapid color change, a slight deepening of the color occurs during a period of gradual temperature rise with continued gas evolution. It can be seen that at this stage the alkanol corresponding to the alkoxide species is generated in an amount sufficient to lower the boiling point of the solvent and is gradually consumed in a rate-related manner along with the remaining reducing metal. The reaction products are at least partially hydrocarbon soluble and are retained in slurry form for convenient subsequent use. The separated viscous to semisolid product exhibits essentially amorphous character by X-ray diffraction analysis. The molar ratios of the components can be varied within a range without significantly adversely affecting the performance of the catalyst precursor in the end use. That is, in order to avoid competing reactions that would make the reaction products undesirably gelatinous or difficult to handle, the transition metal component is usually provided in at least a molar ratio to the reducing metal; The metal ratio is approx.
It may range from 0.5:1.0 to 3.0:1.0 or more, preferably from 1/0.1 to 1/1. An insufficient amount of reducing metal will cause the reaction temperature to drop so that the reflux temperature of the pure solvent is not reached, and excess reducing metal will be immediately recognized from its unconsumed portion. The desired amount of this component is therefore readily ascertainable by one skilled in the art. Within these ranges, a proportion of the reaction products constitute the hydrocarbon-insoluble component, which, upon use,
For example, it can be, and usually is, slurried with soluble components for further reaction with a halide activator to form a catalyst for olefin polymerization. The amount of such insoluble components can be controlled in part by the use of solvents with appropriate partition coefficients, although the use of common hydrocarbon solvents such as octane may be preferred for practical reasons. found that equimolar ratios of eg Ti/Mg/H ₂ O components are most suitable for the formation of homogeneous reaction products. Water or a water-related species is also preferably provided in a molar ratio to the transition metal component for similar reasons of uniformity and ease of reaction. i.e.
In the case of MgCl ₂ 6H ₂ O, an amount of 0.17 mol provides about 1 mol of water during the reaction, and this ratio up to about 2 mol of water is the easiest with 1 mol or more of the transition metal component. Give a reaction. More generally, the _H2O may range from about 0.66 to 3 moles per mole of transition metal. The amount of water present at any stage of the reaction is likely to be quite low over the catalytic proportions to the remaining components, depending on the manner and proportions in which it participates in the currently unknown reaction equation. Nevertheless, the following operational assumptions are intended without limitation: That is, water or rate-controlling water-related species are activated, released, approached or diffused in a manner that provides such species in a regular, continuous, constant or variable rate-related manner. That's true. However, the same molar proportion of free water supplied at the beginning of the reaction has no effect at this temperature or higher in driving the reaction, resulting in undesirable complete hydrolysis. The measured amount of water appears to be in substantial molar balance or molar excess to the reducing metal and related to its consumption in the reaction. This is because a molar deficiency of water has the permanent result of an excess of reducing metal remaining. Generally, 10
A modest water excess of ~40% is suitable to ensure complete reaction. Higher proportions are also suitable without restriction, but it should be kept in stoichiometric balance relative to the transition metal component. The choice of the hydrated complex or hydrated metal salt used is essentially a matter of the controlled water availability it provides to the system. Sodium acetate trihydrate is thus suitable, as are magnesium acetate tetrahydrate, magnesium sulphate heptahydrate and magnesium fluoride silicon hexahydrate. Salts with a maximum degree of hydration consistent with the controlled release afforded by coordination relationships are preferred. Most conveniently, hydrated magnesium halides are used, such as magnesium chloride hexahydrate or magnesium bromide hexahydrate. These salts, like other hygroscopic substances, absorb some water, for example 17 mg/Kg, even when supplied in commercial anhydrous form (see GB 1401708). However, this is much lower than the molar amount contemplated by the present invention.
Therefore, unless specifically modified to suit the purpose,
Anhydrous grade salt is not suitable here. The reaction systems described above do not require, but cannot tolerate, electron donors or Lewis bases, or solvents that partially perform such functions. As shown later in the Examples, this reaction is carried out in a preferred embodiment in which water of crystallization is present and an alcohol component is present in the system. Therefore, it is not known for sure whether proton carrier or electron donor mechanisms participate or compete in this reaction system. Separation is not necessary. at least a portion of the reaction product is soluble in the saturated hydrocarbon used as a solvent or otherwise provides a solvation medium;
Even if precipitation occurs and even after storage,
This is because a reactive slurry that can be manipulated is easily formed. In a preferred aspect of the invention, the reaction product (catalyst precursor) is further interreacted with a halide activator (eg, an alkyl aluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide, or an alkyl boron halide). This catalyst precursor is easily activated by simply combining the product with a chloride activator. Since this reaction is highly exothermic, the chloride activator is typically added slowly to the reaction system. Usually, upon completion of the addition, the reaction is also complete and terminated. The solid reaction product or slurry can then be used immediately or can be stored for later use. Usually, for the best control of the molecular weight properties and especially for the production of low density resins, only solid reaction products washed with hydrocarbons are used as catalysts. The chloride activator is usually supplied to the interaction in a molar ratio of 3:1 to 6:1 (molar ratio of aluminum, silicon or boron to transition metal);
Ratios of 2:1 or higher have also been used successfully. The resulting catalyst product can be used directly in the polymerization reaction, but is typically diluted, bulked up or weakened as necessary to achieve a nominal productivity of greater than 200,000 g polymer/g transition metal in continuous polymerizations (in accordance with the present invention). catalysts usually exceed this) from 80 to
Catalyst amounts corresponding to 100 mg/transition metal are provided in a convenient feed. Adjustments are made by the operator to reflect reactivity and efficiency, usually by simple dilution and feed rate control. Transition metal-containing catalysts are used for polymerization in combination with organometallic cocatalysts such as triethylaluminum or triisobutylaluminum or nonmetallic compounds such as triethylborane. A typical polymerization reactor feed is 42 parts isobutane solvent, 25 parts
parts ethylene, 0.0002 parts catalyst (calculated as Ti)
and 0.009 part cocatalyst (TEA; calculated as Al)
and is fed to a reactor maintained at 650 psig and 160 psig. The amount of cocatalyst used is approximately 30 to 30% calculated as Al or B based on isobutane.
It is calculated to be in the range of 50ppm. Examples of metal cocatalysts include trialkylaluminums such as triethylaluminum, triisobutylaluminum, tri-n-octylaluminium; alkylaluminum halides; alkylaluminum alkoxides; dialkylzinc; dialkylmagnesium; borohydrides of sodium, lithium and potassium; and borohydrides of magnesium, beryllium and aluminum).
Nonmetallic cocatalysts include boron alkyls such as triethylborane, triisobutylborane and trimethylborane; and hydrides or borons such as diborane, pentaborane, hexaborane and decaborane. The polymerization reactor is preferably a ring reactor suitable for slurry operation using a solvent such as isobutane from which the polymer is separated as a particulate solid. The polymerization reaction optionally uses hydrogen to control the molecular weight distribution and is performed at low pressure e.g.
Perform at 200-1000 psig and a temperature of 100-200㎓.
Other alkenes can be fed to the reactor in small proportions relative to the ethylene for copolymerization with the ethylene. Typically, butene-1 or its mixture with hexene-1 is used in amounts of 3 to 10 mole percent, although other alpha-olefin monomers and other proportions can readily be used. When using such n-alkenes, resin densities ranging from 0.91 to 0.96 can be obtained. Furthermore, other olefin monomers such as 4-methyl-pentene-1,3-methyl-butene-1,
Isobutylene, 1-heptene, 1-decene or 1-dodecene can be used from as little as 0.2% by weight, especially when monomer mixtures are used. Nevertheless, the polymerization can be carried out, if desired, in autoclaves or tubular reactors at high pressures, e.g.
It can also be run at 20,000 to 40,000 psig. The term intermetallic "compound" or "complex" as used herein refers to intermetallic "compounds" or "complexes" which, by coordination or association, contain one or more inclusion or occlusion compounds, clusters or other interrelated compounds under the applicable conditions. The overall reaction is generally ascertained by a color change and outgassing that probably reflects reduction-oxidation, rearrangement, and association between unconsumed elements of the reaction system. The following examples, incorporating the foregoing description, serve to further illustrate the invention and to illustrate the preparation and use of catalysts according to the invention. All parts are by weight unless otherwise specified. The melt index provides MI and HLMI values for the powder or resin samples described therein.
Measurements were made under conditions E and F of ASTMD-1238-57T, respectively. HLMI/MI or MIR is the melt index ratio, which is a measure of shear sensitivity that reflects molecular weight distribution. Other tests are as indicated therein or as conventionally performed in the relevant art. Example 1 A 6 parts of Ti(OBu) ₄ [TBT] and 4.2 parts of
CrCl ₃ .6H ₂ O was mixed in the reactor. The chromium salt partially dissolved and some heat was generated during stirring. Complete dissolution was achieved by gentle heating to 60-70°C. An additional 3.3 parts of chromium salt was stirred for 20 minutes to dissolve.
A total of 0.3 grams of magnesium shavings was added in small portions to the green solution. This caused intense gas evolution. The cooled reaction product, without excess magnesium (no magnesium was completely visible), was a viscous green liquid soluble in hexane. B In a similar operation, anhydrous chromium chloride was used with titanium alkoxide, but no reaction occurred even when heated above 100° C. for 30 minutes. Zinc powder was added and further heating was performed above 150°C, but no reaction still occurred. Even when magnesium shavings were replaced, no reaction occurred. It was concluded that hydrated salt is a necessary component of the reaction system. Example 2 A TBT (0.121 mol), CrCl ₃ 6H ₂ O (0.015 mol)
and Mg° (0.007 mol) were combined in a stirred reactor with an electric heating mantle. Chromium salt is about 60
Fully dissolved at 85°C, reaction with magnesium shavings was evident from gas evolution at 85°C. Gas generation was intense at 100°C and stopped at 116°C, leaving some Mg behind. After dissolving the remaining Mg, heating was continued until the total reaction time was 1 hour and 45 minutes. The reaction product at room temperature was a dark green liquid and easily dissolved in hexane. B Similarly, 0.116 mol of TBT, 0.029 mol of
A reaction product was prepared with a proportion of CrCl ₃ .6H ₂ O and 0.029 mol Mg. The reaction product, which was muddy green at 118℃, took on a distinct blue color at 120℃ with gas evolution. The reaction ended after 1 hour and 15 minutes when the magnesium disappeared. The reaction product was soluble in hexane. C 0.116 mol TBT, 0.058 mol CrCl ₃ .
The above operation was repeated again with a reaction reagent amount of 6H ₂ O and 0.0145 mol of Mg. The reaction was completed in 115 minutes and yielded a hexane soluble product. D In a further operation, the ratio of reactants was changed again to 0.115 mol TBT, 0.0287 mol _CrCl3 .
6H ₂ O and 0.0144 mol Mg. At 114℃, the obvious muddy green material turned blue on the Mg surface. The reaction product recovered was hexane soluble. E In a similar operation, 0.176 mol TBT,
0.30 mol CrCl ₃ .6H ₂ O and 0.176 mol Mg° were reacted in octane. The transparent green color of the reaction at 70℃ turns into muddy as gas generation increases90
The color darkened to almost black at ℃. The color changes back to green at 119°C, and the reaction ends at 121°C.
Magnesium completely disappeared. reaction product
6.9 wt% Ti, 3.5 wt% Mg, 1.3 wt%
Mg) was a dark olive green liquid and a darker solid (approximately 50/50 volume) that was separated. In a further operation in F octane,
Reactants were provided in the proportions of 0.150 mol TBT, 0.051 mol CrCl ₃ .6H ₂ O and 0.150 mol Mg. The muddy green color again changed to almost black with vigorous boiling, and at 109°C a dark blue-black reaction product (5.7 wt% Ti, 2.9 wt%
Mg, 21 wt% Cr). Example 3 A The reaction product of Example 2 E was placed in a reactor.
It was mixed with isobutylaluminum chloride added dropwise in such a proportion that the Al/Ti molar ratio was 3:1. The green mixture initially turned brownish-purple at 38°C and changed to a reddish-brown appearance at 39°C when the addition of reagents was complete. After stirring for an additional 30 minutes, the reaction was complete and the product was a dark reddish-brown liquid and a dark brown precipitate. B The reaction product of F in Example 2 was similarly reacted with isobutylaluminum chloride (3.1
Al/Ti molar ratio). The peak temperature at the completion of addition is
Although the temperature was 48°C, no change in brown color was evident. The reaction product was a clear liquid and a dark gray precipitate. Example 4 The catalyst produced in Example 3 was used for the polymerization of ethylene (180〓, 10 mol% ethylene, calculated as Ti).
0.0002 part catalyst, approximately 45 ppm triethylaluminum as Al, _H2 as shown in Table 1). The results are shown in Table 1.

TABLE In the following examples, catalyst components of the invention were prepared from reaction mixtures in the absence of added solvent. Example 5 A 0.1212 mol Ti(OBu) ₄ [TBT], 0.121 mol magnesium shavings and 0.0012 mol
MgCl ₂・6H ₂ O (TBT/Mg/MgCl ₂・6H ₂ O=
1:1:0.01 mol) in a stirred reactor with an electric heating mantle. The magnesium salt completely dissolved at room temperature and formed a homogeneous reaction mixture. The mixture was gradually heated and gas evolution started on the surface of the magnesium shavings at 95°C. The foam became viscous at 140°C with reflux. The solution darkens and foams at 170℃.
The reaction stopped at that point. The reaction product contained excess magnesium (only about 8.5% of the charge had reacted) and was soluble in hexane. B In another operation, the molar ratio of MgCl ₂ 6H ₂ O was increased (TBT/Mg/MgCl ₂ 6H ₂ O=
1:1:0.1 mol). The golden liquid turned gray at 104°C with gas evolution and darkened with further heating to 168°C. After a reaction time of 125 minutes, the reaction product contained some excess magnesium and was about 63% reacted. C In a further run, the molar ratio used was 1:1:0.17. The dark blue reaction product was very viscous and could not be easily diluted with hexane. All of the magnesium has been consumed. The following examples demonstrate preparations carried out in hydrocarbon solvents. Example 6 A 50.2 parts (0.148 moles) of TBT were added to a stirred reactor with an electric heating mantle containing 58.6 parts of octane. Magnesium turnings (0.074 mol) were added and stirring started, then 0.0125 mol MgCl ₂ .6H ₂ O was added over 1 minute with heating. At 75 °C (20 min), the magnesium salt completely dissolves, and at 95 °C (25 min) gas evolution begins on the surface of the magnesium shavings, which increases as the solution turns gray and then deep blue; Refluxing was carried out at 117°C (35 minutes). The magnesium metal reacted completely within 1 hour (128-129°C) and the reaction was complete. The dark blue reaction product dissolved in octane (a small amount of green precipitate remains) is 6.8
Contains wt% Ti and 2.8wt% Mg values (Ti/Mg 3.4:1 by weight, 1.7: by mole)
1) was calculated. B The above procedure was substantially repeated except that the molar ratio of the reactants was changed, and the following results were obtained.

【table】

Table C The above Preparation 1/1/0.34 was repeated except that 63.7 parts of TBT was used with 67.5 parts of hexane as the solvent reaction medium. A dark blue-black liquid was obtained, calculated to contain 8.2% Ti and 1.6% by weight.
It was found that it contained % Mg by weight. The following example illustrates the stepwise preparation of the catalyst components. Example 7 2.61 parts of _MgCl2.6H2O and _34.2 parts of TBT were combined by stirring. Within 30 minutes, the yellow liquid-crystalline salt mixture turned into a milky yellow, opaque viscous liquid. With further stirring, the cloudiness disappeared and within 2 hours it became a clear yellow liquid.
In this operation, the salt completely dissolves within 30 minutes without any intervening precipitation or opacity.
yielded a yellow liquid). Clear yellow liquid prepared as above and 1.83 parts
Using Mg゜, various components in octane are 1/0.75/
A TM Mg reaction product was prepared in the same manner as in the previous example, with a molar ratio of 0.128. This reaction proceeded smoothly and yielded a dark blue-black liquid and a green precipitate, similar to the other previously mentioned reactions. This reaction product was activated with ethylaluminum dichloride in an amount to give an Al/Ti ratio of 3/1 to prepare a catalyst component for olefin polymerization. The following example demonstrates the importance of the level of bound water. Example 8 The molar ratio was 1/0.75/0.128 (TBT/Mg/MgCl ₂ .
A series of identical experiments were performed with 6H ₂ O). When using MgCl ₂ 6H ₂ O (MgCl ₂
In the case of 6H ₂ O, H ₂ O/Mg was 1:1 (in this case 0.68/1), and only 89.1% of the magnesium metal reacted. with the same total molar ratio
When using MgCl ₂・2H ₂ O (H ₂ O/Mg=
0.34/1), only 62.1% of Mg° reacted. In a similar operation, the amount of hydrated salt fed was increased to a H ₂ O/Mg ratio of 1/1. All of the magnesium metal reacted. It was also observed that the amount of insoluble reaction products increased with increasing salt concentration. The following examples illustrate the use of other titanium compounds. Example 9 A 45.35 parts (0.1595 mol) Ti(OPr ⁱ ) ₄ , 0.1595
Add moles of Mg° and 50.85 parts of octane to a stirred reaction flask with an electric heating mantle;
Then 0.027 mol MgCl ₂ .6H ₂ O was added. The milky yellow mixture turned gray with reflux at about 88°C and turned blue with gas bubbling at about 90°C.
Based on residual magnesium, it was determined that the reaction was partially inhibited by the presence of the octane/isopropanol azeotrope. B The reaction in A above was repeated using decalin (boiling point 185-189°C) as a diluent and at a reaction reagent molar ratio of 1/0.75/0.128. After 6 hours, the reflux temperature reached 140°C and the reaction was complete. A dark blue-black liquid was obtained with a small amount of dark precipitate.
Only 8.8% of the magnesium was reacted. C Similarly, a reaction using tetraisobutyl titanate was carried out in a molar ratio of 1/0.75/0.128, yielding a blue-black liquid and a dark precipitate. Approximately 50%
of magnesium reacted. D Titanium tetranonylate was similarly used with magnesium and _MgCl2.6H2O in a _molar ratio of 1/0.75/0.128. A blue liquid was produced and 45% of the magnesium was consumed. E The reaction product of titanium tetrachloride and butanol (believed to be dibutoxytitanium dichloride) was mixed with magnesium and magnesium chloride hexahydrate in a molar ratio of 1/0.75/0.128 under conditions similar to those in the above example. I reacted with Approximately 3
Over time, about half of the magnesium is consumed,
There, a dark blue-black liquid and an olive green precipitate (50/50 by volume) were recovered. The following example uses zirconium metal alkoxide. Example 10 A 12.83 parts of Zr(OBu) _4.BuOH (0.028 mol);
0.34 parts of Mg° (0.14 moles) in the form of commercially available shavings; and 8.8 parts of octane were placed in a reactor and heated at 125 °C for 15 minutes with stirring.
The mixture was heated to reflux for a minute, but no reaction occurred. Upon addition of 0.97 parts of MgCl ₂ .6H ₂ O (0.005 mol), vigorous boiling was observed and the reaction mixture took on a milky appearance. B In a second operation, 31.7 parts of the zirconium compound (0.069 mol) are mixed with magnesium metal shavings (0.0069 mol) and 57.6 parts of mineral spirits (boiling point 170-195°C) and, with stirring, 4.79 parts of MgCl _{2.6H 2} O (0.0235 mol) was added. Heat was supplied to the reactor via an electric mantle. Within 5 minutes, the reaction mixture became opaque in appearance and gas evolution from the magnesium metal surface was evident when the temperature reached 85° C. with a reaction time of 8 minutes. Gas evolution continued with vigorous boiling and a whitish solid was observed when the temperature rose to 108°C. Continuous heating to 133°C (1 hour reaction time) caused all of the magnesium metal to disappear. The reactor contained a milky white liquid and a white solid. The reaction mixture was cooled and 92 parts of the mixture were collected. It contained 6.8% by weight Zr and 2.4% Mg (Zr/Mg weight ratio 28:1, Zr/Mg molar ratio 0.75) and was soluble in hydrocarbons. The reaction product is, for example, an alkyl aluminum halide, conveniently about 3/1 to 6/2
The olefin polymerization catalyst system can be activated in a known manner by reacting it with an Al/Zr molar ratio of 1, and in combination with an organic or organometallic reducing agent leads to the production of polyethylene resins. can do. The following example describes the use of calcium instead of magnesium as the reducing metal. Example 11 A 0.074 mol Ti(OBu) ₄ ; 0.074 mol Ca° (mechanically cut into small pieces from commercially supplied thick shavings); and 0.0125 mol
MgCl ₃ .6H ₂ O was mixed in octane in a stirred reactor with an electric heating mantle. The solution turned dark when it reached 105°C, and at 108°C the solution took on a dark gray appearance with gas evolution.
Rapid gas evolution occurred at 110.5°C followed by formation of a dark blue liquid. The reaction was complete in 90 minutes and the reaction product consisted of a dark blue-black liquid with a discrete green tinge. This operation was repeated at the same molar ratio. 50% of the calcium reacted to give a product consisting of a dark blue liquid and a gray solid. This product is
It contained 6.2 wt% Ti, 26 wt% Ca, and 1.1 wt% Mg (molar ratio: 1/0.5/
0.34) (11−A1). In another run, the same reagents were added at 0.75/
They were combined in a molar ratio of 0.128. Calcium 63
% reacted to give a blue-black liquid and a green solid. The reaction products (1/0.47/0.128 molar ratio) are 6.6 wt% Ti, 2.6 wt% Ca and
It contained 0.4% by weight of Mg (11-A2). B Reaction product 11-A1 at Al/Ti molar ratio 3/1
and further reacted with ethylaluminum chloride at 6/1. The reaction product was diluted with hexane and a halide activator was added slowly to control the highly exothermic reaction. In the operation with an Al/Ti molar ratio of 3/1, the initially formed crude white slurry was redissolved upon completion of the reaction to yield a pink liquid and a white precipitate. In operation with an Al/Ti ratio of 6/1, the color of the slurry changed to gray and then lime green. Reaction products 11-A2 were treated similarly with EtAlCl ₂ at Al/Ti molar ratios of 3/1 and 6/1. The reaction was smooth, and at a molar ratio of 3/1, a deep brown slurry was produced, and at a molar ratio of 6/1, a reddish-brown liquid and a multicolored precipitate were produced. C The reaction product prepared in section B was used in the polymerization of ethylene with the results shown in the following table.

[Table] These runs show a slightly broader molecular weight distribution in the resin compared to when magnesium is used as the reducing metal. The use of zinc as the reducing metal is shown in the following example. Example 12 A 0.204 moles of TBT, 0.153 moles of Zn° particles, and 0.026 moles of MgCl ₂ .6H ₂ O were combined in octane in an externally heated closed system with reflux. Within 13 minutes (85°C), a rapid change to a blue-black color occurred with increased gas evolution resulting in vigorous boiling and bubbling. The reaction product is a blue-black liquid (no precipitate) containing 7.7% Ti, 0.9%
Contains Zn and 0.5% Mg (each in wt%),
When exposed to air, it faded to yellow. B Reaction product TiZnMg (1/0.86/0.128 molar ratio) with isobutylaluminum chloride in 3/1 Al/Ti molar ratio in hexane at 10-13°C
(12-B1). C Production of TiZnMg reaction product (12-A) using Zn
Similar results were obtained using powder. Another run using old zinc utilized only 7% of the zinc and showed the formation of a green layer on the zinc surface. D The activated reaction product 12-B1 prepared as in B above was thoroughly washed in hexane and used for the preparation of low density polyethylene resin. The reactor was precharged with enough butene-1 to obtain the target density and the reaction was heated to 35 psig of _H2 in the presence of triethylaluminum as a cocatalyst.
At 170㎓ under pressure (butene-1 with ethylene
(additionally) was carried out. The recovered resin had the following properties: density 0.9165;
MI1.68, HLMI52.1, and MIR31. The following example involves the use of potassium as the reducing metal. Example 13 62.7 mmol of TBT, 47 mmol of fresh potassium metal (cleaned by scraping its oxide/hydroxide coating in octane), and
8.0 mmol of MgCl ₂ .6H ₂ O was mixed in octane in a closed system with external heating with reflux. 35℃
Within 2 minutes, the color changed to blue-black and foaming was observed. Violent gas evolution and boiling then occurred. The reaction was stopped when the potassium metal disappeared (5 hours). A dark blue-black liquid and a small amount of dark blue precipitate were recovered. Examples 14-15 below describe the use of aluminum as the reducing metal. Example 14 A 112.31 parts Ti(OBu) ₄ (0.33 mol), 8.91 parts
Al° (Alfa Inorganicspherical aluminum powder, -45 mesh) and 11.4 parts _MgCl2 .
6H ₂ O (0.056 mol) [molar ratio 1:1:0.17] was mixed in the reactor with stirring and heat applied using an electric mantle. When the temperature reached 100℃ for about 10 minutes, the yellow color deepened, and at 118℃, intense boiling began with gas release. At 122℃, the reflux liquid exhibits a gray phase;
The temperature stabilized as the reaction mixture changed color from deep gray with a blue tint to dark blue to blue-black over a reaction heating time of 27 minutes. This temperature was maintained and raised to 145°C within 1 hour and 20 minutes, at which point gas evolution was substantially complete and the reaction was complete. The reaction product at room temperature was a viscous liquid containing unreacted aluminum particles. Unreacted aluminum was separated, washed and weighed.
It was found that 6.7 parts of aluminum had reacted. The reaction product contained 7.9 wt% Ti, 3.4 wt% Al and 0.7 wt% Mg (molar ratio 1:
0.75:0.17). B 9.10 of the reaction product prepared as above.
1 part in hexane (13.0 parts) and placed in the reactor in a cooling bath. Gradually add 0.045 mol of ethylaluminum dichloride and reduce the temperature to 15-20
It was kept at ℃. The mixture stirred for 30 minutes gave a dark reddish-brown slurry and a difficult to process solid (B1). A second run was carried out without cooling to a peak temperature of 38°C. A reddish-brown slurry was formed again (B2) with a solid precipitate that was difficult to treat. Example 15 The reaction product of Example 14 was incubated under standard conditions (190〓,
It was used as a catalyst in the polymerization of ethylene under 60 psig H ₂ ). Triethylaluminum was used as a cocatalyst. The following results were obtained. MI HLMI MIR B1 0.14 6.45 46.1 B2 0.38 17.4 45.7 Example 16 A 0.133 mol TBT, 0.100 in the same manner as above
Mol of Al° and 0.017 mole of AlCl ₃ .6H ₂ O were mixed in octane and reacted for 7 hours and 15 minutes to give a dark blue-black liquid and a small amount of gray solid. Approximately 40% of the aluminum reacted to form a reaction product consisting of 6.6 wt% Ti and 1.6% Al (16-A1). Similarly, the same reaction reagents were mixed in a molar ratio of 1/1/0.17. Approximately 58% of the Al reacted to form a reaction product containing 6.5 wt% Ti and 2.7 wt% Al (16-A2). B Reaction products 16-A1 and 16-A2 are mixed in 3/1
Activated with ethylaluminum chloride at Al/Ti molar ratio. C. The solid part of the activated reaction product (16-A2) is separated from the supernatant liquid and used as a cocatalyst.
Together with TEA, it was used in ethylene polymerization at 170ⓓ, 15 psigH ₂ to obtain a resin with the properties of MI 0.02, HLMI 1.01, and MIR 50.5. In the second operation
We obtained a resin with the characteristics of HI0.02, HLMI0.45, and MIR22.5. The following examples relate to catalyst components made using other hydrous complexes. Example 17 A 0.0335 moles of TBT and 0.0335 moles of Mg° are stirred in octane in a reactor;
0.0057 mol of MgBr ₂ .6H ₂ O was added (reaction molar ratio 1/1/0.17). As the gas boiled, a gray color formed and the solution turned blue, then blue-black with a green tinge. After a reaction time of 4 hours and 10 minutes, the reaction was completed at 123° C. (approximately 10% unreacted Mg). (17-A). Similarly (Ti/Mg/MgBr ₂・6H ₂ O=
The reaction product was prepared in a molar ratio of 1/0.65/0.11). The reaction products were a blue-black liquid and a dark green precipitate [6.5 wt% Ti, 2.5 wt%
Mg (calculated)]. B Decanted reaction product (17-A)
isobutylaluminum dichloride and 3/
1 and 6/1 Al/Ti ratio. This was done by gradually adding the alkyl aluminum halide. The first operation (Al/
Ti=3/1) was added at a rate of 1 drop every 2-3 seconds until a peak temperature of 42°C was reached, at which point the green liquid turned brown. The reaction products were a reddish-brown liquid and a brown precipitate (4B-1).
A reaction product (4B-2) with Al/Ti=6/1 was produced in the same manner, and similar results were obtained. In a separate operation, the reaction product (17-A) was similarly combined with SiCl ₄ . The reaction products from the 30 minute reaction at a Si/Ti ratio of 3/1 were a pale yellow liquid and a brown precipitate. A reaction product with a Si/Ti ratio of 6/1 was obtained by a similar operation. C Activated reaction products 17B-1 and 17B-
2 (1 wt% Ti) with hydrogen modifier and triethylaluminum cocatalyst (45 ppm Al).
was used for the polymerization of ethylene (10 mole % in isobutane) at 190% and compared to the same run using magnesium chloride hydrate. The results are shown in the table below.

Table: Example 18 A 42.23 parts of TBT (0.124 mol) were mixed with 3.02 parts of Mg (0.124 mol) in octane (42.8 parts) and 5.7 parts of FeCl ₃ 6H ₂ O (0.02 mol) (Ti/
Mg/Fe=1/1/0.17 mol). Heating was started and gas evolution began within 6 minutes at 65°C. The muddy yellow color is 80℃ (7
The color turned brown and gas evolution increased. about
After 30 minutes, gas generation slows down, then
The reaction subsided due to consumption of Mg°, and the reaction ended. There was no residue in the very dark liquid (18
−A1). In the second operation, the same reaction reagents were mixed with Ti/
Similar results were obtained by mixing Mg/Fe at a molar ratio of 1/1/0.34. Although diluted with hexane, no precipitate or residue was deposited (18-A2). B. Reaction product 18-A1 was mixed with a 50% by weight solution of ethylaluminum chloride in hexane in 3/3
Activated by reaction at an Al/Ti ratio of 1.
A brown liquid and solid containing 16.5 MgTi/g were recovered (18-B1). The reaction product (18-A1) was activated in the same manner. The dark brown liquid turns into a purple slurry;
It then turned into a dark gray slurry. The resulting clear liquid and gray precipitate contained 16 Mg/Ti/g. C Activation reaction product 18-B1 190〓, 60SsiH ₂
It was used for ethylene polymerization. 114320gPE/
gTi/hr was recovered and showed the following properties:
MI5.1, HLMI155.3, MIR30.3. Example 19 A 1.0.160 mol Ti(OBu) ₄ , 0.160 mol Magnesium shavings and 0.027 mol _CoCl2 .
6H ₂ O was combined with 61.2 parts of octane in a stirred reactor. The purple cobalt salt crystals dissolved to give a dark blue solution. The mixture was heated using an electric mantle and gas evolution on the magnesium surface was observed at 58°C. As heating continued, the transparent blue color turned gray, and at 123-125°C, it became almost black. At this time, all the magnesium had disappeared, and the reaction was completed in 90 minutes. The milky blue reaction product was hydrocarbon soluble and redissolved into a dark blue liquid that formed a dark precipitate on standing. This operation was repeated with substantially the same results. B. Shaking the reaction product produced as above,
Isobutylaluminum chloride (0.0333 mol) was added dropwise to the reactor at 0.0111 mol (Ti).
Al). Temperatures peak at 40°C;
A gray precipitate formed and turned brown when more BuAlCl ₂ was added. After heating for an additional 30 minutes, the reaction was complete, yielding a dark reddish-brown liquid and a brown precipitate. C The catalyst component produced in Example 19 above was used for polymerization of ethylene (190〓, 10 mol% ethylene, Ti equivalent)
Using 0.0002 parts of catalyst, about 45 ppm of triethylaluminum in terms of Al, and H ₂ ) shown in the table below, the results shown in the table below were obtained.

[Table] Example 20 A 0.169 mol of Ti(OBu) ₄ [TBT], 0.169 mol of magnesium, and 0.029 mol of AlCl ₃ .
6H ₂ O was mixed in octane as diluent in a stirred reactor with an electric heating mantle. The hydrated aluminum salt partially dissolved and at 111°C the solution rapidly darkened and turned into a black liquid with vigorous boiling due to gas evolution on the magnesium surface. This solution has a blue appearance and
Upon smooth reflux to 122°C, a dark blue-black liquid was formed and some magnesium remained.
At 125℃ all magnesium disappears,
The solution took on a pale green color. The reaction was completed and a dark blue-black liquid and a green precipitate were collected in a volume ratio of about 95/5. B. The above reaction product was mixed with isobutylaluminum chloride by dropwise adding isobutylaluminum chloride to the reactor containing the titanium material such that the Al/Ti molar ratio was 3:1 and 6:1. Mixed. In the first reaction (3:1), the alkyl chloride is
1 every 2-3 seconds until reaching a peak temperature of 42°C.
Added dropwise. The hue changed from blue-green to brown. After stirring for an additional 30 minutes, the reaction product consisting of a reddish-brown liquid and a brown precipitate was separated (20-B). C In a similar manner, a 6:1 Al/Ti reaction product was prepared with similar results (20-C). D reaction products 20-B and 20-C with triethylaluminum cocatalyst (45 ppm Al) at 190
It was used in the polymerization of ethylene (10 mol %) using isobutane as a diluent at the hydrogen pressures shown in Table 1 and below. This operation was terminated after 60 minutes and the results shown in the table below were obtained.

[Table] Example 21 A 0.153 mol of Ti (OBu) ₄ [TBT], 0.153 mol of Ti (OBu)
61.75 Mg° turnings and 0.026 NiCl _{6.6H 2} O in a stirred reactor with an electric heating mantle.
Mixed with octane. Heating to 44°C caused the yellow solution to darken, and gas evolution on the magnesium metal was observed at about 57°C. If you continue to heat it up to 102℃ (15
minute reaction) Gas generation increased and the reaction system turned pale muddy brown. At 126°C, all the magnesium disappeared, and intense gas boiling continued with deep browning until the reaction was complete.
The reaction product (21A-1) was a hydrocarbon-soluble dark brown liquid and a small amount of fine precipitate. In the second operation, 0.149 mol TBT,
0.149 mol Mg, and 0.051 mol _NiCl2 .
6H ₂ O was similarly mixed in octane. Magnesium metal disappears at 115°C in 120 minutes, and the reaction gives a dark brown-black hydrocarbon solution which, on standing, produces a very fine dark precipitate and a yellow solution, about 50/50 volume. Divided (21A−
2). B Shake the reaction product 21A-1 and place a portion of it (0.0137 mol Ti) into the reactor with hexane diluent to which iBuAlCl ₂ (0.0411 mol Al)
at a rate of 1 drop per 2-3 seconds at 28°C and at a rate of 1 drop per second up to a peak temperature of 39°C.
Added dropwise. After the addition was complete, the contents of the reactor were stirred for 30 minutes and the reaction product consisting of a dark reddish-brown liquid and a dark gray precipitate was separated (21B-1). The same reaction product (21A-1) was also mixed with ethylaluminum dichloride and 3/1 Al/Ti.
Mixed in molar ratio. The reaction products were a dark reddish-brown liquid and a dark gray solid (21B-2). In substantially the same manner, reaction product 21A-2
(Ti/Mg/Ni molar ratio is 1/1/0.34)
The same results were obtained when mixed with iBuAlCl ₂ at an Al/Ti molar ratio of 3:1. However, the supernatant liquid was pale reddish brown. (21B-3). In a further operation, reaction product 21A-2
is mixed with iBuAlCl ₂ at an Al/Ti molar ratio of 6:1,
A dark liquid and a dark precipitate were obtained in the same manner. (21B−
4). The same reaction product 21A-2 was similarly combined with ethylaluminum chloride to give a dark reddish-brown liquid and a dark gray solid. (21B-5). Example 22A Example 21-A was repeated with the reactants fed in a Ti:Mg:Ni molar ratio of 1:0.65:0.11. During the reaction, which lasted for 6 hours, the color changed from deep tan to dark brown, then to grayish brown, and then to dark blue upon depletion of magnesium with the evolution of gas. (22-A). B Reaction product 22-A was mixed with ethylaluminum chloride and 3:1 Al/A in the same manner as in Example 21-B.
Mixed with Ti molar ratio. A reddish-brown liquid and a reddish-brown precipitate were collected. (22-B). Example 23 Example 22-A was repeated by feeding the reactants in a molar ratio of 1/0.75/0.128. The dark brown reaction product contains 5.9% Ti, 2.2% Mg, and 0.97%
Contains Ni. The reaction product was treated with isobutylaluminum chloride at 3/1 Al/Ti mole. Example 24 A series of Ti-Mg-Ni catalysts prepared as shown in Examples 21-B and 22-B were used for the polymerization of ethylene (190〓, 10% mole % ethylene, Al equivalent
45ppm triethylaluminum, used as a catalyst component in _H2 pressure) shown in the table below.
The results shown in the table below were obtained.

[Table] Example 25 A TBT, Mg゜, and MgSiF _{6.6H 2} O were mixed with octane in a heating reactor equipped with a reflux device in the same manner as in the previous example, and the molar ratios were 1/1/0.34 and 1/1/0.34.
Reaction products of 0.75/0.128 were obtained, respectively. B The above reaction product was activated by reaction with ethylaluminum chloride in an Al/Ti molar ratio of 3/1. C The resulting brown precipitate was separated from the supernatant red bicolor liquid and subjected to ethylene polymerization (190〓,
60 psigH ₂ ) and 107500g PE/resin with properties of MI2.85, HLMI84.5 and MIR29.6.
It was obtained at a rate of gTi/hr. D The 1/1/0.34 reaction product prepared above was likewise activated with isobutylaluminum chloride at an Al/Ti ratio of 3/1. The solid reaction product was washed several times with hexane and used with TEA in a polyethylene polymerization reactor prefilled with butene-1 to form a resin of desired density from ethylene/butene- ₁ at 170㎓, 30 psigH2. was manufactured. The resulting resin has a density of 0.9193,
It had MI1.91, HLMI60.8 and MIR31.8. In the following examples, various catalyst components were activated by reaction with various nalide components. Example 26 A In each of the following operations, the TMMg reaction product was reacted with a halide component that was added slowly, usually dropwise, to control the exothermic reaction. Reactions were carried out under ambient conditions for 10-30 minutes after the onset of peak temperature, sufficient time to complete the addition with stirring of the reactants (if applicable, TMMg
The solid and liquid components were intermixed into a slurry and used in this form). The reaction reagents and their proportions are shown below.

【table】

[Table] Example 27 A Catalyst samples activated with Bu ⁱ AlCl ₂ (3:
An Al/Ti ratio of 1) was used in a series of polymerization runs with the results shown in the following table.

[Table] As can be seen from the comparison of the molar ratio of Ti/MgCl ₂ 6H ₂ O, the melt index of the peak is 9:
1 (Ti/H ₂ O of 1.5:1). B In the next additional operation, activated
The effect of Al/Ti ratio in TMMg (molar ratio 1/0.65/0.11) was investigated in the polymerization of ethylene. The results are shown in the table below.

TABLE The effect of the activator was analyzed in a further series of experiments using a TMMg catalyst with a molar ratio of C 1/0.75/0.128. The results are shown in the table below.

【table】

[Table] D With TMMg1/0.75/0.128 catalyst (slurry separated from supernatant and washed with hexane) and TEA cocatalyst, using ethylene and butene-1 as comonomer and feed rate of butene-1, Large-scale polymerization runs were carried out at 160 ml by varying the activators and their ratios. The results are shown in the table below.

[Table] Each batch of resin collected as above
100ppm calcium stearate and
Stabilized with 1000 ppm Irganox 1076; characterized by conventional testing; and in a 1 1/2 inch Harting extruder (60 rpm screw, 3 inch die in 0.082 inch die gap, cooling air 37-40 mm). Further tests were conducted on blown film. All of these are shown in Tables XI and XII.

【table】

【table】

[Table] E Molar ratio 1/0.75/0.128 (3/1 Al/Ti,
In a similar large-scale polymerization using TMMg catalyst (slurry separated from the supernatant and washed with hexane) of EADC), hexene-1
was fed to the reactor along with ethylene as a comonomer and then butene-1 was replaced with tracking by off-gas analysis to produce ethylene/butene-1/hexene-1 copolymers and terpolymers in this run. The results are shown in the table below.

Table: Example 28 TMMg catalyst prepared according to the previous example and activated with isobutylaluminum chloride (3/1 Al/Ti) is used to produce other comonomers by changing the pre-filled copolymer. did. Isobutane diluent, reactor temperature of 170〓, 30-40 psig _H2 and TEA (60 ppm Al
The comonomer production was carried out using

The polymerization or copolymerization of other α-olefin monomers, such as propylene, 4-methylpentene-1, alkyl acrylates, alkyl methacrylates and alkyl esters, can be carried out in a similar manner. The following comparative experiment was also conducted. Comparative experiment A In the same reactor used for other productions, TBT,
Mg゜ and anhydrous MgCl ₂ in octane
The mixture was mixed at a molar ratio of 1/0.34 and heated to reflux for 15 minutes, but there was no sign of reaction. Anhydrous MgCl ₂ remained undissolved. See also Example 1 B above. B In the same system, 1/0.34 Mg゜/MgCl ₂ 6H ₂ O
and equal amounts of free water were added together, but there was no sign of change. C TBT and Mg° were mixed in a 2/1 molar ratio in octane and heated to reflux. The yellow color became slightly darker, but no signs of reaction occurred. D Add 1/0.34 Mg/MgCl ₂ to the above system C.
6H ₂ O and an equal amount of free water were added. A small amount of pale yellow precipitate formed indicating hydrolysis of the titanium compound, but the magnesium remained unreacted. E TBT and MgCl ₂ .6H ₂ O were mixed in octane in a molar ratio of 1/0.34 and heated to reflux.
After the salt was completely dissolved, refluxing was continued for 3 hours, and the solution became cloudy and viscous, but still transparent, and when left overnight, it separated into a cloudy yellow liquid and a whitish precipitate. did. molar ratio 1/
In another run at 0.128, heating to reflux for only 16 minutes produced a clear golden yellow liquid. At a molar ratio of 1/1.17, foaming and formation of a thick cream colored gel stopped the reaction after 45 minutes. This is a comparative example with the above-mentioned Example 7.

Claims (1)

[Claims] 1. A multimeric transition metal oxide alkoxide obtained by reacting an alkoxide of a transition metal selected from the group consisting of titanium and zirconium with a hydrate of a salt of aluminum, cobalt, iron, magnesium, or nickel. 1. A method for producing an intermetallic compound, which comprises preparing an intermetallic compound and contacting the intermetallic compound with a reducing metal selected from the group consisting of magnesium, calcium, zinc, aluminum, and mixtures thereof. 2. The method of claim 1, further comprising the step of contacting the intermetallic compound with a halide activator having aluminum, boron, titanium or silicon atoms. 3. The method according to claim 1, wherein the transition metal alkoxide is a titanium alkoxide and the hydrate is a hydrate of an aluminum salt. 4. The method of claim 3, further comprising the step of contacting the intermetallic compound with an aluminum-containing halide activator.