JPS637561B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of spraying suspensions of solids in liquids, the use of solid products to produce certain components of catalyst systems, and the polymerization of unsaturated monomers, especially olefin monomers, such as ethylene and propylene. Concerning the use of catalyst systems for. Many of the catalyst systems used for the polymerization of unsaturated monomers, such as ethylene and propylene, contain solid transition metal components. The solid transition metal component is
Solid transition metal compounds, solid transition metal compounds containing compounds of other metals, such as the many commercially available titanium trichloride materials available as materials containing aluminum compounds in the titanium trichloride lattice, or suitable A transition metal compound supported on a carrier material. For the most efficient production of olefin polymers, it is desirable that the polymer be recovered in a recovery process with a minimum number of processing steps. Thus, it is desirable that the catalyst system be able to produce polymer in such high yield that removal of catalyst residues is not required. For the polymerization of higher olefin monomers, such as propylene, it is also desirable to minimize the formation of undesirable atactic polymers, thereby allowing the removal of this atactic material to be omitted. Many catalyst systems with high polymerization activity and high stereospecificity require
It is produced by a process that involves grinding a solid material, usually in a substantially dry state. Dry milling of solid materials results in particles having an irregular shape and a broad particle size distribution. The particle shape of the ground solid material is such that handling of the solid material can be problematic. Furthermore, in the manufacture of propylene polymers, the polymer typically mimics, to a large extent, the particle shape and particle size distribution of the catalyst material, and therefore polymers formed using such milled materials are desirable. They often have poor powder flow properties. British Patent Specification 1527736 discloses that by mechanically pulverizing a magnesium dihalide and an aromatic carboxylic acid ester and contacting this pulverized product with a titanium halide without mechanical pulverization. Concerning the production of catalyst components. British Patent Specification 1559194 relates to a catalyst component comprising on its surface the reaction product of a magnesium halide compound with a tetravalent titanium compound and an electron-donating compound, the product containing specific properties including the insolubility and surface area of the Ti compound. It has the characteristics of The method for preparing such catalyst components is similar to that of British Patent Specification 1527736. British patent specification 1421943 relates to a polymerization process in which one component of the catalyst is obtained by comminution of titanium trichloride and a specific electron donor. Grinding is carried out without the presence of auxiliaries or additives,
Grinding in the presence of inert liquids violates the clear requirement of the absence of auxiliaries and additives. British Patent Specification 1512703 relates to a process for producing modified titanium-containing components by simultaneously grinding titanium trichloride and an organophosphorus compound under specific milling conditions. The grinding is carried out dry (claim 1 and page 2, lines 3 and 4). Similarly, the British patent specification
No. 1485181 relates to a method for producing modified titanium-containing components by simultaneously grinding titanium trichloride and an organophosphorus compound under specific milling conditions.
Grinding is also carried out drying (claim 1, 1st
Pages 28, lines 31-33 and 75, and page 2, 34-37.
line). Belgian patent specification 862135 relates to a process for producing modified titanium-containing components by simultaneously grinding titanium trichloride and an ester having a specific formula. The grinding is carried out under specific conditions, including the absence of diluents (claim stage
(2), (3) and (6)). In both of these operations, the resulting product provides somewhat poor particle shape. Alternatively, grinding may be performed in the presence of a liquid medium. However, we have found that such grinding processes can yield materials of fine particle size, which are difficult to handle and unsuitable for use in commercial polymerization systems. British Patent Specification 1292853 discloses a catalyst component obtained by contacting a halide of titanium in a valence state less than tetravalent with anhydrous magnesium halide in the active state. In one of the examples (Example 8), a mixture of titanium trichloride and magnesium chloride is ground in a ball mill in the presence of n-heptane. However, it is stated that milling is preferably carried out without the presence of an inert diluent (page 2, lines 3 and 4 and lines 33 and 34). Therefore, although grinding the solid material and liquid medium is disclosed, this is not a preferred process. It is also expected that this will result in a material with such fine particle size that it is difficult to handle. JP 55-120608 relates to an ethylene polymerization process, which is carried out using a catalyst obtained by spray drying a precursor in an electron donor.
We attempted to polymerize propylene using the catalyst system disclosed in JP-A-55-120608, but we were unable to polymerize propylene. In order to improve the particle shape of the solid catalyst component, suspensions containing transition metal-containing substances can be prepared, for example, by
56-155209 (not a prior document), it was proposed to subject it to a spray drying process. However, some of the particles present in the initial solid material may have a size and shape such that they are not easily spray dried or do not exhibit improved particle shape as a result of spray drying. GB Patent Specification 2006227 discloses a method for spray drying a catalyst carrier which is a halogen-free, oxygen-containing magnesium compound and then after-treating the spray-dried material with titanium tetrachloride. The suspension of the magnesium compound in water is ground prior to spray drying and the resulting mixture is then spray dried. The spray-dried product contains water, and the presence of water is generally considered undesirable in olefin polymerization catalysts. Although this process provides an active catalyst for the polymerization of ethylene, when this catalyst is used for the polymerization of propylene, the resulting polymer exhibits insufficient stereospecificity, with substantially less than 90% of the polymer Insoluble in heptane. According to the invention, the solid substance is a liquid hydrocarbon,
a liquid medium that is a liquid halohydrocarbon, a liquid compound of a transition metal of groups A to A of the periodic table, or a liquid solution of a compound of a transition metal of groups A to A of the periodic table in a liquid hydrocarbon or a liquid halohydrocarbon; mix,
(1) exposing a mixture of a solid substance and a liquid medium to mechanical action to reduce the particle size of the solid substance, spray drying the resulting mixture, and collecting the spray-dried solid substance; Solid substances are A, A or A of the periodic table.
(2) after exposure to mechanical action; or (2) after exposure to mechanical action; A method is provided, characterized in that, before or after spray drying, the solid material is brought into contact with at least one compound of a transition metal of groups A, A or A of the Periodic Table. In particular, the present invention provides a method for producing the transition metal component of an alpha-olefin polymerization catalyst, which method comprises mixing a solid material with a liquid hydrocarbon or halohydrocarbon medium; (1) subjecting a mixture of a substance and a liquid medium to mechanical action to reduce the particle size of the solid substance, spray-drying the resulting mixture, and recovering the spray-dried solid substance; TiCl ₃ 1/3 optionally containing Lewis base compounds and/or wear inhibitors
or ( ₂ ) the solid material is MgCl ₂ , an aromatic carboxylic acid ester, and optionally a wear inhibitor and/or
It is characterized by being a substance obtained by contacting a component containing SOCl ₂ with TiCl ₄ . All references in this specification to the periodic table are from JR Partington, “General and lnorganic
Chemistry” “General and Inorganic Chemistry”, 2nd edition,
MacMillan and Company Limited (London)
Refer to the short periodic table on the inside back cover of the 1954 issue. For convenience, the term "milling" will be used hereinafter to mean exposing the mixture to mechanical action to reduce the particle size of the solid material. For convenience, the term "transition metal" will hereinafter be used to mean a transition metal of Groups A, A, or A of the Periodic Table. The transition metal can be, for example, vanadium or zirconium, preferably titanium. Preferred transition metal compounds are halides or oxyhalides, such as vanadium tetrachloride, vanadium oxytrichloride, zirconium tetrachloride, particularly preferably titanium halides, such as titanium tetrachloride and titanium trichloride. . Transition metal compound 1
More than one species can be used, for example mixtures of vanadium and titanium halides, such as mixtures of vanadium tetrachloride and titanium tetrachloride on a suitable carrier, but especially when the final product is When used in the polymerization of higher alpha olefin monomers, it is generally preferred to use only one transition metal compound, preferably titanium halide. If the solid substance is a solid compound of a transition metal,
This is preferably titanium trichloride, the term being used here to cover not only pure titanium trichloride, but also the products of reduction of titanium tetrachloride with organoaluminum compounds or aluminum metal; The material contains aluminum halides and possibly organoaluminum compounds in the lattice. Alternatively, the solid material can be a compound of a transition metal compound on a suitable support. Suitable support materials are metal oxides, in particular metal oxides of the periodic table ~
It is a metal oxide containing silicon. thus,
The support can be an oxide such as magnesia, alumina, silica, or a mixture or compound of one or more of these materials, although other metal oxides can also be used. However, highly active and at the same time highly stereospecific catalyst systems, the support materials are metal halides,
Specifically disclosed is magnesium chloride. Therefore, the use of metal halides, or transition metal compounds on metal halides, is a preferred aspect of the invention. As solid substance, it is possible to use substances that do not contain transition metal compounds. If such a solid material is used, the solid material is treated with a transition metal compound after comminution of the mixture and before or after spray drying. This transition metal treatment is preferably carried out by treating the solid material with a liquid medium that is a liquid transition metal compound or a solution of the transition metal compound in a suitable solvent. A preferred transition metal compound for this subsequent treatment is titanium tetrachloride, which can be used in undiluted form or as a solution in a suitable solvent, especially a hydrocarbon solvent such as an aliphatic hydrocarbon. According to yet another procedure, more than one solid material can be used, in particular one material is or contains at least one transition metal compound and one material is a transition metal compound. Contains no metal compounds. Examples of the use of more than one solid substance are mixtures of titanium trichloride and silica or mixtures of silica and the product of contacting titanium tetrachloride with magnesium chloride. If more than one solid substance is used, it is possible to use one of the solid substances in all stages in the process of the invention and to add other solid substances in subsequent stages before the spray drying stage. It is. however,
The solid material added after pulverizing the mixture of solid material and liquid medium is of fine particle size, in particular when essentially all of the particles are smaller than 10 microns.
In particular, it is preferred to have a maximum dimension of less than 5 microns. Typically, prior to mixing with a liquid medium, comminution and spray drying, the solid material is subjected to an optional preliminary step, in particular a pre-grinding step, in which the solid material is subjected to essentially the absence of a liquid medium. and grinding in the presence of a modifying substance, for example a Lewis base compound. "Essentially in the absence of a liquid medium" means that the liquid present, other than the modifying substance, does not form a separate liquid phase. It will be appreciated that some liquid may be absorbed by the solid material and therefore the complete absence of added liquid medium is not necessary. Typically, the amount of liquid medium is less than 0.2 cm ³ and especially less than 0.1 cm ³ per gram of solid substance. The Lewis base compounds that can be used as modifiers can be any Lewis base compounds, especially organic Lewis base compounds, that have hitherto been proposed for use in olefin polymerization catalyst systems. Thus, Lewis base compounds include ethers, esters, ketones, alcohols, orthoesters, sulfides (thioethers), esters of thiocarboxylic acids (thioesters), thioketones, thiols,
Sulfones, sulfonamides, fused ring compounds containing heterocyclic sulfur atoms, organosilicon compounds such as silanes or siloxanes, amides such as formamide, urea and substituted derivatives thereof such as tetramethylurea, thiourea, alkanolamines, amines (the term encompasses cyclic amines, diamines or polyamines), e.g.
Pyridine, quinoline, or tetramethylethylenediamine, or organophosphorus compounds, e.g.
It can be an organic phosphine, an organic phosphine oxide, an organic phosphite or an organic phosphate. The use of organic Lewis base compounds is described in British patent specifications numbered, among others: 803198, 809717, 880998, 896509, 920118,
921954, 933236, 940125, 966025, 969074,
971248, 1013363, 1017977, 1049723, 1122010,
1150850, 1208815, 1234657, 1324173, 1359328,
1383207, 1387890, 1423658, 1423659, 1423660,
1495031, 1527736, 1554574 and 1559194. Lewis bases disclosed as being particularly useful in the preparation of polymerization catalysts include ethers, esters,
Includes organosilicon compounds and organophosphorus compounds. Particular examples of ethers are aliphatic ethers such as di-n-butyl ether and di-iso-amyl ether. Esters can be esters of saturated or unsaturated acids, such as ethyl acetate and methyl methacrylate, but
Particular preference is given to using esters of carboxylic acids containing aromatic groups, such as ethyl benzoate, butyl benzoate, methyl p-methylbenzoate, ethyl p-methoxybenzoate and ethyl phenyl acetate. Other esters that can be used are mono- and poly-esters of saturated and unsaturated polycarboxylic acids (the term includes dicarboxylic acids), such as dialkyl phthalates. The organosilicon compound may include one or more Si-OR, Si-OCOR or Si- _NR2 (wherein R
is a hydrocarbyl group) and includes phenyltriethoxy-silane, diphenyldi-isobutoxysilane and isobutyl-triethoxysilane. Processes for comminution of solid compounds of transition metal compounds, such as titanium trichloride, in the presence of Lewis base compounds are described in numerous publications, for example in British patent specifications.
1421943, 1485181 and 1512730, and Belgian patent specification 862135. Grinding of solid substances such as magnesium chloride in the presence of Lewis base compounds is described, for example, in the British Patent Specification
1527736 and 1559194. The amount of Lewis base compound used in any pre-grinding can be any amount conventionally used, but typically does not exceed one mole of Lewis base compound for each mole of solid material. When the solid substance is or contains a transition metal compound, the amount of Lewis base compound preferably does not exceed 1 mole for each mole of transition metal compound, in particular Lewis base compound for each mole of transition metal compound. The metal compound ranges from 0.1 to 0.5 mole. Optional pre-milling is carried out for a time depending on the intensity of the milling, which with a rotary ball mill or a vibratory ball mill is from 0.5 to 100 hours, with a vibratory ball mill generally requiring less time. The milling temperature can range over a wide range, for example from -50°C to 100°C, and the temperature can be changed during milling. For many materials, temperatures in the range 0°C to 50°C are suitable. The optional preliminary step is preferably carried out by milling the solid material in the presence of a Lewis base compound, but the preliminary step is preferably carried out by contacting the solid material with the Lewis base compound in the absence of milling. Can be implemented. More specifically, the solid material can be contacted with a liquid Lewis base compound or with a solution of the Lewis base compound in a suitable liquid medium. Contacting with the Lewis base compound is preferably carried out at an elevated temperature for a suitable period of time, which can be from 5 minutes to 10 hours. Treatment of solid materials with Lewis bases without grinding is disclosed, for example, in British Patent Specification 1391067. When the solid material is a transition metal on a support material,
Contacting the transition metal compound with the support material and optionally the Lewis base compound can be carried out using optional preliminary steps. Such contacting can be carried out with or without a grinding step, but typically includes a grinding step as at least a portion of such contact. After subjecting the solid material to an optional preliminary step in which it can be contacted with a modifying substance, the solid is then mixed with a liquid medium;
Finely ground and spray dried. however,
It is not necessary to use solid materials treated with Lewis base compounds. If a Lewis base compound is used, the treatment with the Lewis base compound can be carried out simultaneously with one of the steps of the method of the invention, and at the same time this treatment can be combined with the step of comminution of the mixture of solid substance and liquid medium. can be done.
More specifically, milling in the presence of a liquid medium can be carried out in the presence of a Lewis base compound, and the Lewis base compound is present as a liquid medium or as a solution in the liquid medium in which the solid substance is suspended. do. When using such a procedure, the liquid medium is preferably a solution containing a dissolved Lewis base compound. Alternatively, treatment with a Lewis base compound can be carried out between the steps of the process of the invention, or after the spray drying step. When the solid material does not contain a transition metal compound, the transition metal compound can be present in a liquid medium that is mixed with the solid material before comminution of the mixture. Thus, a solid material can be mixed with a solution of a transition metal compound in a suitable liquid medium or even in a liquid transition metal compound, and this mixture can then be pulverized and subsequently spray-dried. . Furthermore, the solid material can be mixed with a liquid medium that is or contains both a Lewis base compound and a transition metal compound. However, the mixing of a solid substance with a liquid medium that is or contains a Lewis base compound and/or a transition metal compound, comminution of this mixture and spray drying of the comminution mixture is not a preferred embodiment of the invention. . When the solid material to be mixed with the liquid medium and milled is not a transition metal compound or a solid containing it, the solid material is after-treated with the transition metal compound before or after spray drying. Suitable treatments with transition metal compounds are described, for example, in British Patent Specifications 1527736 and 1559194 and also in British Patent Specification 2103627A by the applicant entitled "Transition Metal Compositions, Manufacture and Use". In the aforementioned co-pending application, a composition of magnesium halide and an ester of a carboxylic acid is formed, typically by co-milling the magnesium halide and the ester, and this composition is prepared from hot titanium tetrachloride. and repeated contact with hot titanium tetrachloride, followed by gentle washing of the resulting product, which washing is sufficient to remove only a portion of the soluble titanium species from the product. In the preferred procedure of British Patent Specification 2103627A,
The transition metal composition is prepared by co-milling magnesium chloride with ethyl benzoate, suspending the co-milling product in titanium tetrachloride at a temperature of at least 60°C, separating the solids from the titanium tetrachloride, and subjecting it to treatment with titanium tetrachloride. It is obtained by repeating and washing the product obtained no more than twice with heptane at a temperature of at least 60°C. In the titanium chloride composition thus obtained, a substantial proportion of the titanium, which may be more than 50%, can be extracted by successive washings with hot heptane. Alternatively, the method of the present invention may be described in US Pat.
109509 method. Japanese Unexamined Patent Publication 1983-
109509, a titanium-containing composition is prepared by contacting magnesium halide with at least one compound of a non-metallic element, other than oxygen, from Groups ~ of the Periodic Table, and contacting the resulting product with titanium tetrachloride. obtained by contacting with a liquid phase containing,
Where the compound of the non-metallic element also contains oxygen and halogen, one or two atoms of oxygen per molecule and enough to satisfy the residual valence of the non-metallic element, which can be carbon, phosphorus or sulfur. There are many halogens. It is also preferred to contact the halogenated magnesium material with a Lewis base compound, for example an ester such as ethyl benzoate. Compounds of nonmetallic elements are hereinafter referred to as "nonmetal halides" and are typically thionyl chloride (SOCl ₂ ). According to the preferred procedure of JP-A-58-109509, magnesium halide is ground with thionyl chloride and an ester such as ethyl benzoate, followed by heating at least 60°C.
and at least once in heptane at a temperature of at least 60°C. The milling and spray drying according to the invention can be incorporated at appropriate steps in the procedure of JP-A-58-109509. A mixture of a solid substance and a liquid medium can be, for example,
Between the milling stage and the spray drying, an intermediate treatment step can be carried out by contacting with a transition metal compound, but it is preferred to carry out the milling and spray drying in succession without an intermediate stage. After spray drying, the spray-dried solid is or contains a transition metal compound, e.g.
Further treatment with Lewis base compounds, or non-metal halides, or transition metal compounds can be performed. Such further treatment can be carried out using a Lewis base compound or non-metal halide that is the same or different from the Lewis base compound or non-metal halide previously used to treat the solid material. Similarly, the transition metal compound used in such further processing can be the same as or different from the transition metal compound used in the preparation of the spray-dried material. The liquid medium that mixes with the solid substance is preferably
When a spray-dried solid material containing a transition metal compound is used as a polymerization catalyst component, it should not have any deleterious effects on the spray-dried solid material. In general, it is preferred to use an inert liquid, especially a hydrocarbon or an inert halohydrocarbon, as the liquid medium, especially when the contact with the transition metal compound is carried out after the milling step and before the spray drying step. preferable. Thus, the liquid medium is preferably an aliphatic hydrocarbon, such as hexane, heptane, octane, decane, dodecane or mixtures thereof, or an aromatic hydrocarbon, such as
Benzene, toluene or xylene or halohydrocarbons such as chlorobenzene or 1,2-dichlorobenzene. Alternatively, the liquid medium can be or contain a transition metal compound, when it is necessary to contact the solid substance with the transition metal compound;
Preferably, this contacting is carried out as a separate step from the step of pulverizing the liquid medium and the solid material, which is or contains the transition metal compound. The relative proportions of solid and liquid substances are preferably such that at the end of the milling stage the mixture is a mobile suspension of solid substances in a liquid medium. It is thus preferred to use liquid medium in a ratio of at least 1 cm ³ of liquid substance for each gram of solid substance. It is particularly preferred to use at least 3 cm ³ of liquid medium for each g of solid substance, but generally the amount of liquid medium does not exceed 20 cm ³ and in particular does not exceed 10 cm ³ for each g of solid substance. Milling of a mixture of a solid substance and a liquid medium is a process in which mechanical action reduces the particle size of the solid substance.
It can be performed using any technique. Particle size reduction here means that the weight average particle size of the solid material after exposure to mechanical action is smaller than the weight average particle size of the solid material before exposure to mechanical action. The particle size of the solid material after the milling stage will depend on the nature of the solid material, the initial particle size of the solid material, and the duration and intensity of the milling. Generally, the weight average particle size of the finely divided solid material is less than 15 microns, and in particular does not exceed 10 microns. One milling method that can be used in accordance with the present invention is
It is the grinding of a mixture of solid material and liquid medium. This grinding can be carried out in the same type of grinding equipment that can be used to carry out any pre-grinding step, such as a rotary ball mill or a vibratory ball mill. When carrying out the optional pre-grinding step, comminution by comminution of a mixture of solid material and liquid medium is carried out in the same comminution device by adding the desired amount of liquid medium to the comminution device and then continuing the comminution for the desired period of time. It can be implemented accordingly. When the comminution is carried out by comminution of the mixture, the comminution time depends on the intensity of the comminution, but by comminution of the mixture for a time of from 5 minutes to 10 hours, in particular from 15 minutes to 5 hours, the mixture can be satisfactorily spray-dried. I discovered that it is possible. Another comminution method that can be used according to the invention is to simultaneously expose a suspension of solid material in a liquid medium to vigorous stirring and shearing action.
This process is conveniently carried out using a stirring device that is rapidly rotatable and includes means for generating a shearing action. This device preferably has at least
It can be rotated at 1000 rpm, conveniently at least 5000 rpm, for example 10000 rpm. The shearing action is
This is accomplished by providing spaced upright concentric projections on a disc mounted on the stirring shaft, and also placing similar stationary projections that fit into the gaps between the spaced projections on the stirring shaft. can. The protrusion has a slot formed therein, by means of which the liquid medium is drawn through the thread when the stirring shaft is rotated. The gap between the rotatable and stationary projections is small, typically no more than 1 millimeter. The relative movement of the protrusions on the rotating stirring shaft with respect to the stationary protrusions, and the narrow gaps between the protrusions, generate high shearing effects and break up particles of solid material. A combination of vigorous stirring and shearing action can be achieved using suitable equipment to emulsify the oil in a liquid with which it is immiscible. Suitable equipment for this purpose is the Ultra Turrax type stirrer (Janke and
available from Kunkel KG IKA Werke) or high shear mixer (Silverson Machines
Limited of Chesham, Buckinghamshire;
available from England). A suspension of solid material in a liquid medium is pulverized by exposure to simultaneous vigorous stirring and shear, the time of which depends on the equipment used to effect the simultaneous vigorous stirring and shearing. The time period typically ranges from 10 seconds to 5 hours, conveniently from 2 minutes to 2 hours. Using an Ultra Turax type stirrer, times are typically 10 seconds to 1 hour, conveniently 1 hour.
~20 minutes, most preferably 2 minutes to 10 minutes. Using a Silverson high shear mixer, a time of 1 to 2 hours is generally required.
It is desirable to cool the mixture during simultaneous vigorous stirring and shearing. This is because heat is generated as a result of the simultaneous vigorous stirring and shearing and the temperature of the liquid medium can increase considerably. Simultaneous vigorous stirring and shearing is conveniently carried out with a suspension of solid material in a liquid medium when the suspension is initially at ambient temperature. It has been discovered that simultaneous vigorous stirring and shearing, in addition to generating heat, can result in highly viscous dispersions. It is therefore preferable to use suspensions of solid substances in a liquid medium, the solids content of which is not more than 50% by weight, preferably not more than 35% by weight of the total weight of the suspension. Preferably, the suspension contains at least 5% by weight, preferably at least 15% by weight, relative to the total suspension. It has been discovered that the milled mixture can form a gel if not continuously stirred between the end of the milling stage and the subsequent processing stage. The formation of such gels depends on the liquid medium and the Lewis base compound present; for example, if the liquid medium is toluene and the solid material is magnesium chloride milled with ethyl benzoate, then the When the molar ratio was 3:1, a gel was obtained, but when the molar ratio was higher, for example 6:1 or 12:1, the tendency for gel to form was greatly reduced. When a gel forms, the mixture can be converted to a suspension by adding more liquid medium and stirring the mixture. The additional amount of liquid medium may be equal to or even greater than the volume of the gel. The mixture obtained after comminution may be treated, if desired or if necessary, with a transition metal compound and/or a Lewis base compound and/or with a non-metal halide, for example in EP-A-0037182. subject to a spray-drying process as described in No. An apparatus that can be used in the spray drying process of the present invention is shown in the accompanying drawings. A finely divided mixture of a solid substance and a liquid medium is
Spray drying is optionally performed before or after contacting the transition metal compound, and this spray drying can be carried out using conventional spray drying techniques. This mixture is then passed through a suitable atomizer to generate a spray or dispersion of droplets of the mixture, a stream of hot gas is arranged to contact the droplets and evaporate the liquid medium, and the solid product is separated. Collect. Examples of suitable atomizers for producing droplets of suspension are nozzle atomizers and rotating disk atomizers. As is well known, the transition metal component of olefin polymerization catalysts is sensitive to oxidation, so when the solid material is or contains a transition metal, the spray drying step is preferably essentially oxygen free. Carry out in a moisture-free and water vapor-free medium. However, if the solid material does not contain transition metals, it is not necessary to use an oxygen-free and water vapor-free medium, although the use of such a medium is preferred to avoid undesirable substances in the spray-dried product. Sometimes. A suitable gaseous medium for carrying out the spray drying is high purity nitrogen, but other gaseous mediums can be used, especially those that do not have an adverse effect on the transition metal compound. Thus, examples of other gaseous substances that can be used are hydrogen and inert gases such as argon or helium. In order to prevent the ingress of oxygen-containing substances into the spray drying apparatus, the apparatus is preferably operated at a slightly higher pressure, for example about 1.2 Kg/cm ² absolute. Although the temperature can be below the boiling temperature of the liquid medium under the pressure conditions existing within the spray dryer, the temperature must be lower than the boiling temperature of the liquid medium before the droplets reach the walls or discharge point of the spray dryer. The temperature should be sufficient to steam and dry at least the outer surface of the droplets. The temperature at which the spray drying is carried out is preferably relatively low to avoid adversely affecting the spray dried solid material, which is important for the components of the olefin polymerization catalyst. Therefore, especially when transition metal compounds are present, the temperature of the hot gas introduced into the spray drying apparatus does not exceed about 200°C and the temperature of the droplets or spray-dried material does not exceed 150°C, preferably the droplets or The temperature of spray-dried material is 80℃~130℃
Preferably, the temperature is within the range of .degree. It will be appreciated that the temperature of the hot gas will be at least equal to the maximum temperature achieved by the drops or spray dried material. Although the hot gas can be arranged to pass in countercurrent to the droplets of the mixture, co-current flow of the hot gas and the mixture is typically used. When using cocurrent flow, the atomizer is placed at the top of the atomizing device, and the hot gas is introduced into the top of the device and withdrawn near the bottom of the device. Some of the spray-dried solids collect at the bottom of the apparatus, from where they are fed, preferably continuously, by suitable means, such as a star feeder valve,
It can be removed by means of a screw conveyor or into a hot gas stream. The hot gas cooled by passing through the spray dryer can be separately withdrawn from the spray dryer. The hot gas can be passed through a cyclone to remove entrained solids, and the solids removed in the cyclone can be added to the solids removed separately from the spray dryer. The vapor of the liquid medium present in the hot gas is preferably condensed in a suitable condenser, and the condensed liquid medium can be reused and mixed with the solid material and subsequently pulverized. This gas can then be reheated and recycled to the spray dryer. Spray drying conditions can be adjusted to obtain the desired particle size, and essentially all of the particles of the final spray dried material, i.e.
At least 90% by weight is between 5 and 100 microns, especially
A range having an average size of 10 to 80 microns, such as about 30 microns, is preferred. The spray-dried solid material can be used as a component of the olefin polymerization catalyst, or can be used to make a component of the olefin polymerization catalyst, so that the form of the spray-dried solid material is such that the resulting olefin polymer is It should be such that it has a satisfactory particle shape. The solid material is subjected to a pretreatment in which it is ground with a Lewis base compound in the essential absence of a liquid medium, after which an inert liquid medium is added and the mixture is ground and subsequently spray-dried. It is preferable. Thus, in accordance with a preferred aspect of the invention, a solid material is ground with a Lewis base compound in the essential absence of a liquid medium below the Lewis base compound, an inert liquid medium is added to the ground material, and the material is milling to form a dispersion of the solid material in an inert liquid medium, spray-drying the dispersion, and collecting the spray-dried solid material, where (1) the solid material comprises at least one of the transition metal compounds; 1
or (2) after spray-drying the dispersion, contacting the spray-dried solid material with at least one transition metal compound. The process of the present invention, together with a preferred optional pre-grinding step, is based on the prior art, e.g.
1421943, 1485181, 1512730, 1527736 and
1559194, in the preparation of the catalyst disclosed in 1
or as an additional step. The spray-dried solid obtained by the method of the invention is an agglomerate of small particles obtained by milling a mixture of solid material and liquid medium. Generally, when using a spray-dried solid, it is exposed to shear from agitation or circulation through piping, and these shear forces break up at least a portion of the spray-dried solid into small particles. To minimize such breakage, it is preferred to add to the spray-dried solid substances that can make the spray-dried solid more resistant to abrasion and also promote particle agglomeration during the spray-drying process.
For convenience, such substances will hereinafter be referred to as "wear inhibitors." The wear inhibitor is preferably present during the spray drying process and is typically present as a solution in a liquid medium in which the solid material is suspended. The attrition inhibitor is such that it has no appreciable adverse effect on the activity and stereospecificity of the olefin polymerization catalyst system containing the solid material obtained by the process of the invention, or should be used in such amounts. When the material obtained by spray drying is subsequently suspended in a liquid medium, the attrition inhibitor preferably reduces the spray-dried solid material into small particles in the presence of the liquid medium in which the solid material is to be suspended. It should be such that it causes at least minimal dispersion. Therefore, the attrition inhibitor is preferably soluble in the liquid medium used in the spray drying process, but is inert or has a low It has solubility. Wear inhibitors include, for example, polystyrene, polymethyl methacrylate, polyvinyl acetate,
It can be atactic polypropylene, or an AB block copolymer such as t-butylstyrene/styrene. Not all wear inhibitors are equally effective. The use of an attrition inhibitor during spray drying of a suspension results in a spray dried solid material that is in the form of a harder agglomerate than a similar spray dried solid material obtained without its use. The amount of wear inhibitor is between 0.5 and 10% by weight with respect to the solid material present in the suspension. The suspension containing the wear inhibitor can be prepared by conventional spray drying techniques,
For example, the applicant's European patent application publication no.
Spray dry using the technique described in 0037182. Although the attrition inhibitor can be present during milling of the mixture of solid material and liquid medium, it can also be added at the completion of milling and before spray drying. The products obtained by the method of the invention can be used together with non-transition metals to form polymerization catalyst systems. Thus, other aspects of the invention include (1) a transition metal composition that is a spray-dried product produced by the process of the invention; and (2) an organic compound of aluminum, a member of Group A of the Periodic Table. A polymerization catalyst is provided which is a product obtained by mixing together an organic compound of a metal or a complex of an organic compound of a metal from group A or group A of the periodic table and an organoaluminum compound. Ru. The transition metal composition, component 1 of the catalyst system, is the product obtained in the method described above. Component 2 of the catalyst can be an organomagnesium compound, for example a dihydrocarbylmagnesium compound, a hydrocarbylmagnesium halide compound, or an alkoxymagnesium compound, preferably one containing an alkyl group in addition to an alkoxy group. Alternatively, as the complex of a magnesium compound and an aluminum compound, for example, a complex of a magnesium alkyl and an aluminum alkyl can be used. Component 2 can be a complex of a group A metal and an organoaluminum compound, for example a compound of the lithium aluminum tetraalkyl type. Preferably component 2 is an organoaluminum compound,
For example, aluminum hydrocarbyl sulphate, or aluminum hydrocarbyl hydrocarbyloxy or more preferably aluminum hydrocarbyl halides such as dihydrocarbyl halides or particularly preferably aluminum trihydrocarbyl compounds or dihydrocarbyl aluminum halides. Particularly preferred aluminum compounds are aluminum trialkyls, especially those in which the alkyl group contains 2 to 10 carbon atoms, such as aluminum triethyl, aluminum tri-isobutyl and aluminum trioctyl. The catalyst system may be only two components, especially if the monomer to be polymerized is ethylene or contains sufficient ethylene to produce a polymer containing a substantial proportion of ethylene, e.g., at least 70% by weight ethylene. It can consist of
However, when component 2 of the catalyst system is an aluminum trihydrocarbyl compound and the catalyst system is used for the polymerization of higher olefin monomers such as propylene, it is preferred that the catalyst system also contains a Lewis salt compound. Lewis base compounds that can be used as further components of this catalyst system are Lewis base compounds of the type disclosed herein as suitable for use in the preparation of transition metal compositions that are milled and spray dried in accordance with the present invention. be. Particularly preferred Lewis base compounds for use as further components of this catalyst system are esters and organosilicon compounds, such as esters of carboxylic acids containing aromatic groups, such as ethyl benzoate, butyl benzoate, methyl p- Methyl benzoate, ethyl p-methoxybenzoate, and ethyl phenyl acetate and also dialkyl phthalates and phenyl alkoxysilanes. In addition to or instead of Lewis base compounds that can be present as further components of the catalyst system,
Substituted or unsubstituted polyenes, acyclic polyenes, e.g. 3-
methylheptanetriene (1,4,6) or cyclic polyenes, such as cyclooctatriene, cyclooctatetraene,
or cycloheptatrienes, or alkyl- or alkoxy-substituted derivatives of such cyclic polyenes, or tripyrium salts or complexes, or tropones or tropones can be present. The proportions of components 1 and 2 of this catalyst system can vary within wide limits, as is well known in the art. Although the particularly preferred ratios will depend on the type of material used and the absolute concentration of the components, it is generally preferred that at least 1 mole of component 2 be present for each gram atom of transition metal present in component 1 of the catalyst system. . The number of moles of component 2 per each gram atom of transition metal in component 1 can be as high as 1000, but preferably does not exceed 500, and in some transition metal compositions can be as low as 25,
For example, it may be 5 to 10. When the catalyst system contains a Lewis base as its further component, the Lewis base compound comprises each one of component 2.
Preferably it is present in an amount of up to 1 mol per mole, especially from 0.1 to 0.5 mol. However, depending on the particular organometallic compound and Lewis base compound, the proportions of Lewis base compounds may need to be varied to achieve an optimal catalyst system. When the catalyst system contains a polyene, the polyene is present in an amount of not more than 1 mol, especially 0.01 mol, for each mol of component 2.
Present in an amount of ~0.20 mol. When the catalyst system contains both a Lewis base component and a polyene, both of these materials are present in amounts of up to 1 mole for each mole of component 2. The catalyst system according to the invention is suitable for the polymerization and copolymerization of unsaturated monomers, in particular ethylenically unsaturated hydrocarbon monomers, such as olefinic monomers. Thus, as a further aspect of the invention, a polymer or copolymer of unsaturated monomers comprising contacting at least one ethylenically unsaturated hydrocarbon monomer with a polymerization catalyst as defined above under polymerization conditions. A manufacturing method is provided. The monomers that can be contacted with the catalyst system are preferably those having the formula CH ₂ =CHR ¹ where R ¹ is a hydrogen atom or a hydrocarbon group. Thus, the monomers are ethylene, propylene,
Butene-1, Pentene-1, Hexene-1, 4-
Methylpentene-1, styrene, 1,3-butadiene or other monomers satisfying the above formula. The monomers are preferably olefinic monomers, especially aliphatic monoolefins containing up to 10 carbon atoms. The monomers can be homopolymerized or copolymerized together. When copolymerizing propylene, it is preferred that the copolymerization with ethylene is carried out, preferably using a sequential copolymerization process as described in British Patents 970478, 970479 and 1014944. When ethylene is copolymerized according to the method of the present invention, a mixture of ethylene and the desired comonomer, such as butene-1 or hexene-1, is used, such that the mixture of monomers is of essentially the same composition throughout the polymerization process. It is preferable to carry out the copolymerization. Component (1) of the catalyst can be mixed with one or more of the other components of the catalyst in the presence of the olefin monomer. When the catalyst contains a Lewis base compound, it is preferable to premix the organometallic compound as component (2) with the Lewis base compound, and then mix this premix with the reaction product as component (1). As is well known, Ziegler-Natsuta type catalysts are sensitive to the presence of impurities in the polymerization system. Therefore, a high degree of purity of monomer, and a diluent (if used), e.g.
It is desirable to use monomers containing less than ppm by weight of water and less than 1 ppm by weight of oxygen. High purity substances are included in the UK patent specification
1111493, 1226659 and 1383611. The polymerization can be carried out in known manner, for example in the liquid phase using an excess of liquid monomer as polymerization medium, in the presence or absence of an inert diluent such as a suitably purified paraffinic hydrocarbon, or in the gas phase. It can be carried out in Here, gas phase means the essential absence of liquid medium. When the polymerization is carried out in the gas phase, it is possible to introduce the monomer, for example propylene, as a liquid into the polymerization vessel, and the liquid monomer evaporates, thereby creating an evaporative cooling effect, and all of the polymerization takes place. Establishing temperature and pressure conditions in the polymerization vessel such as occur with gaseous monomers,
This can be done by manipulating. Polymerization in the gas phase can be carried out using conditions such that the monomer is at a temperature and partial pressure close to its dew point temperature and pressure, for example as detailed in British Patent Specification 1532445. . Polymerization in the gas phase is
It can be carried out using any technique suitable for carrying out gas-solid reactions, such as fluidized bed reactor systems, stirred bed reactors or ribbon blender type reactors. When using the catalyst system of the present invention, ethylene can be polymerized or copolymerized with butene-1 as a comonomer in a fluidized bed reactor system to produce polymers in high yields. The fluidizing gas is the gas mixture to be polymerized with hydrogen present as a chain transfer agent to adjust the molecular weight. Thus, about
In the copolymerization of ethylene and butene-1 to produce ethylene copolymers with densities less than 940 Kg/m ³ , the gas composition is typically between 50 and 60
mol % ethylene, 15-25 mol % butene-1 and the balance, excluding inerts and impurities, is hydrogen. The polymerization can be carried out in a batch or continuous manner, and the catalyst components can be added separately to the polymerization vessel or all catalyst components can be mixed together before introduction into the polymerization reactor.
If all of the catalyst components are premixed, this premixing is preferably carried out in the presence of monomers, and such premixing is such that the monomers are at least partially polymerized before the catalyst is introduced into the polymerization vessel. Dew. If the polymerization is being carried out in the gas phase, the components of the catalyst can be added to the polymerization reactor suspended in the gaseous monomer or monomer mixture stream. The polymerization can be carried out in the presence of a chain transfer agent, such as hydrogen or zinc dialkyl, to adjust the molecular weight of the resulting product. When hydrogen is used as a chain transfer agent in the polymerization of propylene, it is 0.01 to 5.0 mol% with respect to the monomer,
In particular, it is preferably used in an amount of 0.05 to 2.0 mol%.
When the monomer to be polymerized is ethylene or a mixture in which ethylene is the main polymerizable component (mono basis), the amount of hydrogen used is higher, for example in the homopolymerization of ethylene the reaction mixture is
It can contain more than mol % hydrogen, while when copolymerizing ethylene, hydrogen proportions of up to 35 mol % are typically used. The amount of chain transfer agent depends on the polymerization conditions, especially the temperature, which is typically 20°C when the polymerization pressure is below 50Kg/ ^cm2 .
~100°C, preferably 50°C to 85°C. Polymerizations can be carried out at pressures previously suggested for carrying out polymerizations of monomers such as olefinic monomers. However, polymerization
Although it can be carried out at pressures up to 3000 Kg/cm ² and the polymerization temperature at that pressure can be as high as 300°C, it is preferred that the polymerization is carried out at relatively low pressures and temperatures. Although the polymerization can be carried out at atmospheric pressure, it is preferable to carry out at slightly higher pressure, so that the polymerization
It is preferred to carry out at a pressure of Kg/cm ² to 50 Kg/cm ² , preferably 5 to 30 Kg/cm ² . Polymerization temperature is preferably above ambient temperature, typically 100°C
will not exceed. Referring to Figure 2 of the accompanying drawings, the airtight spray drying container 1 consists of an upper cylindrical part 2 and a lower generally conical part 3. Upper part 2 is cover plate 4
has. The spray nozzle assembly 5 is located within a plenum chamber 6, which is mounted on the cover plate 4. Spray nozzle assembly 5 contains an inner conduit 7 and an outer conduit 8. Conduit 7 is a continuation of conduit 9. Conduit 9 is connected to a source (not shown) of a suspension containing a finely divided mixture of solid material and liquid medium. Conduit 8 is connected to an inert gas source (not shown). Conduits 7 and 8 are essentially coaxial and taper at their lower ends. Nozzle assembly 5 has an orifice 10 at its lower end, which orifice 10 is formed by an opening in both conduits 7 and 8. Conduit 11 is connected to plenum chamber 6 and to a source of heated inert gas (not shown). Near the bottom of the container 1 there is a conduit 12 which exits from inside the container 1 through the side of the conical section 3 . A conduit 13 in which the valve means 14 is located is connected to the bottom of the conical part 3;
and also connected to a hopper (not shown) for storing dry solids. In practice, the gas flow through conduit 8 draws the suspension through conduits 9 and 7. The gas and suspension pass through orifice 10 and form a spray of droplets. The hot inert gas passing through conduit 11 and plenum chamber 6 passes through orifice 10 and evaporates the fluid medium from the suspension droplets. The inert gas containing the evaporated liquid medium and some entrained spray-dried solids is passed from within the vessel 1 into the conduit 12.
go outside through. Most of the spray-dried solids collect at the bottom of the conical section 3 and from there into the conduit 1.
3 through operation of the valve means 14. The inert gas passing through conduit 11 is preferably
The temperature ranges from 130 to 150°C. The apparatus shown in FIG. 2 is essentially the same as that shown in FIG. 2, except that the spray nozzle has been replaced with a disk atomizer. In FIG. 3, corresponding parts are designated with the same reference numerals as in FIG. A disc atomizer 15 mounted on the end of the output shaft 16 of the high speed gearbox/motor assembly 17 is
It is located near the top of the container 1. The disc 15 consists of two plates 18 and 19, between which a series of radial vanes 20 are fixed. Room 21
is a plate 18 surrounding the drive shaft 16 and above the disk 15.
extends to Plate 18 has a central opening indicated at 22. Plenum chamber 16 surrounds chamber 21 . Conduit 23
is connected to chamber 21 and to a source of suspension containing solid material (not shown). In the example, the disc 15 is rotated at a speed in the range of 500 to 25,000 rpm. A suspension, which is a finely divided mixture of solid material and an inert liquid medium, such as magnesium chloride-ethylene zoate product in toluene, is passed through conduit 23 and chamber 21 to plate 18 of disk 15. and 19. The high speed rotation of the disc 15 and the blade 20 is
The suspension is advanced around the disk 15, from where it is thrown off as a spray of droplets. The hot inert gas passes through conduit 11 and flows around rotating disk 15 through plenum chamber 6. The hot inert gas evaporates the liquid medium from the suspension. The evaporated liquid medium and some entrained spray-dried solids leave the container 1 through the conduit 12. The bulk of the spray-dried solids collects at the bottom of the conical section 3 from where it is extracted from the conduit 13 by operation of the valve means 14. The inert gas through conduit 12 goes to a cyclone (not shown) to recover entrained solids, then to a cooler (not shown) to recover liquid vapor, and finally to a reheater (not shown). Go to ). The reheated inert gas is then recycled to conduit 11. The spray-dried solids passing through conduit 13 are
Go to storage hopper (not shown). Other alternative arrangements and spray drying techniques will be apparent to those skilled in the art and may be used without departing from the scope of the invention as defined herein. The following illustrative examples of the invention illustrate various aspects of the invention. In the examples, all operations are performed under an atmosphere of nitrogen unless otherwise indicated. All glass equipment was dried in an air oven at 120°C for at least 1 hour and purged with nitrogen. Note that Examples 1 to 25 and 42 to 56 are shown as reference examples, and are not examples of the present invention. Examples 1 to 9 illustrate the incorporation of the method of the invention into the manufacture of transition metal compositions carried out in accordance with the applicant's UK patent specification 2103627A entitled “Transition metal compositions, manufacture and use” do. In Examples 1 to 10, fine grinding was carried out by grinding in a ball mill. Example 1 (A) Milling of Magnesium Chloride and Ethyl Benzoate Siebtechnik SM6 Vibromill chamber with a total usable volume of approximately 1.5 dm ³ and containing 180 stainless steel balls of 25 mm diameter. sealed, 0.3×10 ^-3
Evacuate to a pressure of Kg/cm ² and purge with nitrogen to provide a nitrogen atmosphere in the mill. A mixture of nitrogen and ethylene glycol at 0°C was passed through the jacket of the mill, and the mill was operated at a frequency of 1500 oscillations/min and 2
It was vibrated with an amplitude of mm. 182 g of essentially anhydrous magnesium chloride (BDH technical grade) was added to the mill chamber while the mill was vibrating. After adding the magnesium chloride, the mill was allowed to vibrate for approximately 15 minutes and then 91 cm ³ of ethyl benzoate was added to the vibrating mill over a period of approximately 5 minutes. The mill was then shaken for an additional 24 hours while the 0°C water and ethylene glycol mixture continued to be passed through the mill jacket. (B) Milling with toluene After 24 hours, 500 cm ³ of toluene was added to the mill chamber while the mill was kept vibrating. Milling continued for an additional 3 hours at 0° C. in the presence of added toluene. After 3 hours, the mill was inverted, the inverted mill was vibrated, and the milled magnesium chloride-ethylbenzoate was collected under a nitrogen atmosphere. The mill chamber was washed with 800 cm ³ of toluene, which was added to the previously removed suspension. The molar ratio of magnesium chloride to ethyl benzoate in the mill was about 3 to 1. Add polystyrene (“Styron”) in toluene to the milled mixture while stirring it.
A 10% weight/volume solution of 686/7--available from Dow Chemical Company) was added to provide 2% by weight polystyrene with respect to the milled magnesium chloride-ethyl benzoate. After standing overnight, the mixture became solid and it was necessary to add more toluene and stir the mixture to resuspend the solid particles. The diluted mixture had a solids content of approximately 15% by weight. (C) Spray Drying of the Magnesium Chloride/Ethyl Benzoate Suspension In step (B) all of the suspension is dried in a glass laboratory scale spray similar to that shown in Figure 2 of the accompanying drawings and described above. Spray drying was performed using a drying device. This spray drying device has a diameter of 15cm,
0.7 m in length, using a substantially hemispherical bottom instead of the conical section 3, omitting the conduit 12, omitting the valve 14 in the conduit 13, and connecting the conduit 13 directly to the cyclone; had a receiver that collected the solid material. The spray nozzle used was a 1/4 JAU automatic air spray nozzle (Spraying Systems Co., Ltd., with a 0.72 mm diameter nozzle).
(obtained from USA). A nitrogen stream preheated to a temperature of 140-150℃ is introduced into conduit 1.
Spraying was carried out by passing through 170-180 dm ² /min. Nitrogen at a pressure of approximately 2.3 Kg/cm ² absolute was introduced into the spray nozzle. The suspension obtained in step (B) is transferred from the stirred storage flask to the spray nozzle and an overpressure of 0.25 Kg/cm ² of nitrogen is applied to the storage flask (i.e. the total pressure in the storage flask is approximately 1.28 Kg/ ^cm2 ). (D) Sample of spray-dried product from step (C) (96
g) was transferred to a 1.8 dm ³ jacketed glass vessel equipped with a stirrer. 1 dm ³ of titanium tetrachloride was added to the vessel, the stirrer was started and heat was applied to the jacket. Heating was continued until a temperature of 100°C was reached, which took 0.5 hours.
The temperature was maintained at 100°C and stirring continued for 3 hours.
At the end of 3 hours, stirring was stopped and the solids were allowed to settle while continuing to heat the contents of the vessel. Four hours after stirring is stopped, the upper liquid is siphoned off, leaving behind the settled solids. The heating is stopped and the contents of the container are allowed to cool by standing overnight. The contact with titanium tetrachloride is repeated by adding 1 dm ³ of titanium tetrachloride to the cooled residue remaining from the previous contact, the process conditions being as described above. (E) Washing: Adding to the residue obtained from step (D) a sufficient amount of a heptane fraction, at least 90% of which is n-heptane (hereinafter referred to as "n-heptane fraction").
at ambient temperature to give a total volume of 1.5d
^m3 . The mixture was stirred and heated to reflux (approximately
100℃). Stirring at reflux temperature was continued for 1 hour and then stopped. After an additional 2.5 hours, the upper liquid, still heated, was siphoned off, leaving behind the settled solids. The heating is stopped and a sufficient amount of n-heptane fraction is added to the hot residue at ambient temperature to approximately 45°C.
Let the total volume be ^1.5dm3 . The mixture was stirred for 15 minutes without heating. The stirrer was stopped and the solids were allowed to settle. After 1.25 hours, the upper liquid was siphoned off, leaving behind the settled solids. To the residue obtained from the previous washing step, a sufficient amount of n-heptane fraction at ambient temperature was added to give a total volume of 1.5 dm ³ at ambient temperature. The mixture was stirred and allowed to settle for 15 minutes without heating.
After 1.25 hours, the upper liquid was siphoned off, leaving behind the settled solid. The cold residue obtained from the third step washing was
Diluted with heptane fraction to a final volume of 1.0 dm ³ and transferred the mixture to a storage vessel under nitrogen atmosphere. Example 2 The procedure of Example 1 was repeated with the changes described below. In step (A), 255 g of magnesium chloride and
32 cm ³ of ethyl benzoate was used. The molar ratio of magnesium chloride to ethyl benzoate is approximately 12
It was 1 to 1. In step (B), 400 cm ³ of toluene is used;
The mixture was then milled for 0.5 hours. The mill chamber was flushed with 300 cm ³ of toluene. The mixture was allowed to stand overnight without adding polystyrene, and the mixture was still fluid the next morning. The polystyrene solution was added while stirring the mixture to provide 1.5% by weight polystyrene with respect to the milled magnesium chloride-ethyl benzoate. In step (C) heated nitrogen was passed at a rate of 190 dm ³ /min. Nitrogen at a pressure of approximately 1.25 Kg/cm ² absolute was introduced into the spray nozzle. The excess pressure applied to the storage flask was 0.14 Kg/cm ³ . In step (D) an 800 cm ³ jacketed glass vessel with a stirrer was used. 25.5 g of the spray dried from step (C) were used and 255 cm ³ of titanium tetrachloride were used for each treatment with titanium tetrachloride. At the end of the second treatment with titanium tetrachloride, the solid was allowed to settle for 1.5 hours and the upper liquid was removed, but the mixture was not cooled. In step (E), four washes are carried out, each wash step consisting essentially of the dodecane isomer and
300 cm ³ of aliphatic hydrocarbons (hereinafter simply referred to as “aliphatic hydrocarbons”) with a boiling point in the range 170°C to 185°C
It was carried out using The first and second washes were carried out by heating the mixture to 100° C. and stirring at this temperature for 1 hour. 1st
A second wash was carried out by adding an aliphatic hydrocarbon to the hot residue obtained after the second treatment with titanium tetrachloride. A second wash was carried out by adding aliphatic hydrocarbons to the hot residue obtained after the first wash. Heating was stopped after the second wash and a third wash was performed by adding the aliphatic hydrocarbon to the hot residue from the second wash and stirring for 15 minutes without heating. After removing the top liquid from the third wash, the mixture was cooled overnight and a fourth wash was performed on the cold residue of the third wash. The residue was brought to a final volume of 255 cm ³ with aliphatic hydrocarbon. Example 3 The procedure of Example 2 was repeated with the changes described below. In step (A), 207 g of magnesium chloride and
52 cm ³ of ethyl benzoate was used. The molar ratio of magnesium chloride to ethyl benzoate was approximately 6:1. In step (B), the mill chamber was flushed with 200 cm ³ of toluene. After standing overnight, the mixture was still fluid but viscous. After adding the polystyrene solution, an additional 100 cm ³ of toluene was added. In step (C), nitrogen at a pressure of about 1.35 Kg/cm ² absolute was introduced into the spray nozzle. In step (D) 25 g of the spray-dried product from step (C) were used and for each treatment with titanium tetrachloride 250 cm ³ of titanium tetrachloride were used. For each titanium tetrachloride treatment, the solids were allowed to settle for approximately 1 hour before the upper liquid was siphoned off. In step (E), washing was carried out using an n-heptane fraction. The residue was cooled overnight after the first hot wash. A second hot wash was performed, and immediately after the second hot wash, two cold washes were performed in succession. The residue was diluted with n-heptane fraction to a final volume of 250 cm ³ . Example 4 The procedure of Example 3 was repeated with the changes described below. In step (A), 196 g of magnesium chloride and
62 cm ³ of ethyl benzoate was used. The molar ratio of magnesium chloride to ethyl benzoate is approximately 4.8
It was 1 to 1. In step (B), after adding the polystyrene solution, an additional 200 cm ³ of toluene was added. In step (C), the preheated nitrogen is at a temperature of 140°C and the overpressure applied to the storage flask is 0.05
It was Kg/ ^cm3 . In step (D) 28 g of the spray-dried product from step (C) were used and for each treatment with titanium tetrachloride 280 cm ³ of titanium tetrachloride were used. In step (E), 330 cm ³ of n-heptane fraction was used for each washing step. The residue was diluted with aliphatic hydrocarbon to a final volume of 280 ^cm3 . Example 5 The procedure of Example 3 was repeated with the changes described below. In step (A), 236 g of magnesium chloride and
78 cm ³ of ethylbenate was used. Molar ratio of magnesium chloride to ethyl benzoate is 4.6:1
It was hot. In step (B), the mill chamber was flushed with 340 cm ³ of toluene. The polystyrene solution and a further 265 cm ³ of toluene were added while stirring and the mixture was allowed to stand overnight without stirring. In the morning,
The mixture was very viscous and an additional 300 cm ³ of toluene was added to the mixture while stirring. In step (C), the preheated nitrogen was at a temperature of 140°C. In step (D), 28.5 g of the spray-dried product from step (C) was used and 285 cm ³ of titanium tetrachloride were used for each treatment with titanium tetrachloride. A second treatment with titanium tetrachloride was carried out immediately after the first treatment without cooling the residue. After the second treatment with titanium tetrachloride, the residue was cooled overnight. In step (E), washing was carried out using 340 cm ³ of aliphatic hydrocarbon for each wash. Each wash was performed immediately after the previous wash. The residue was diluted with aliphatic hydrocarbon to a final volume of 285 ^cm3 . Example 6 The Example 3c procedure was carried out with the modifications described below. In step (A), 205 g of magnesium chloride and
63 cm ³ of ethyl benzoate was used. The molar ratio of magnesium chloride to ethyl benzoate is approximately 4.9
It was 1 to 1. In step (B), the mill chamber was flushed with 300 cm ³ of toluene. Add polystyrene solution to 1% by weight with respect to magnesium chloride-ethylbenzoate
of polystyrene was supplied. No further toluene was added. In step (C), the preheated nitrogen is at a temperature of 135-138°C and the overpressure applied to the storage flask is 0.07
Kg/cm ² and about one-fifth of the mixture was spray dried. In step (D) 24 g of the spray-dried product from step (C) were used and for each treatment with titanium tetrachloride 240 cm ³ of titanium tetrachloride were used. In step (E), washing was carried out using 360 cm ³ of aliphatic hydrocarbon for each wash. The residue was diluted with aliphatic hydrocarbon. Example 7 After spray drying one-fifth of the suspension in step (C) of Example 6, a polystyrene solution was further added to the remaining suspension to give 2% by weight with respect to the milled magnesium chloride-ethylbenzoate. of polystyrene and another 5 of the original suspension.
One portion was spray dried under conditions as in step (C) of the example. Further polystyrene solution was then added to the remaining suspension to provide 4% by weight polystyrene with respect to the milled magnesium chloride-ethyl benzoate. This suspension was then subjected to conditions as in step (C) of Example 6.
Spray dried (approximately 1/5 of the original suspension). 28 g of the spray-dried product in the presence of 4% by weight polystyrene were treated with titanium tetrachloride and washed as in steps (D) and (E) of Example 6, except that 280 cm ³ of titanium tetrachloride and 420 cm ³ of aliphatic hydrocarbon were used, and the residue was diluted to a final volume of 290 cm ³ . Example 8 The procedure of Example 3 was repeated with the changes described below. In step (A), 212.4 g of magnesium chloride;
53.5 cm ³ of ethyl benzoate and 53.5 cm ³ of toluene were used. The molar ratio of magnesium chloride to ethyl benzoate was approximately 6:1. In step (B), the mill chamber was flushed with 300 cm ³ of toluene. The total suspension was divided into two approximately equal parts. A polystyrene solution was added to one part of the suspension to provide 2% by weight polystyrene with respect to the milled magnesium chloride-ethyl benzoate. This suspension was diluted with sufficient amount of toluene to obtain a final suspension with a solids content of 25% by weight. In step (C), nitrogen at a pressure of about 1.42 Kg/cm ² absolute was introduced into the spray nozzle and the overpressure applied to the storage flask was 0.2-0.25 Kg/cm ² . The spray nozzle was located at the bottom of the spray dryer and introduced hot nitrogen into the top of the spray dryer so that the spray was directed upwards against a countercurrent flow of hot nitrogen. In step (D), 30 g of the spray-dried product from step (C) were used and with titanium tetrachloride 300 cm ³ of titanium tetrachloride were used for each treatment. In step (E), washing was carried out using 350 cm ³ of aliphatic hydrocarbon for each wash. The residue was cooled after the first thermal wash, a second thermal wash was performed immediately after the first thermal wash, and the residue was allowed to cool overnight after the second thermal wash. A cold wash was performed on the cold residue of the second hot wash. The residue was brought to a final volume of 300 cm ³ with aliphatic hydrocarbon. Example 9 The remainder of the milled suspension obtained in step (B) of Example 8 was used. The remainder is polymethyl methacrylate (MH254 class - Imperial
A 10% weight/volume solution of (available from Chemical Industries PLC) in toluene was added. This polymethyl methacrylate solution was added to provide 2.0% by weight polymethyl methacrylate with respect to the milled magnesium chloride-ethyl benzoate. This suspension was diluted with toluene to obtain a final suspension with a solids content of 25% by weight. The resulting suspension was then subjected to step (C) of Example 8,
Spray dried, treated with titanium tetrachloride, washed and diluted as in (D) and (E). Example 10 The procedure of Example 3 was repeated with the changes described below. In step (A), 214.3 g of magnesium chloride;
16.9 g of ethyl benzoate and 16 cm ³ of toluene were added to the mill. The molar ratio of magnesium chloride to ethyl benzoate was 20:1. In step (B), the mill chamber was flushed with 300 cm ³ of toluene. To this suspension was added polymethyl methacrylate (as in Example 9) in toluene.
Add 46 ^cm3 of 10% wt/vol solution, then 200 cm3
cm ³ of toluene was added. In step (C), nitrogen at a pressure of about 1.45 Kg/cm ² was introduced into the spray nozzle. The overpressure applied to the storage flask was 0.05 Kg/cm ² . In step (D), the spray-dried product of step (C)
29.5g was used. Only one titanium tetrachloride treatment was performed. The amount of titanium tetrachloride was 295 cm ³ and the solid was allowed to settle for 2 hours and 40 minutes, then the upper liquid was siphoned off and the residue was cooled overnight. In step (E), aliphatic hydrocarbons were used.
350 cm ³ of aliphatic hydrocarbon were added to the residue and the mixture was cooled to 100° C. and kept at that temperature for 1 hour. The solids were allowed to settle for 2 hours and 20 minutes and heating was discontinued. Three further washes were carried out by adding 350 cm ³ of ambient temperature aliphatic hydrocarbon to the residue from the previous wash. The mixture was stirred for 15 minutes, allowed to settle for 1 hour in the second and third wash steps, and overnight in the final wash step. The residue is 300 cm ³ using aliphatic hydrocarbons.
diluted to a volume of Examples 11-21 Polymerizations were carried out in an 8 dm ³ volume stainless steel autoclave. 3 dm ³ of aliphatic hydrocarbon was charged into the autoclave and degassed at 70° C. for 15 minutes at a pressure of 0.07 Kg/cm ² absolute. Next, add 1.1Kg/propylene to this container.
Put in an amount that produces a pressure in cm ² absolute. The aliphatic hydrocarbon was stirred and stirring continued throughout the next procedure. 20 mmol of aluminum tri-isobutyl was added to the autoclave as a 25% by weight solution in aliphatic hydrocarbon. Then 7 mmol of methyl p-methylbenzoate was added to the autoclave as a solution in aliphatic hydrocarbon. A quantity of the suspension of the spray-dried magnesium chloride-supported titanium halide composition obtained in one of Examples 1-10 was then added. The autoclave was maintained at 70° C. while propylene was passed through the autoclave to establish a pressure of 11.5 Kg/cm ² absolute. Then 10 mmol of water was added. The pressure was maintained at 11.5 Kg/cm ² by feeding propylene. After 0.5 hours and again after 1 hour, a further amount of 10 mmol of hydrogen was added to the autoclave. After 2 hours, the propylene feed was stopped and the autoclave was vented to atmospheric pressure. The polymer suspension was placed in a receiver and the polymer was passed through air. Samples of the polymer were dried at 100° C. in a fluidized bed using nitrogen as the fluidizing gas. Further details of the polymerization conditions and properties of the products obtained are given in Table 1.

TABLE Some of the polymer products were subjected to particle size analysis by sieving and the results are listed in Table 2.

[Table] Examples 22-24 Polypropylene was continuously polymerized in the gas phase as described below. To initiate the polymerization, the reactor initially contained approximately 5 Kg of polypropylene powder. This powder had a flexural modulus of 1.45 GN/m ² and contained 4% by weight of polymer soluble in boiling heptane by Soxhlet extraction for 24 hours. Polymerizations were carried out in a 25 dm ³ stainless steel autoclave equipped with a stirrer and a heating jacket. Initially, polypropylene powder was placed in an autoclave. The pressure was reduced to 75 mbar and then a pressure of 1 bar of nitrogen was applied and this procedure was repeated a total of three times. The stirrer was rotated at 60 rpm and stirring continued throughout the next procedure. The autoclave was heated to 80°C and the pressure was reduced to 75 mbar. Liquid propylene was added to the autoclave and evaporated to increase the pressure to 25 Kg/cm ² gauge. Hydrogen was added separately in a proportion of 1.5% by weight with respect to propylene. A solution of trialkylaluminum compound and ester in aliphatic hydrocarbon was fed into an autoclave. A suspension containing the titanium composition was also introduced into the autoclave. The trialkylaluminium compound, ester and titanium composition were added until initiation of polymerization was observed. Liquid propylene continued to be introduced and gaseous propylene was bubbled while catalyst addition continued. Once the polymerization has started, stop the aeration and add liquid propylene at 20°C to the autoclave for 26 hours.
Polypropylene saturated with propylene is introduced discontinuously from the autoclave at a rate that maintains a pressure of Kg/cm ² (approximately 2 Kg/hr) and at the desired rate, typically approximately 2 Kg polymer/hr. I pulled it out. Temperature and pressure were maintained at 70°C and 26Kg/ ^cm2 , respectively. The rate of addition of the titanium composition suspension was adjusted to maintain the desired rate of polymer production. During the autoclave run, the nature of the titanium composition, aluminum trialkyl compound and ester were varied, and the autoclave run continued with a variety of different catalyst systems. After allowing the polymerization to proceed for 60 hours, the catalyst system was changed again to include the use of the product of Example 7.
The titanium composition of Example 7 was approximately 1/cm ³ of suspension.
added as a settled suspension containing g of solids;
And this settled suspension is divided into ^0.08cm3 portions.
Added at a rate of 150 such parts/hour. The trialkylaluminum compound was tri-isobutylaluminum and the ester was methyl p-methylbenzoate. The aluminum compound and ester were mixed with the aliphatic hydrocarbon at ambient temperature and then stored for at least 12 hours before use, both mixing and storage being carried out under a propylene atmosphere at 1 atmosphere of propylene pressure. The premixed solution was 0.68 molar with respect to tri-isobutylaluminum and this solution was added to the autoclave at a rate of 28 cm ³ /hour. Samples of the polymer were taken at various times during the polymerization, and the properties of the polymer products taken at various times are listed in Table 3.

【table】

TABLE A sample of the product taken after 8 hours of polymerization was sieved and the results are listed in Table 4.

Table: Examples 25 and 26 demonstrate the incorporation of the process of the invention into the manufacture of transition metal compositions carried out in accordance with the applicant's UK patent specification 2103627A entitled “Transition metal compositions, manufacture and use” Explain.
In Examples 25-26, milling was carried out with simultaneous vigorous stirring and shearing action. Example 25 (A) Milling of Magnesium Chloride and Ethyl Benzoate A Siebtechnik SM10 Vibromill having a total volume of approximately 38 dm ³ and containing 119 Kg 25 mm diameter stainless steel balls was sealed; The inside of the mill was made into a nitrogen atmosphere by purging with nitrogen. A mixture of water and ethylene glycol at 0°C was passed through the jacket of the mill and the mill was vibrated at a frequency of 1500 vibrations/min and an amplitude of 2 mm. 4Kg of essentially anhydrous magnesium chloride (BDH technical grade) was introduced into the mill while the mill was vibrated. After the magnesium chloride addition, the mill was shaken for about 15 minutes and 2 dm ³ of ethyl benzoate was added to the vibrating mill over a period of about 15 minutes. The mill was then shaken for an additional 24 hours while the 0° C. water and ethylene glycol mixture continued to pass through the mill jacket. After 24 hours, the mill was inverted, the inverted mill was vibrated, and the milled magnesium chloride-ethyl benzoate was collected under a nitrogen atmosphere. The molar ratio of magnesium chloride to ethyl benzoate in the mill was about 3 to 1. (B) Dispersion of milled magnesium chloride-ethyl benzoate in a 1 dm ³ -necked glass flask with heating/cooling jacket in an Ultra Turrax T45 high shear homogenizer (Janke and Kunkel KG IKA Werke (available from ). 630g in this flask
of nitrogen-sparged toluene, 245 g stage (A)
Milled material obtained at and 1.62
g of polystyrene (“Lustrex” HF66-
available from Monsanto Limited). Ambient temperature water was passed through the heating/cooling jacket. The mixture was then simultaneously exposed to vigorous stirring and shear with the homogenizer running at maximum power (initial stirring speed of 10000 rpm) for 5 minutes. During stirring and shearing, the temperature of this mixture increased but did not exceed 50°C. The dispersion was then transferred to a storage container (a 2 dm ³ three-necked glass flask equipped with a stirrer) and an additional 0.8 g of polystyrene was added while stirring. This mixture was stirred for an additional 30 minutes. (C) Spray drying of the magnesium chloride-ethyl benzoate dispersion The dispersion obtained in step (B) was prepared in Example 1.
Spray drying was performed in a glass laboratory scale spray drying apparatus as described in step (C).
The spray nozzle used was a 1/4 JAU automatic air atomizer nozzle (obtained from Spraying Systems Co., USA) with a 0.52 mm diameter nozzle. A nitrogen stream preheated to a temperature of 130°C is introduced into conduit 11.
Atomization was carried out in a nitrogen atmosphere by passing at a rate of 190 dm ³ /min. Nitrogen at a pressure of approximately 0.5 Kg/cm ² gauge was introduced into the spray nozzle through conduit 8. The suspension obtained in step (B) was fed from a 2 dm ³ volume three-necked glass flask to a spray nozzle by applying an excess nitrogen pressure of 0.07 Kg/cm ³ to the flask. (D) Contact with titanium tetrachloride 100 g of the spray-dried product from step (C) are
Transferred to a 2 dm ³ jacketed glass container equipped with a stirrer. 1 dm ³ of titanium tetrachloride was added to the vessel, the stirrer was started and the jacket was heated. Heating was continued until the temperature reached 100°C, which took 0.5 hours. Maintain the temperature at 100℃,
Stirring was continued for 3 hours. At the end of 3 hours,
The stirrer was stopped and the solids were allowed to settle while continuing to heat the contents of the vessel. Two hours after cessation of stirring, the upper liquid was siphoned off, leaving behind the settled solids. Heating was stopped and the contents of the vessel were allowed to cool by standing overnight. The contact with titanium tetrachloride was repeated by adding 1 dm ³ of titanium tetrachloride to the cold residue obtained from the previous contact, and the process conditions were as described above. (E) Washing To the residue obtained from step (D) 1.5 dm ³ of ambient temperature n-heptane fraction was added. The mixture was stirred and heated to reflux temperature (approximately 100°C).
Stirring at reflux temperature was continued for 1 hour and then stopped. After another 30 minutes, while still heating, the upper liquid was siphoned off, leaving behind the settled solid. After 10 minutes, a further 1.5 dm ³ of ambient temperature n-heptane fraction is added to the hot residue and this mixture is
℃ and stirred at that temperature for 1 hour. The stirrer was stopped and the solids were allowed to settle. 1 hour later
The upper liquid layer was siphoned off, leaving behind the settled solids. The heater was turned off and the precipitated solids were allowed to cool overnight. To the residue obtained from the previous cleaning step, add 1dm ³
of n-heptane fraction at ambient temperature was added. The mixture was stirred and allowed to settle for 15 minutes without heating. After 35 minutes, the upper liquid was siphoned off, leaving behind the settled solid. This step 1
Repeated times. The cold residue obtained from the fourth washing step is diluted with n-heptane fraction to a final volume of 1 ^dm3 ;
This mixture was transferred to a storage container under nitrogen atmosphere. A sample (5 cm ³ ) of this mixture was treated with 2N sulfuric acid and the aqueous layer was subjected to spectrophotometric analysis. This mixture contains 2.7 mg atoms/dm ³ of titanium, 72 mg atoms/dm ³
of magnesium and 160 mg atoms/dm ³ of chlorine. The solid component had a titanium content of 1.64% by weight. Example 26 The procedure is similar to that described in Example 25, but
The main difference is that the various steps are carried out in a different order.
The dispersed and spray-dried material was previously treated with titanium tetrachloride and washed. (A) Milling of Magnesium Chloride and Ethyl Benzoate The milled magnesium chloride-ethyl benzoate used was obtained by the procedure of step (A) of Example 25. (B) Contact with titanium tetrachloride The procedure described in Step D of Example 25 was repeated for 5 dm ³
Each treatment with titanium tetrachloride was repeated using a jacketed glass vessel with a volume of 205 g of the product of step (A) of Example 25 and 2 dm ³ of titanium tetrachloride. (C) Cleaning The residue obtained from step B is
3 dm ³ of n-heptane fraction were added. The mixture was stirred and heated to reflux temperature (approximately 100°C). Stirring at reflux temperature was continued for 1 hour and then stopped. After another 3 hours and 20 minutes, the upper liquid was siphoned out, leaving behind the settled solids.
During this time it was still heated. Heating was then stopped and the residual material was allowed to cool overnight. A further washing step was carried out by adding 3 dm ³ of ambient temperature n-heptane fraction to the cold residue. This mixture was stirred and heated to 70 °C for 40 min.
heated to. Stirring was stopped and the solids were allowed to settle while maintaining the temperature at 60°C. 2 hours and 20 minutes later,
The upper liquid was siphoned off, leaving behind the settled solids, heating was discontinued, and the remaining material was allowed to cool by standing for about 68 hours. To the cold residue obtained from the previous washing step, 2.5 dm ³ of n-heptane distillate at ambient temperature was added. The mixture was stirred and allowed to settle without heating. After 2 hours, the upper liquid was siphoned off leaving behind the settled solid. This procedure was repeated twice. The cold residue obtained from the fifth washing step is diluted with n-heptane fraction to a final volume of 1 ^dm3 ;
The mixture was transferred to a storage container under nitrogen atmosphere. (D) Dispersion of Magnesium Chloride-Titanium Tetrachloride Product A sample containing approximately 200 g of the product of step (C) was allowed to settle and the upper n-heptane fraction was removed by siphoning. 1.5 dm ³ of toluene was added, the mixture was stirred for 5 minutes at ambient temperature, allowed to settle and the upper liquid was siphoned off. This step 2
Repeated times. The residual mixture from the third wash (approximately 600 cm ³ ) was
It was introduced into a flask equipped with an Ultra Turax homogenizer as described in step (B) of Example 25. An additional 100 cm ³ of toluene was used to wash the residue from the storage container into the flask. 2.5 g of polystyrene ("Lustrex" HF66) was added to the flask. Ambient temperature water was passed through the heating/cooling jacket. The homogenizer was operated at maximum power for approximately 2.5 minutes. After 1.5 minutes and again after 2.0 minutes, extra toluene (100 cm ³ ) was added. When the stirring is completed, add another 100 cm ³ of toluene and equip the stirrer.
Facilitate the transfer of the dispersion to a 2 dm ^3- volume three-necked glass flask, and with stirring further 2.0
g of polystyrene was added. (E) Spray Drying of Magnesium Chloride-Titanium Tetrachloride Dispersion The dispersion obtained in step (D) was subjected to essentially the same procedure as used in step (C) of Example 25 with the following exceptions: Spray-dried. The diameter of the spray nozzle was 0.72 mm. The preheated nitrogen was at a temperature in the range of 140-145°C. conduit 8
The nitrogen passed through was at a pressure of about 0.56 Kg/cm ² gauge. Initially, the excess nitrogen pressure applied to the mixture in a 2 dm ³ three-necked glass flask was 0.1 Kg/cm ² . The product collected is hereinafter referred to as reference 26L. Since the initial rate of spraying was low, the pressure in the flask containing the dispersion was increased to 0.25 Kg/cm ² .
This high applied pressure is hereinafter referred to as reference 26H. Examples 27-30 illustrate simultaneous vigorous stirring and shear milling and subsequent spray drying of the titanium trichloride material. Example 27 (A) Dispersion of titanium trichloride 280 g of titanium trichloride material (Stauffer TiCl ₃
-AA) was suspended in 750 cm ³ of toluene. This suspension was then placed in a 1.2 dm ³ three-necked glass flask. The flask had a heating/cooling jacket and an Ultra Turax T45 high shear homogenizer. Ambient temperature water was passed through the heating/cooling jacket. Then run the homogenizer at maximum power for 2.5 minutes, switch off, add 200 cm ³ of toluene, and run the homogenizer at maximum power for a further 2.5 minutes.
Operated for minutes. Remove about half of the mixture;
100 cm ³ of toluene was added to the remainder and the homogenizer was operated at maximum power for an additional minute. The dispersion thus obtained was transferred to a storage flask and stirred until spray drying as described in step (B). (B) Spray Drying of Dispersed Titanium Trichloride Polystyrene ("Lustrex" HF66) was added to the dispersion obtained in step (A) in an amount of 1% by weight with respect to the weight of titanium trichloride. Then,
The dispersion was spray dried according to the general procedure of step (C) of Example 25 with the following exceptions. The diameter of the spray nozzle was 0.72 mm. The preheated nitrogen was at a temperature of approximately 140°C. The nitrogen passed through conduit 8 was at a pressure of approximately 0.25 Kg/cm ² gauge. The nitrogen overpressure applied to the dispersion in the storage flask was 0.1 Kg/cm ² . When about half of the dispersion was spray dried, spraying was stopped and more polystyrene was added to provide 2% by weight polystyrene with respect to titanium trichloride. Spraying was resumed and product was collected. The product obtained in the presence of 2% by weight of polystyrene is hereinafter referred to as reference 27. Example 28 (A) Dispersion of titanium trichloride-butyl benzoate The procedure of step (A) of Example 27 was repeated with the following modifications. The homogenized mixture contained 119 g of titanium trichloride,
26 cm ³ of butyl benzoate, 390 cm ³ of toluene and 3 g of polystyrene (“Lustrex”)
HF66). After operating the homogenizer at maximum power for 2.75 minutes, the contents of the flask form an immobile gel-like product, and the temperature decreases to 50
It had risen above ℃. Stop homogenization, 500
cm ³ of toluene was added to facilitate the transfer of the dispersed solids to a storage vessel. (B) Spray Drying of Dispersed Titanium Trichloride The dispersion of step (A) was prepared as described in the Examples with the following exceptions
The general procedure of step (C) in step 25 was followed for spray drying. The diameter of the spray nozzle was 0.72 mm. The preheated nitrogen was at a temperature of approximately 140°C. Example 29 (A) Milling of titanium trichloride and tri-n-butylphosphine The procedure of Example 2 of GB Patent Specification 1485181 was followed by
It was repeated using titanium trichloride (Stauffer TiCl ₃ -AA) and tri-n-butylphosphine in a molar ratio of 4.2:1. During milling, the temperature is maximum
The temperature rose to 85℃. 521 g of milled product was suspended in 1086 g of toluene. 5.2 g of polystyrene ("Lustrex" HF66) was added to the suspension. (B) Dispersion of titanium trichloride-tri-n-butylphosphine About 700 cm ³ of the suspension prepared in step (A) was
Transferred to a 1 dm ³ volume flask as described in step (B) of Example 25. The homogenizer was run for 5 minutes to form a thick dispersion. During this process the temperature is 69
The temperature rose to ℃. The thick dispersion was transferred to a 2 dm ³ storage vessel, the 1 dm ³ flask was washed with 200 cm ³ of toluene, and the washings were added to the contents of the storage vessel and stirred. (C) Spray Drying of Dispersed Titanium Trichloride The dispersion of step (B) was spray dried according to the general procedure of step (C) of Example 25, with the following exceptions. The preheated nitrogen was at a temperature in the range of 130-135°C. The nitrogen overpressure applied to the dispersion in the storage flask was 0.13 Kg/cm ² . Spray drying is stopped after approximately 30 minutes, at which time the end of conduit 8 is connected to orifice 10.
It was blocked in . Example 30 (A) Milling of titanium trichloride and tri-n-butylphosphine The milling procedure of step (A) of Example 29 was repeated. (B) Washing of titanium trichloride-tri-n-butylphosphine 457 g of the milled product of step (A) was added to 2 dm ³
The mixture was suspended in 1.5 dm ³ of toluene in a three-necked flask, and the mixture was allowed to settle overnight. The upper liquid was removed with a siphon and 1 dm ³ of toluene was added. The flask was transferred to a water bath. The contents of the flask were stirred and the temperature of the water bath was increased to 100°C over 25 minutes. The heating of the water bath was stopped.
Stirring of the contents of the flask was continued for 20 minutes, by which time the temperature of the water bath had fallen to 82°C. Stirring was then stopped and the solids were allowed to settle for 90 minutes. The upper liquid was then removed with a siphon. The flask was removed from the water bath. A further 1 dm ³ of toluene was added and the mixture was stirred for 1 hour at ambient temperature. Stirring was stopped and the solids were allowed to settle over the weekend (approximately 65 hours). The upper liquid was siphoned off and fresh toluene was added to bring the solids content to 30% by weight of the total weight of the suspension. 4.57 g of polystyrene ("Lustrex" HF66) was added. (C) Dispersion of washed titanium trichloride The dispersion obtained in step (B) was divided into two approximately equal parts. Each portion was homogenized for 15 minutes using the equipment and procedure of step (B) of Example 25. The two samples of dispersed titanium trichloride were placed in a storage container and stirred together until spray-dried. (D) Spray Drying of Dispersed Titanium Trichloride The combined dispersion of step (C) was spray dried according to the general procedure of step (C) of Example 25 with the following exceptions. The diameter of the spray nozzle was 0.72 mm. The preheated nitrogen was at a temperature in the range of 140-145°C.
The nitrogen through the conduit was at a pressure of approximately 0.42 Kg/cm ² gauge. Unlike spray drying step B of Example 29,
No nozzle blocking occurred. Examples 31-33 Polymerizations were carried out in a 8 dm ³ stainless steel autoclave in a manner similar to that used in Examples 11-21, with the following exceptions. 40 cm 3 of a solution in aliphatic hydrocarbon containing 20 mmol of aluminum tri-isobutyl is added to the autoclave, followed by 40 cm ³ of a solution in aliphatic hydrocarbon containing 7 mmol of methyl p-methylbenzoate.
Added ^40cm3 . The spray-dried magnesium chloride-supported titanium halide composition obtained in Example 25 or 26 was then added as a suspension of the spray-dried solid in n-heptane. The autoclave was maintained at 70° C. while propylene was passed into the autoclave to establish a pressure of 10 Kg/cm ² absolute. Then 10 mmol hydrogen was added. Pressure is increased to 10Kg/cm ² by supplying propylene.
I definitely kept it. After 0.5 hours and again after 1 hour, a further 10 mmol of hydrogen was added to the autoclave. After 2 hours, the propylene feed was stopped and the autoclave was vented to atmospheric pressure. The polymer suspension was placed in a receiver and the polymer was passed through air. Samples of the polymer were dried at 100° C. in a fluidized bed using nitrogen as the fluidizing gas. Further details of the polymerization conditions and properties of the products obtained are given in Table 5.

Table: Example 34 The procedure of Examples 31-33 was repeated with the changes described below. Polymerizations were carried out using a two-component catalyst system consisting of 30 mmol of diethylaluminum chloride and sufficient amount of the product of Example 27 to provide 10 mmol of titanium trichloride. Polymerization pressure is 10.4
Kg/cm ² gauge hot. 40 mmol of hydrogen was added to the autoclave when the pressure was 1.1 Kg/cm ² absolute, again when the polymerization pressure was 10.4 Kg/cm ² gauge, and again after the polymerization had been carried out for 1 hour. The resulting polymer had a flexural modulus of 1.60 GH/m ² and a packing density (as defined in note (h) to Table 1) of 476 g/dm ³ . The polymer product was screened and subjected to particle size analysis and the results are listed in Table 6.

Table: Examples 35-37 A stainless steel autoclave with a total capacity of 8 dm ³ equipped with a stirrer was charged with 400 g of polypropylene powder. This powder has a flexural modulus of 1.45 GN/m ² and 4.0% by weight of it remains molten after refluxing 1 g of polymer with 50 cm ³ of xylene and cooling the solution to ambient temperature. Ta. The autoclave was evacuated to 75 mbar and then nitrogen was introduced to restore the pressure to 1 bar absolute.
This procedure was repeated a total of three times. The stirrer was started at 60 rpm and the autoclave was heated to 80° C. while nitrogen was passed through the autoclave. pressure 75
The pressure was reduced to mbar and liquid propylene was added to increase the pressure to atmospheric pressure (1 bar absolute). 20 mmol of diethylaluminum chloride was added as a 1.3 molar solution in aliphatic hydrocarbon. The product of one of Examples 28, 29 or 30 was then added in an amount equal to 2 mmol of titanium trichloride,
An additional 10 mmol of diethylaluminium chloride was added as a suspension in a 1.3 mmol solution of diethylaluminium chloride in an aliphatic hydrocarbon sufficient to provide 10 mmol of diethylaluminium chloride. The autoclave was pressurized to 28 Kg/ ^cm2 absolutely by addition of liquid propylene. During pressurization, 17 mmol of hydrogen was added to give a pressure of 7 Kg/cm ² , 14 Kg/cm ² , 21 Kg/cm ² and finally 28 Kg/cm ² . Polymerization was carried out in the gas phase for 3 hours while maintaining an autoclave pressure of 28 Kg/cm ² absolute with further addition of liquid polypropylene. During the polymerization, 13 mmol of water was added for every 200 cm ³ of liquid polypropylene added. The results obtained are listed in Table 7 below.

TABLE The polymer products of Examples 36 and 37 were subjected to particle size analysis by sieving and the results are listed in Table 8.

[Table] (l) Average of two experiments.
The product of Example 36 had a packing density of 455 g/dm ³ and the product of Example 37 had a packing density of 488 g/dm ³ . Examples 38-41 Having a heating jacket and equipped with a stirrer
In a 100dm ³ volume stainless steel autoclave,
Contains 36Kg of polypropylene powder. This powder is
It has a flexural modulus of 1.45GN/ ^m3 , and its 4.0
The weight percent was soluble in hot heptane as determined by weight loss after 24 hour Soxhlet extraction with boiling heptane. Reduce the pressure to 75 mbar,
Nitrogen was then added to a pressure of 1 bar and this procedure was carried out a total of three times. The stirrer was rotated at 60 rpm and stirring continued throughout the next procedure. Heat the autoclave to 80 °C while passing nitrogen through the autoclave. The pressure was reduced to 75 mbar and liquid propylene was added to the autoclave and evaporated to raise the pressure to 28 Kg/cm ² gauge. 1.5% by weight with respect to propylene apart from hydrogen
added at the ratio of A solution of diethylaluminium chloride in an aliphatic hydrocarbon and a 40% by weight suspension of a titanium trichloride material in an aliphatic hydrocarbon were placed in an autoclave 8:1 until polymerization was observed to begin.
were introduced at a molar ratio of Introducing liquid propylene,
The gaseous propylene was then vented while the catalyst was added. Once the polymerization has started, stop venting the autoclave, introduce liquid propylene at 20 °C into the autoclave at a rate (approximately 15 Kg/hr) to maintain a pressure of 28 Kg/cm ² gauge, and saturate with propylene. The polypropylene was withdrawn from the autoclave in batches at a rate of about 10-12 kg of polymer/hour. Temperature and pressure were maintained at 75° C. and 28 Kg/cm ² gauge, respectively. Diethylaluminium chloride solutions and suspensions were added to the autoclave continuously at a molar ratio of 8 to 1 diethylaluminium chloride to titanium trisalt and at a rate that maintained the polymer production rate at the desired rate of 10-12 Kg/hour of polymer. It was introduced in Initially, the polymerization was carried out using the titanium trichloride product obtained as described in step (A) of Example 29 and without further treatment (this product is designated hereinafter with reference A29). carried out. Subsequently,
The product of Example 30 was used. Some properties of the polymer product removed at various times during the polymerization are listed in Table 9, and Table 10 shows the results of particle size analysis by sieving of the two samples.

【table】

Table: The product of Example 39 has a packing density of 513 g/ ^dm3 , whereas the product of Comparative Example B has a packing density of 364 g/dm3.
It had a packing density of dm ³ . The product of Example 39 is in the form of essentially spherical particles, and the material is more free-flowing than the product of Comparative Example B. In the following examples, Examples 42, 43, 45 and
No. 47 describes the process of the invention, in which the comminution is carried out by grinding in a ball mill during the procedure detailed in JP-A-58-109509 by the applicant entitled "Compositions, products and uses". Reveal the incorporation of Example 42 (A) Milling of Magnesium Chloride, Thionyl Chloride and Ethyl Benzoate The procedure of step (A) of Example 1 was repeated with the modifications described below. 180.5 g of magnesium chloride and 6.6 cm ³ of thionyl chloride were introduced into the mill chamber and milling with thionyl chloride was carried out for 2 hours, during which time water at ambient temperature was passed through the jacket of the mill chamber. The mill chamber was then passed through the mill chamber jacket with a mixture of water and ethylene glycol at -12 DEG C. while the mill assembly continued to vibrate. The mill was cooled to 0° C. for 1.25 hours while milling continued, then 45.5 cm ³ of ethyl benzoate was added and milling at 0° C. continued for an additional 24 hours. The molar ratio of magnesium chloride to ethyl benzoate in the mill chamber was approximately 6:1. (B) Milling with toluene 400 cm ³ of toluene was added to the mill chamber while the mill was kept vibrating. Milling continued for an additional 30 minutes at 0° C. in the presence of added toluene. After 30 minutes, the mill was inverted, the inverted mill was vibrated, and the mixture of milled solids and toluene was collected under a nitrogen atmosphere. The mill chamber was rinsed with an additional 300 cm ³ of toluene, which was added to the previously removed suspension. After standing for 65 hours, the milled mixture was still fluid but viscous. This mixture was stirred and polystyrene ('
A 10% weight/volume solution of Styton'686/7 (available from Dow Chemical Company) was added to provide 2.0% by weight polystyrene with respect to the milled solids. This mixture had a solids content of 24% by weight. (C) Spray drying of the milled solid/toluene mixture All of the dispersion obtained in step (B) was
Spray drying was carried out in the glass laboratory scale spray drying apparatus used in step (C) of Example 1. Spray drying was carried out under a nitrogen atmosphere by passing a nitrogen stream preheated to 145° C. through the spray dryer at a rate of 190 dm ³ /min. about
Nitrogen at a pressure of 0.4 Kg/cm ² gauge was introduced into the spray nozzle. The suspension obtained in step (B) is
The spray nozzle was fed from a 2 dm ³ volume three-necked flask by applying an excess nitrogen pressure of 0.04 Kg/cm ² to the flask. (D) Contact with titanium tetrachloride Sample of spray-dried product from step (C) (39
g) was transferred to an 800 cm ³ jacketed glass vessel equipped with a stirrer. 390 cm ³ of titanium tetrachloride was added to the vessel, the stirrer was started and the jacket was heated. Heating was continued until a temperature of 100°C was reached. The temperature was maintained at 100° C. and stirring continued for 3 hours. At the end of the 3 hours, the stirrer was stopped and the solids were allowed to settle while continuing to heat the contents of the vessel. Fifty minutes after stirring was stopped, the upper liquid was siphoned off, leaving behind the settled solids. Heating was stopped and the contents of the container were allowed to cool overnight. (E) Washing The residue obtained from step (D) is
450 cm ³ of aliphatic hydrocarbon was added. The mixture was stirred and heated to a temperature of 100°C. Stirring at 100°C was continued for 1 hour and then stopped. After an additional 75 minutes, the upper liquid was siphoned off, leaving behind the settled solids, while heating continued.
Heating was stopped and 450 cm ³ of aliphatic hydrocarbon at ambient temperature was added to the hot residue. The mixture was stirred for 15 minutes without heating, then the stirrer was stopped and the solids were allowed to settle. After 1 hour, the upper liquid was siphoned off leaving behind the settled solids. This washing procedure was repeated twice. The cold residue obtained from the fourth washing step was diluted with aliphatic hydrocarbon to a final volume of 390 cm ³ and the mixture was transferred to a storage container under nitrogen atmosphere. Example 43 (A) Milling of Magnesium Chloride and Ethyl Benzoate with a total volume of about 165 and a diameter of 570 Kg 25
Siebtechnik SM50 Vibromill containing mm steel balls
was thoroughly purged with nitrogen to provide a nitrogen atmosphere in the mill. 16 Kg of anhydrous magnesium chloride (as used in Example 1) was introduced into the mill and the mill was cooled to -10°C by passing a mixture of water and ethylene glycol at about -20°C through the jacket of the mill. did. Once the desired temperature was reached, the mill was oscillated at a frequency of 1500 oscillations/min and an amplitude of 2 mm while a mixture of water and ethylene glycol at -20°C was passed through the jacket of the mill. 4 dm ³ of ethyl benzoate was added to the vibrating mill over a period of 2.25 hours, during which time the temperature rose to approximately 20°C. Milling continued for a total of 24 hours, during which time the mill was still cooled. The molar ratio of magnesium chloride to ethyl benzoate in the mill is approximately 6 to 1.
It was hot. (B) Milling with toluene without removing the milled magnesium chloride-ethyl benzoate product of step (A);
25 dm ³ of toluene and 4 dm ³ of a 10% weight/volume solution of polystyrene in toluene (as used in Step B of Example 42) were added to the vibrating mill. Milling was continued for a further 30 minutes with cooling, and the resulting magnesium chloride suspension was poured into a volume of 100 d under nitrogen atmosphere.
Transferred into a cm ³ drum. Add ^25dm3 of toluene to the mill and start milling.
This continued for 20 minutes and the liquid was transferred to a drum along with any remaining magnesium chloride. (C) Spray Drying of the Milled Solid/Toluene Mixture The contents of the drum obtained as described in step (B) are dried in a spray drying apparatus essentially as described with reference to FIG. Spray dried. This spray drying container has a diameter of 2.2m,
It had a cylinder height of 1.95 m and a cone of 60°. The cycle gas was nitrogen, which was preheated to approximately 140°C before entering the spray drying vessel. The nitrogen feed rate was approximately 650 Kg/hr. The suspension was not preheated and was therefore at ambient temperature when fed to the spray drying vessel. The rotation speed of the spray disc is 18000 rpm, and the time to feed the suspension into the spray drying container is 20
It was hot in minutes. (D) Contact with thionyl chloride A sample of the spray-dried product from step (C) (16
g) was transferred to an 800 cm ³ glass vessel equipped with a stirrer. 160 cm ³ of aliphatic hydrocarbon and 0.4 cm ³ of thionyl chloride were added to the vessel, the stirrer was started and the jacket was heated. Heating was continued until a temperature of 50°C was reached. The temperature was maintained at 50° C. and stirring continued for 1 hour. At the end of 1 hour, the stirrer was stopped and the solids were allowed to settle while continuing to heat the contents of the vessel. 10 after stopping stirring
After minutes, the upper liquid was siphoned off leaving behind the settled solid. (E) Contact with titanium tetrachloride 160 cm ³ of titanium tetrachloride were added to the hot residue from step (D). The stirrer was started and the jacket heated. Heating was continued until the temperature reached 100°C. The temperature was maintained at 100° C. and stirring continued for 3 hours. At the end of 3 hours, stop the stirrer and
The solids were allowed to settle while continuing to heat the contents of the vessel. Forty minutes after stirring was stopped, the upper liquid was siphoned off, leaving behind the settled solid. Heating was stopped and the contents of the vessel were allowed to cool overnight. The treatment with titanium tetrachloride was repeated, but the solids were allowed to settle for 45 minutes, the upper liquid was siphoned off, and the residue was not cooled. (F) Cleaning The hot residue obtained from step (E) is exposed to ambient temperature.
200 cm ² of aliphatic hydrocarbon was added. The mixture was stirred and heating continued to bring the temperature to 100°C. Stirring at 100°C was continued for 1 hour and then stopped. After an additional 25 minutes, the upper liquid was siphoned off to remove the settled solids while heating was continued. Heating was stopped and 200 cm ³ of aliphatic hydrocarbon at ambient temperature was added to the hot residue. The mixture was stirred for 10 minutes without heating, then the stirrer was stopped and the solids were allowed to settle. After 1 hour, the upper liquid was siphoned off leaving behind the settled solids. This washing procedure was repeated two more times. The cold residue obtained from the fourth washing step is diluted with aliphatic hydrocarbon to a final volume of 160 ^cm3 ;
The mixture was transferred to a storage container under nitrogen atmosphere. Example 44 The spray-dried product of step (C) of Example 43 was used and subsequently processed in a manner analogous to that described for steps (D) and (E) of Example 42. This material was contacted with thionyl chloride. (D) Contact with titanium tetrachloride The procedure of step (D) of Example 42 was repeated in step (D) of Example 43.
Repeat with 27 g of the spray-dried product of (C) and 270 cm ³ of titanium tetrachloride. The solids were allowed to settle for 15 minutes and the upper liquid was siphoned off without cooling the residue. (E) Washing The procedure is essentially as described in step (E) of Example 42, except that the hot residue from step (D) is used and 300
cm ³ aliphatic hydrocarbons were used. After the second wash,
The solids were cooled and allowed to settle for approximately 65 hours. After the fourth wash, the residue was diluted to a volume of 270 cm ³ . Example 45 The spray-dried product of step (C) of Example 43 was
43 as generally described in steps (D), (E) and (F), but processed on a larger scale. (D) Contact with thionyl chloride This was carried out in a container with a volume of 6 dm ³ . 500g of the spray-dried product of step (C) of Example 43, 5d
m ³ of aliphatic hydrocarbon and 13 cm ³ of thionyl chloride were used. 80 minutes after the stirring was stopped, the upper liquid was extracted using a siphon. (E) Catalysis with titanium tetrachloride This is carried out in the same vessel as in step (D) with 3 dm ³ of titanium tetrachloride for each contact,
The temperature of 100°C was then maintained for 2 hours. After the first contact, the solids were allowed to settle for 1 hour, and after the second contact, the settling time was 1.5 hours. (F) Washing 5.5 dm ³ of aliphatic hydrocarbon is added to the hot residue from step (E) and the mixture is washed without heating.
It was left to stand for 18 hours. The mixture was then stirred and heated to 100°C, maintained at 100°C for 1 hour, allowed to settle for 10 minutes, and the upper liquid was siphoned off. Stop heating and for each wash
Three consecutive washes were carried out using 5.5 dm ³ of aliphatic hydrocarbon. The residue was finally diluted to a total volume of ^4.5dm3 . Example 46 The procedure is similar to that of Example 45, except that steps (D), (E) and (F) are carried out using small amounts of reagents and
And thionyl chloride in step (D) was omitted. (D) Contact with aliphatic hydrocarbons 200 g of the spray-dried product of step (C) of Example 43
and 2dm ³ aliphatic hydrocarbons were used. 35 minutes after the stirring was stopped, the upper liquid was extracted using a siphon. (E) Contact with titanium tetrachloride 1.5 dm ³ of titanium tetrachloride was used for the first contact,
The solids were then allowed to settle for 1.75 hours. 2 dm ³ of titanium tetrachloride were added to the residue and the mixture was allowed to stand for 18 hours without heating. The mixture was stirred, heated to 100°C, maintained at 100°C for 3 hours, and allowed to settle for 1 hour and 20 minutes. (F) Washing 2 dm ³ of aliphatic hydrocarbon was used for each wash. Aliphatic hydrocarbons were added to the hot residue from step (E) and the temperature was increased to 100°C. After 1 hour at 100°C, the solids were allowed to settle for 40 minutes. Wash 3 times in succession without heating, and remove the residue for 2d
Diluted to a total volume of m ³ . Example 47 The procedure was similar to that of Example 45, except that steps (D), (E) and (F) used small amounts of reagents and only one contact step was performed in step (E). . (D) Contact with thionyl chloride 200 g of the spray-dried product of Example 43, 2 dm ³ of aliphatic hydrocarbon and 5.2 cm ³ of thionyl chloride were used. (E) Contact with titanium tetrachloride One contact with 2 dm ³ of titanium tetrachloride was carried out at 100° C. for 3 hours. (F) Washing Washing was carried out immediately after contact with titanium tetrachloride using 2 dm ³ of aliphatic hydrocarbon for each wash. Example 48 The procedure was as described in Example 47, except step (D) was omitted. Examples 49-56 Polymerizations were carried out in an 8 dm ³ stainless steel autoclave essentially as described in Examples 11-21, with the following modifications. 20
40 cm ³ of a solution in aliphatic hydrocarbon containing mmol of aluminum tri-isobutyl were added to the autoclave followed by 40 cm ³ of a solution in aliphatic hydrocarbon containing 7 mmol of methyl p-methylbenzoate. 4 cm ³ of the suspension of the titanium halide composition obtained in one of Examples 42-48 were then added. The autoclave was maintained at 70° C. while propylene was passed through the autoclave to achieve a pressure of 11.5 Kg/cm ² absolute. Then 10 mmol of hydrogen was added. The pressure is increased to 11.5Kg/cm ² by supplying propylene.
I definitely kept it. 10 mmol of hydrogen, 11.5 kg/
^cm2 was added after 0.5 and 1.0 hours of absolute pressure. After 2 hours, the propylene feed was stopped and the autoclave was vented to atmospheric pressure. The suspension of polymer was placed in a receiver and the polymer was passed through air. Samples of the polymer were dried at 100° C. in a fluidized bed with nitrogen as the fluidizing gas.
Some properties of the obtained polymer are listed in Table 11.

[Table] For each polymer, a sample of the filtered polymer was washed with 60-80% petroleum ether and placed in a vacuum furnace for 50 mm.
Drying was carried out for 4 hours at a pressure of Hg and a temperature of 60°C. The dried polymer was sieved and analyzed for particle size and the results are listed in Table 12.

Table: Example 57 (A) Milling of Magnesium Chloride, Thionyl Chloride and Ethyl Benzoate Milling was carried out in a vibratory mill as described in step (A) of Example 43. Magnesium chloride is anhydrous magnesium chloride (Steetley Chemicals
Trading Division, of Basing View;
(obtained from Basingstoke, Hampshire, England) and was subsequently ground and passed through a 6 mm mesh sieve plate. The mill was purged with nitrogen as in Example 43 and shaken without cooling. 16 Kg of magnesium chloride were introduced into the vibrating mill, followed by 500 cm ³ of thionyl chloride. Milling was carried out for 2.5 hours, during which -20℃
A mixture of water and ethylene glycol was fed to the jacket of the mill and the temperature was controlled at a maximum of 50°C. Vibration and cooling were then stopped and the mill was allowed to stand for 16 hours. The mill was cooled to about 5° C. by passing refrigerant through the mill jacket and 8 dm ³ of ethyl benzoate was slowly added over about an hour. The mill was then vented for 24 hours while cooling, and the milled product was then removed from the mill and stored under a nitrogen atmosphere. (B) Contact with titanium tetrachloride 15Kg of milled product from Example (A)
was transferred to a jacketed 200 dm ³ steel reactor equipped with a stirrer. 100 dm ³ of titanium tetrachloride was added to the reactor, the stirrer was started and the jacket was heated. Heating was continued until the temperature reached 100°C. The temperature was maintained at 100° C. and stirring continued for 3 hours. At the end of the 3 hours, the stirrer was stopped and the solids were allowed to settle while continuing to heat the contents of the vessel. Two hours after the stirrer was stopped, the upper liquid was siphoned off, leaving behind the settled solid. The settled solid was allowed to stand for 4.5 hours, during which time a temperature of 100°C was maintained. (C) Washing The residue obtained from step (B) is
Add 120 dm ³ of aliphatic hydrocarbon over 0.5 h,
Meanwhile, the mixture was stirred. When adding aliphatic hydrocarbons, the temperature decreases and after 40 minutes the temperature is 100℃
rose to Stirring was continued at 100° C. for 1 hour, then the stirrer was stopped while heating continued. After an additional 2 hours, the upper liquid was siphoned off from the settled solids. After 40 minutes, 120 dm ³ of aliphatic hydrocarbon at ambient temperature was added to the hot residue from the first wash. The mixture was stirred for 45 minutes, during which time it was heated to a temperature of 100°C. When 100°C was reached, stirring was continued for 1 hour, the stirrer was stopped and the solids were allowed to settle out while still heating. After 2 hours, the upper liquid was removed from the settled solids by siphoning and heating was stopped. To this hot residue was added 120 dm ³ of ambient temperature aliphatic hydrocarbon. The mixture was stirred for 10 minutes without heating, stirring was stopped, the solids were allowed to settle for 2 hours, and the upper liquid was siphoned off leaving the settled solids behind. This washing procedure was then repeated once more. The residue was finally washed once with 80 dm ³ of toluene, otherwise the procedure was similar to that used for the previous two washing steps. (D) Dispersion of the titanium-containing composition Steps (A), (B) and (C) are repeated and the products of both of these repeated steps are placed in a 200 dm ³ steel vessel with a stirrer. Mixed. Add polystyrene (“Lustrex” HF66) in toluene to the mixed product while stirring it.
5 dm ³ of a 10% w/v solution of was added. This mixture was stirred for an additional 0.5 hour. The mixture was then dispersed by repeated circulation through a circulation loop connected to a 200 dm ³ steel vessel. The circulation loop is a 275L SiLverson shear mixer (Silverson Machines Limited, of
Chesham, Buckinghamshire, England). After circulating the mixture for 2 hours, the resulting dispersion was transferred into a nitrogen-purged stainless steel drum with a capacity of 100 dm ³ . This mixture was stored under nitrogen and had a solids content of 32% w/w with respect to the mixture;
And the polystyrene content was 2% w/w with respect to methane-containing solids. (E) Spray Drying of the Titanium-Containing Dispersion Spray drying of the product of step (D) was carried out using equipment as used in step (C) of Example 43. Nitrogen preheated to 140°C was supplied at a flow rate of 700 kg/hour. The rotation speed of the spray disc is 18000rpm
It was hot. The dispersion was passed through the device at a rate of 135 Kg/hr. The spray-dried solid was free-flowing and had an average particle size of 40 x 10 ^-6 m. The spray dried solids were suspended in aliphatic hydrocarbon. Examples 58-61 Following the procedure generally described in Examples 22-24,
The product of Example 57 was used to polymerize propylene continuously in the gas phase. The polymerization was carried out in a 0.8 m ³ stainless steel autoclave equipped with a stirrer and a heating jacket. The autoclave was fed with 90Kg of dry, dechlorinated polypropylene powder (obtained from a previous experiment using a similar type of catalyst). The heating jacket was heated and the contents of the reactor were stirred. When the temperature was approximately 70° C., nitrogen was introduced into the autoclave to a pressure of 5 bar absolute and the overpressure was released to a pressure of 1 bar absolute.
This procedure was repeated a total of 5 times. This procedure was then repeated for 5 minutes using liquid propylene instead of nitrogen.
Repeated times. Liquid propylene was then added to increase the pressure to the desired operating pressure of 28 bar gauge. Hydrogen was added separately in a proportion of 1.5% by volume with respect to propylene. A 1.5 molar solution of tri-isobutylaluminum in an aliphatic hydrocarbon and a 0.6 molar solution of methyl p-methylbenzoate in an aliphatic hydrocarbon are separately prepared.
These two materials were added in amounts to obtain the desired relative proportions. Ester solution is 155cm ³ /
Added at the speed of time. containing the product of Example 57;
and a suspension having a solids content of about 50% by weight,
It was also introduced into an autoclave. Once the polymerization has started, increase the temperature and pressure.
It was maintained at 73°C and 28 bar gauge. Once polymerization began, the propylene withdrawn from the autoclave was passed through a recirculation loop containing a refrigerant system and returned to the autoclave. Additional amounts of fresh liquid propylene were added to the autoclave to replenish the amount of propylene consumed as or with the polymer. The temperature and pressure inside the autoclave were controlled by the addition rate of liquid propylene (recycled propylene and fresh propylene). The product of Example 57 is 45
Addition was made at a rate sufficient to maintain the desired rate of polymer production in Kg/hr. Further details of the polymerization conditions and some of the properties of the products obtained are listed in Table 13.

【table】

Table: The polymer product, removed from the autoclave after 20 hours and otherwise obtained under the polymerization conditions used for Examples 58 and 59, was analyzed for particle size by sieving and
The results are listed in Table 14.

【table】 [Brief explanation of the drawing]

FIG. 1 is a flowchart showing steps for preparing an α-olefin polymerization catalyst related to the method of the present invention. or FIG. 2 is a cross-sectional side view of a spray drying device with a spray nozzle. FIG. 3 is a cross-sectional side view of another spray drying apparatus having a rotating disk atomizer. 1... Airtight spray drying container, 2... Upper part, 3
... lower part, 4 ... cover plate, 5 ... spray nozzle assembly, 6 ... plenum chamber, 7 ...
...Inner conduit, 8...Outer conduit, 9...Conduit, 10
... Orifice, 11 ... Conduit, 12 ... Conduit,
13... Conduit, 14... Valve means, 15... Disc sprayer, 16... Output shaft, 17... High speed gear box/motor assembly, 18, 19... Plate, 20...
... radial vanes, 21 ... chamber, 22 ... central opening, 23 ... conduit.

Claims (1)

[Claims] 1. A method for producing a transition metal component of an α-olefin polymerization catalyst, comprising: mixing a solid substance with a liquid hydrocarbon or halohydrocarbon medium; (1) The solid material optionally comprises a Lewis base compound and/or or TiCl ₃・1/3 containing wear inhibitor
or ( ₂ ) the solid material is MgCl ₂ , an aromatic carboxylic acid ester, and optionally a wear inhibitor and/or
A method characterized in that the substance is obtained by contacting a component containing COCl ₂ with TiCl ₄ . 2. Subjecting the mixture of solid substance and liquid medium to mechanical action by grinding it using a rotary ball mill or a vibrating ball mill, Claim 1
The method described in section. 3. A method according to claim 1, wherein the mixture is subjected to mechanical action by subjecting the suspension of the solid substance in the liquid medium to simultaneous vigorous stirring and shearing action. 4. When the product is mixed with an organic compound of aluminum, an organic compound of a metal from group A of the periodic table, or a complex of an organic compound of a metal from group A or group A of the periodic table and an organoaluminum compound, α - The method according to claim 1, which is for producing an olefin polymerization catalyst.