JPH0561282B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to the separation of solid materials from suspensions, and in particular to the separation of transition metal catalyst components from an inert liquid medium in which they are suspended or dissolved. Olefin monomers such as ethylene, propylene and higher α-olefin monomers can be polymerized using so-called "Ziegler-Natsuta" catalysts. The term "Ziegler-Natsuta" catalyst generally refers to a catalyst system obtained by mixing a compound of a transition metal of Group A of the Periodic Table with an organic compound of a non-transition metal of Group IA to A of the Periodic Table. used as something. In many of the catalyst systems, the transition metal compound is present as a solid compound or as a compound supported on a solid support. In the polymerization of propylene and higher α-olefins, the catalyst is capable of producing a polymer in a high yield relative to the amount used, and the resulting polymer contains a high proportion of the desired isotactic polymer. It is desirable to do so. The catalyst systems initially reported by Natsuta had relatively low activity and stereospecificity, requiring the separation of catalyst residues from the polymer at the end of the polymerization process and the removal of relatively large amounts of undesired atactic polymers. Ta. Currently developed catalyst systems have relatively high activity, and some of these catalysts do not require complex catalyst separation operations or removal of atactic polymers. Furthermore, in order to simplify the polymerization process, it has been proposed to carry out the polymerization in the absence of a liquid medium by bringing the gaseous monomer into contact with a solid phase consisting of catalyst particles and the resulting polymer. The particle morphology of the catalyst is important for carrying out such polymerization processes. Certain catalysts with excellent activity and stereospecificity cannot be easily used in gas phase polymerization processes. This is because the particle morphology of the catalyst may cause various problems in the gas phase polymerization reaction, or produce polymers with undesirable particle morphology or particle size. In the method for preparing the solid particulate titanium halide-containing catalyst component for olefin polymerization according to the present invention, the particles of at least one solid substance and the substance that promotes agglomeration of the solid particles are aliphatic, alicyclic or aromatic carbonized. By forming a suspension in an inert liquid medium that is hydrogen, the titanium halide is dissolved in the inert liquid medium or the titanium halide is suspended in the inert liquid medium. preparing a suspension present as a solid material or supported on a solid material to be suspended in the suspension; spray-drying the suspension; and recovering the spray-dried titanium halide-containing catalyst component. It is characterized by Although French Patent No. 1146287 discloses a spray drying method, it does not suggest spray drying transition metal compounds useful as polymerization catalyst components. British Patent No. 1248953 discloses the use of silylchromate catalysts as catalysts for gas phase polymerization of olefin monomers. Various techniques have been disclosed for producing catalysts in suitable forms, and
Since siliculromate is a soluble compound obtained from a solution, it is conceivable that the solution could be spray-dried, but although this patent mentions spray-drying, the details of this technique are not explained, and the technique is not implemented. It's not even mentioned in the example. European Patent Publication No. 20818 (JP 55-120608) describes a method for polymerizing ethylene using a catalyst obtained by spray drying a precursor in an electron donor. However, when the present inventor carried out polymerization of propylene using the catalyst of this patent, in contrast to the system of the present invention, polymerization was not possible. Preferably, the particles of at least one solid substance in the suspension spray-dried according to the invention are particles of titanium halide or particles comprising titanium halide. In addition to particles of titanium halide or particles containing titanium halide, other solid substances not containing titanium halide can be included in the suspension. According to a preferred embodiment of the invention, therefore, particles of a solid material that is a titanium halide or a solid material containing a titanium halide are optionally combined with particles of a solid material that does not contain titanium halides in an inert liquid medium. This suspension is spray-dried and the solid material that is then spray-dried is recovered. Alternatively (and less preferably), the suspension consists of particles of one or more solid substances suspended in a solution of titanium halide in an inert liquid medium. Preferably, the suspension contains particles of only one type of solid substance. The inert liquid medium may be any liquid medium that does not affect the properties of the solid material to be spray dried when it is used as a component of the olefin polymerization catalyst. Although aliphatic hydrocarbons such as pentane, hexane or heptane can be used as the inert liquid medium, aromatic hydrocarbons such as benzene, toluene or xylene are preferred. When the transition metal compound is present as or in particles of said at least one solid substance, the inert liquid medium is preferably an aliphatic, aromatic or cycloaliphatic hydrocarbon. Although aliphatic hydrocarbons such as pentane, hexane or heptane can be used as inert liquid medium, aromatic hydrocarbon media such as benzene, toluene or xylene are preferred. In addition to the particles of at least one solid substance and the dissolved or suspended titanium halide, a small amount of a substance that promotes agglomeration of the solid particles is incorporated into the suspension. This substance (hereinafter referred to as "flocculation aid") is preferably present as a solution in an inert liquid medium. The titanium halide present in the suspension is preferably titanium chloride. The particles of at least one solid substance can consist essentially of a solid compound of titanium halide, and can also contain suitable amounts of other substances. Thus, when the solid material is titanium chloride, the solid material may be substantially pure solid titanium trichloride, or titanium tetrachloride may be substituted with titanium tetrachloride, such as aluminum metal, an organoaluminum compound, or an organomagnesium compound. It may also be a material containing titanium trichloride, such as a product prepared by reduction with a reducing agent. Alternatively, titanium chloride may be a product obtained by contacting titanium tetrachloride with silica, alumina, magnesia, mixtures or complexes of two or more of these compounds, or magnesium chloride. In addition to, or instead of, components such as those mentioned above, Lewis base compounds such as ethers, esters, organophosphorus compounds, or sulfur-containing organic compounds can be included in the titanium halide. The Lewis base compound can be incorporated into the titanium halide at various stages of manufacturing the titanium halide. That is, when the titanium halide is a product obtained by reducing titanium tetrachloride with a non-transition metal organic compound, the reduction product can be treated with a Lewis base compound such as an ether. Alternatively, if the titanium halide is a product obtained by contacting titanium tetrachloride with a carrier, the Lewis base compound may be mixed into the carrier to form a mixture or complex with the titanium halide. A supported compound containing a Lewis base compound can be obtained by adding the Lewis base compound to a carrier or by adding the Lewis base compound to already supported titanium halide. Titanium halides supported on magnesium halides are particularly useful in British Patent No. 904510;
No. 1271411, No. 1286867, No. 1310547 and No.
It is described in the specification of No. 1527736. Titanium halides supported on metal oxides such as alumina or silica are particularly useful in European Patent Application Publications.
It is described in specifications No. 14523 and No. 14524.
These types of supported titanium halides can be used in the process of the present invention. An alternative method of incorporating a Lewis base compound into a titanium halide consists of grinding a solid titanium halide in the presence of a Lewis base compound. After the grinding step, the ground titanium halide can be subjected to one or more extraction steps by washing with a suitable liquid medium. Through these washing steps, titanium halide having a fine particle morphology can be obtained. The fine particles thus obtained from solid materials that are or contain titanium halides are particularly suitable for use in the process of the invention. Accordingly, in another aspect, the invention provides one or more extraction steps by grinding a solid titanium halide in the presence of a Lewis base compound and washing the ground titanium halide with a suitable liquid medium. and forming a suspension in which the solids thus ground and washed are dispersed in an inert liquid medium, spray-drying the suspension, and recovering the spray-dried solid material. do. When the titanium halide is a solid titanium halide, it is preferably titanium trichloride. In this specification, titanium trichloride refers not only to pure titanium trichloride, but also to titanium trichloride associated or complexed with other substances, such as aluminum chloride or organoaluminum halides. Titanium trichloride containing aluminum chloride to be associated or to form a complex can be obtained by reducing titanium tetrachloride with metal aluminum. When titanium halides are dissolved in an inert liquid medium, titanium halides can be dissolved in hexane, heptane,
It may be a simple compound such as a dodecane isomer mixture, titanium tetrachloride soluble in a hydrocarbon solvent such as benzene or toluene. Suspensions of particles of at least one solid substance dispersed in a solution of such titanium halides can also be used in the process of the invention. When a titanium halide, e.g. titanium tetrachloride, is dissolved in an inert liquid medium, e.g. a hydrocarbon solvent, the at least one solid material is preferably a material capable of acting as a support for the catalyst or catalyst components for olefin polymerization. . Thus, the solid material may be silica, alumina, magnesia, a mixture or complex of two or more of these compounds, or magnesium chloride, or the resulting polymer, e.g. a polymeric material such as polyethylene or polypropylene. It may be hot. The suspension containing at least one solid substance and the titanium halide dissolved or suspended can optionally contain a flocculation aid, which is an inert substance in which the solid substance particles are suspended. Desirably, it is soluble in a liquid medium. The flocculation aid is one that does not or does not substantially adversely affect the activity and stereospecificity of the catalyst system for olefin polymerization containing the spray-dried solid material that is the product of the process of the invention. should be used in such amounts. If the solid substance to be spray-dried is subsequently suspended in a liquid medium, a flocculation aid is preferably used, preferably one capable of forming a dispersion of the solid substance to be spray-dried into at least small particles in the presence of the liquid medium in which the solid substance is suspended. Should be. Coagulation aids include polystyrene, polyvinyl acetate, atactic polypropylene or AB block copolymers, such as t-butylstyrene-styrene block copolymers. or,
The flocculation aid may be a sulfur-containing organic compound such as diphenyl sulfone, or it may be aluminum chloride or a mixture or complex of a sulfur-containing organic compound and aluminum chloride or titanium tetrachloride. It is to be understood that not all flocculation aids are equally effective on all types of solid material particles. Certain flocculation aids cause swelling of the solid material when added to a suspension of solid material particles. The use of a flocculation aid in the suspension spray drying process can result in a spray-dried solid material having a higher degree of cohesion compared to a similar spray-dried solid material prepared without the use of a flocculation aid. The amount of the coagulation aid used is preferably 1 to 10 mol % based on the titanium halide present in the suspension. The suspension containing the flocculation aid is spray dried in the manner described herein. The suspension to be spray-dried can contain Lewis base compounds which are normally associated with titanium halides. However, when the titanium halide is dissolved in an inert liquid medium, the Lewis base compound can be combined with the solid material, for example by using a solid material that has been previously milled with the Lewis base compound or exposed to the Lewis base compound. We can meet. When a Lewis base compound is present in the suspension, it is preferred that the compound be an organic Lewis base compound. The organic Lewis base compound may be any compound proposed for use in Ziegler polymerization catalysts and which affects the activity or stereospecificity of such catalyst systems. Therefore, Lewis base compounds include ethers, esters, ketones, alcohols, ortho esters, sulfides (thioethers), esters of thiocarboxylic acids (thioesters), thioketones, thiols, sulfones, sulfonamides, and heterocyclic sulfur atoms. fused ring compounds such as silanes or siloxanes, amides such as formamide, urea and its substituted derivatives such as tetramethylurea, thioureas, amines (not only simple amine compounds but also alkanolamines, pyridines or quinolines). and diamines such as tetramethylethylenediamine), or organophosphorus compounds such as organophosphines, organophosphine oxides, organophosphites or organophosphates. The use of organic Lewis base compounds is described in the British patent specifications listed below. 803198, 809717,
880998, 896509, 920118, 921954, 933236,
940125, 966025, 969074, 971248, 1013363,
1017977, 1049723, 1122010, 1150845, 1208815,
1234657, 1324173, 1359328, 1383207, 1423658,
1423659, 1423660, 1495031, 1550810, 1553291
and 1554574. The preferred Lewis base compound depends on the titanium halide and other solid materials present in the suspension of titanium halide. Thus, when using a solid material prepared, for example, by grinding and contacting magnesium dichloride with titanium tetrachloride, the preferred Lewis base compound is an ester, especially an aromatic ester such as ethyl benzoate. When using solid titanium halides, especially titanium trichloride, ground with Lewis base compounds, it is preferred to use sulfur-containing organic compounds or organophosphorus compounds as described in GB 1495031. The particles of at least one solid substance present in the suspension usually have a particle size of less than 10μ, in particular less than 5μ. Titanium trichloride prepared as described in GB 1554574 can be used in the process of the invention. In particular, by adding titanium tetrachloride and diphenyl sulfone or other sulfur-containing organic compound to a material obtained by grinding titanium trichloride and aluminum chloride together, grinding the mixture, and then washing the ground material, at least one solid Particles of the substance can be prepared.
The product thus obtained is usually a finely divided solid. When this solid is used as a component of an olefin polymerization catalyst, the catalyst exhibits high activity and stereospecificity, but due to the fine particle size of this solid component, this catalyst is not necessarily suitable for polymerization in the gas phase. . Suspensions of such finely divided solids can be spray dried according to the method of the invention. Therefore, in still another aspect, the present invention provides titanium trichloride, aluminum chloride, and titanium tetrachloride in the presence of a sulfur-containing organic compound selected from compounds represented by the following formulas A), B), or C). and the solid thus ground is dissolved in aluminum chloride and/or titanium tetrachloride and a sulfur-containing organic compound, or the sulfur-containing organic compound and at least aluminum chloride or titanium tetrachloride are dissolved in the solid. The solid to be ground and washed is suspended in an inert liquid medium, the resulting suspension is spray-dried, and then the spray-dried solid material containing titanium trichloride is washed with a liquid medium capable of dissolving the complex with one side. A method for preparing a transition metal composition is provided. In the above formulas A), B) and C), X is a halogen atom, alkyl, aryl, alkoxy, aryloxy, alkylthio or arylthio group, or -NR ¹ R ² group, and two Xs are bonded together. may be combined with at least one carbon atom in the phenyl group to form an unsaturated hydrocarbon ring. Furthermore, when there is a plurality of X's, they may be the same or different. Y is a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio or arylthio group, or -NR ¹ R ² group,
Furthermore, two Y's may form an unsaturated hydrocarbon ring together with at least two hydrocarbons in the phenyl group to which they are bonded. Furthermore, when there is a plurality of Y's, they may be the same or different. In addition, one X and one Y can _be directly bonded or -
O-, -CH ₂ -, -NR ¹ -, -S- or -CO-
may be replaced by a bond selected from Z is a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio or arylthio group, or -NR ¹ R ² group,
Two Z's may be combined with at least two carbon atoms in the phenyl group to which they are bonded to form an unsaturated hydrocarbon ring. Moreover, when Z is plural, they may be the same or different. D is a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio or arylthio group, or -NR ¹ R ² group,
When D is plural, they may be the same or different. T is -S-, -O-, ^-NR2- or -CO-. R ¹ is a hydrogen atom or a hydrocarbon radical. R ² is a hydrocarbon radical. R ³ is a hydrocarbon radical or a group represented by the following formula D). n, m, p and q are each 0 or 1 to 5
are integers that may be the same or different. x is a positive integer. The titanium trichloride used in the method described above is a substance containing aluminum chloride, for example with the formula _TiCl3 .
A substance expressed by 1/3 AlCl ₃ is preferable. The titanium chloride is first ground with additional aluminum chloride, then the ground product is mixed with titanium tetrachloride and a sulfur-containing organic compound, and further grinding is continued. The amount of additional aluminum chloride used is usually 10 to 80 mol %, particularly preferably 25 to 60 mol %, based on titanium trichloride. The amount of titanium tetrachloride added to the mixture is usually 5 to 50 mol %, particularly preferably 10 to 20 mol %, based on titanium trichloride. The amount of sulfur-containing organic compound added to the mixture is usually 50 to 100 mol% based on titanium trichloride. The ground material is then washed several times with a suitable liquid medium. The liquid medium used is usually preferably
A hot aromatic solvent such as toluene maintained at a temperature of 80 to 120°C. It is desirable to repeat washing with the liquid medium several times. Finally, the washed solids are suspended in a suitable inert liquid medium. Preferably, the liquid medium used is a different amount of the same liquid medium used for cleaning. The suspension of the material to be ground and washed is spray dried, which can be carried out by conventional spray drying techniques. That is, the suspension is passed through a suitable atomizer which forms an atomization or dispersion of droplets of the suspension, and a stream of hot gas is brought into contact with said droplets to evaporate the liquid medium and recover the separated solid product. do. Atomizers suitable for forming droplets of suspension include nozzle atomizers and spinning disk atomizers. As is well known, the transition metal component of the catalyst for olefin polymerization is sensitive to oxidation, so spray drying is carried out in a substantially oxygen- and water vapor-free medium. The preferred gas medium for spray drying is high purity nitrogen, but other gas mediums can be used as long as they do not disturb the transition metal components. Other gases used include hydrogen and inert gases such as argon or helium. In order to prevent oxygen-containing substances from entering the spray drying apparatus, it is desirable to operate at slightly higher pressures, for example about 1.2 Kg/cm ² absolute. The temperature can be below the boiling point of the liquid medium under the pressure conditions in the spray drying chamber, but at least enough to dry the surface of the droplets before they reach the walls or discharge point of the spray drying device. Sufficient evaporation of the liquid medium must occur. It is desirable that the spray drying temperature be relatively low so as not to interfere with the properties of the spray dried solid material, which are important when the solid material to be spray dried is used as a component of a catalyst for olefin polymerization. The temperature of the hot gas introduced into the spray drying equipment is approximately
200℃ and the temperature of the droplets or spray-dried material does not exceed 150℃, especially the maximum temperature of the droplets or spray-dried material is 80℃~
It is desirable to have a range of 130°. It will be appreciated that the temperature of the hot gas is at least equal to the maximum temperature of the droplets or spray dried material. The hot gas can flow countercurrently to the suspension droplets, but typically the hot gas and suspension flow in the same direction. When flowing in the same direction, the atomizer is usually placed at the top of the spray drying device, with the hot gas being introduced at the top of the device and exiting near the bottom. Some of the solids to be spray dried will accumulate at the bottom of the apparatus and are preferably continuously removed from the bottom using suitable means such as star feeder valves or screw conveyors or by means of a hot gas stream. can do. The hot gas that has passed through the spray dryer and cooled can be separated and removed from the spray dryer. Entrained solids can then be removed by passing the hot gas through a cyclone, and the cyclone removed solids are added to the solids exiting the spray dryer. The vapor of the inert liquid medium present in the hot gas is preferably condensed in a suitable condenser, and the condensed inert liquid medium can be reused. The gas is then reheated and recycled to the spray dryer. Spray drying conditions can be adjusted depending on the desired particle size. The preferred particle size of the final spray-dried material is between 20 and 100μ, particularly between 40 and 80μ, such as 50μ. The spray-dried solid material is one of the catalysts for olefin polymerization.
For use as a component, the morphology of the spray-dried solid material should be such that the resulting olefin polymer has a satisfactory particle morphology. Particularly when used as a component of a catalyst for polymerizing more than 1000 g of olefin monomer per millimol of transition metal present in the catalyst system, a polymer product substantially free of lumps and fines is obtained. It is desirable to choose the spray drying conditions accordingly.
Here, the term "substantially free of lumps or fine powder" means that the content of lumps in the polymer product is 10% by weight or less, and the content of fine powder polymer is also 10% by weight. It means that: In particular, it is desirable to obtain solid materials such that the content of lumps and fines in the polymer product is less than 5% by weight, in particular less than 2% by weight. By "lump" we mean polymer particles having a dimension in one direction of 1 cm or more. "Fine powder" refers to polymer particles whose maximum size is less than 75 microns. The spray-dried solid material, along with a non-transition metal organic compound, can be a catalyst for olefin polymerization. Accordingly, in yet another aspect, the present invention provides: 1. a transition metal composition consisting of a solid material obtained by spray drying a suspension by the method as described above; 2. aluminum or a transition metal composition from periodic table A The present invention provides a catalyst for olefin polymerization comprising a product obtained by mixing an organic compound of a group metal or a complex of an organic compound of group A or group A of the periodic table with an organoaluminium compound. Component 2) of the catalyst can be a magnesium-containing compound represented by the following general formula E or a magnesium-containing complex represented by the following general formula F. R ⁴ _a MgQ _(2-a) E R ⁴ _a MgQ _(2-a) bR ⁴ _c ALQ _(3-c) F R ⁴ is a hydrocarbon radical, and R ⁴ are different even if they are the same. Q is an ^OR5 group or a halogen atom other than fluorine, Qs may be the same or different, ^R5 is a hydrocarbon radical or a substituted hydrocarbon radical, and a is b is a numerical value greater than 0 and less than or equal to 2, and c is a numerical value greater than 0 and less than or equal to 3. R ⁴ is usually all an alkyl group, especially preferably an alkyl group having 1 to 20 carbon atoms, especially an alkyl group having 1 to 6 carbon atoms. The value a is preferably at least 0.5, with a particularly preferred value being 2.
The numerical value b is usually between 0.05 and 1.0. The numerical value c is usually at least 1, preferably 3. When component 2) is a complex of a group A metal and an organoaluminum compound, this compound may be a compound such as lithium tetraalkylaluminum. The above component 2) is preferably an organoaluminum compound, and as the organoaluminum compound, for example, aluminum hydrocarbyl halide such as dihydrocarbyl aluminum halide, aluminum hydrocarbyl sulfate or aluminum hydrocarbyl hydrocarbyloxy is used. However, aluminum trihydrocarbyl or dihydrocarbyl aluminum hydride is preferred. Among the aluminum trihydrocarbyls, aluminum trialkyl having an alkyl group having 1 to 8 carbon atoms, especially aluminum triethyl, is preferred. When a higher olefin monomer such as propylene is polymerized using an aluminum trihydrocarbyl compound as component 2), it is desirable to further include a Lewis base compound in the catalyst system. The Lewis base compound may be any type of Lewis base compound suitable for inclusion in the suspension to be spray dried, but organic Lewis base compounds are preferred. Suitable Lewis base compounds include esters represented by general formula G below. R ⁶ COOR ⁷ G In the above formula, R ⁶ is a hydrocarbon radical, and includes one or more halogen atoms and/or
or may be substituted with hydrocarbonoxy, R ⁷ is a hydrocarbon radical, and 1 or 2
It may be substituted with any of the above halogen atoms. R ⁶ and R ⁷ in the above formula G may be the same or different, but it is preferable that only one of R ⁶ and R ⁷ contains an aryl group, but not both. R ⁶ is preferably an optionally substituted alkyl or aryl group, such as methyl, ethyl or especially a phenyl, tolyl, methoxyphenyl or fluorophenyl group. Preferably R ⁷ is an alkyl group having up to 6 carbon atoms, such as an ethyl or butyl group. It is particularly preferred that R ⁶ is an aryl or haloaryl group and R ⁷ is an alkyl group. Esters of formula G include ethyl benzoate and esters of anisic acid (4-methoxybenzoic acid) such as ethyl anisate. Substituted or unsubstituted polyenes can be included in the catalyst system in addition to or in place of the Lewis base compound. The polyene to be blended may be an acyclic polyene such as 3-methylheptatriene (1,4,6), or a cyclic polyene such as cyclooctatriene, cyclooctatetraene or cycloheptatriene, or It may also be an alkyl- or alkoxy-substituted derivative of a cyclic polyene such as a tripylylium salt or complex, tripolone or tropone. The proportions of the above components 1) and 2) in the catalyst system can vary over a wide range, as is well known to those skilled in the art. Particularly preferred proportions will vary depending on the type of materials used and the absolute concentrations of both components, but generally there will be at least 1 mole of component 2) for every 2 gram atoms of transition metal present in component 1) in the catalyst system. It is desirable to do so. The number of moles of component 2) per gram atom of transition metal in component 1) is
Although numbers as high as 1000 are possible, it is preferable not to exceed 500, and in some transition metal compositions less than 25, such as from 5 to 10. When a Lewis base component is added to the catalyst system in addition to component 2), the amount of the Lewis base compound added is desirably 1 mol or less, particularly 0.1 to 0.5 mol, per mole of component 2). However, depending on the type of organic compound and Lewis base compound used,
The proportions of Lewis base compounds should be varied to obtain the best catalyst system. When polyene is blended into the catalyst system, the blending amount is desirably 1 mole or less, particularly 0.01 to 0.20 mole, per mole of component 2). When both a Lewis base component and a polyene are blended into the catalyst system, the total amount of these two components is 1 mole per mole of the above component 2).
It is desirable that the amount is less than mol. The catalyst according to the invention can be used for the polymerization or copolymerization of olefin monomers. Accordingly, in yet another aspect, the present invention provides a process for olefin polymerization comprising contacting at least one olefin monomer with a catalyst as described above under polymerization conditions. The olefin monomer contacted with the catalyst system is represented by the general formula H: CH ₂ =CHR ⁸ H In the above formula, R ⁸ is a hydrogen atom or an alkyl radical. The olefins used are ethylene, propylene, butene-1, pentene-1, and hexene-1.
1,4-methylpentene-1 or the above general formula H
There are other olefins that satisfy. The olefin monomer preferably has 10 or less carbon atoms. Olefin monomers can be homopolymerized or copolymerized. When copolymerizing propylene, British Patent Nos. 970478, 970479 and
Preferably, it is copolymerized with ethylene according to a sequential copolymerization process such as that described in US Pat. No. 1,014,944. When copolymerizing ethylene in the process of the invention, it is desirable to copolymerize ethylene in a mixture with, for example, butene-1 or hexene-1, such that the composition remains substantially the same during the polymerization process. . The above component 1) of the catalyst can be mixed with the other components of the catalyst in the presence of the olefin monomer. When a Lewis base compound is added to the catalyst, component 2)
It is preferable to mix the organometallic compound and the Lewis base compound in advance, and then mix this mixture with the reaction product, which is component 1). As is well known, Ziegler-Natsuta type catalysts are susceptible to impurities in the polymerization system.
Therefore, it is desirable that the monomers used in the polymerization and the diluent used if necessary be of high purity. For example, 5ppm as a monomer
It is desirable to use one containing less than (by weight) water and less than 1 ppm (by weight) of oxygen. High purity substances are available in British Patents Nos. 1111493, 1226659 and
It can be prepared by methods such as those described in US Pat. No. 1,383,611. The polymerization is carried out according to known techniques, for example, using an excess of liquid monomer as the polymerization medium in the presence or absence of an inert diluent such as a suitably purified paraffinic hydrocarbon. It can be carried out in phase or in gas phase (gas phase meaning substantially free of liquid medium). When polymerization is carried out in the gas phase, an evaporative cooling effect is achieved by introducing a monomer, such as propylene, in liquid form into the polymerization reactor and then evaporating the liquid monomer in the polymerization reactor. However, the temperature and pressure conditions of the reactor can be manipulated so that substantially all of the polymerization is carried out with the gaseous monomer. Polymerization in the gas phase is described, for example, in British patent no.
It can be carried out under conditions such that the temperature and partial pressure of the monomers are close to the dew point temperature and pressure for the monomers as described in detail in US Pat. No. 1,532,445. The gas phase polymerization reaction can be accomplished by any suitable means for carrying out gas-solid phase reactions, such as a fluidized bed reaction system, a spread bed reaction system, or a ribbon blender type reactor. The catalyst system according to the invention can be used to homopolymerize ethylene in a fluidized bed reactor or e.g.
A polymer can be obtained in high yield by copolymerizing with. Fluidized bed gas is a gaseous mixture consisting of the monomers to be polymerized and hydrogen, which is used as a chain transfer agent to control the molecular weight. That is, by copolymerizing ethylene and butene-1, the density is approximately
The gas composition used to produce ethylene copolymers with densities below 940 Kg/ ^m3 usually contains 50 to 60 mol% ethylene and 25 mol% butene-1, with the remainder being inert components and impurities. Except for hydrogen. The polymerization can be carried out either batchwise or continuously, and the catalyst components can be charged separately into the polymerization reactor or all catalyst components can be premixed and then charged into the polymerization reactor. When all the components of the catalyst are mixed in advance, it is desirable to mix them in the presence of the mixed monomers. Such mixing results in at least some polymerization of the monomers before the catalyst system is introduced into the polymerization reactor. If the polymerization is carried out in the gas phase, the catalyst components can be introduced into the polymerization reactor in suspension in a stream of gaseous monomer or monomer mixture. Polymerization can be carried out in the presence of hydrogen or a chain transfer agent such as dialkylzinc to control the molecular weight of the resulting polymer. When hydrogen is used as a chain transfer agent in the polymerization of propylene, the amount relative to the monomer is 0.01 to
It is preferably 5.0 mol%, particularly 0.05 to 2.0 mol%. If the monomer to be polymerized is ethylene or a mixture based on ethylene, the amount of hydrogen used can be higher, for example in the case of homopolymerization of ethylene, when more than 50 mol % of hydrogen is present in the reaction mixture. However, when copolymerizing ethylene, the amount of hydrogen is usually up to 35 mol %. The amount of chain transfer agent used will vary depending on the polymerization conditions, especially the polymerization temperature. The polymerization temperature is usually 20 to 100°C, preferably 50 to 85°C, at a pressure of 50 kg/cm ² or less. Polymerization can be carried out at any pressure previously proposed for the polymerization of olefin monomers. However, if the polymerization is carried out under a high pressure of up to 3000 Kg/cm ² , the polymerization temperature will be as high as 300° C., so it is desirable to carry out the polymerization at a relatively low pressure and temperature. Polymerization can be carried out at normal pressure, but it is preferable to perform the polymerization under slightly increased pressure.
It is preferable to carry out the reaction under a pressure of 50 kg/cm ² , particularly 5 to 30 kg/cm ² . The polymerization temperature is preferably higher than room temperature, but is usually 100°C or lower. The particle morphology of the resulting polymer is the component 1) of the catalyst system.
It should be understood that this depends on, or is influenced by, the particle morphology of the spray-dried solid material used as the spray-dried solid material. Therefore, the particle morphology of the resulting polymer can be controlled by adjusting the spray drying conditions. Apparatus suitable for carrying out the method according to the invention will now be described with reference to the accompanying drawings. 1 is a cross-sectional view of a typical spray drying apparatus that can be used to carry out the method of the present invention; FIG. 2 is a cross-sectional view of another apparatus equipped with a spray nozzle; and FIG. FIG. 4 is a cross-sectional view of another apparatus with a spray nozzle near the bottom of the apparatus, and FIG. 4 is a flow diagram of the entire apparatus including the spray dryer. In FIG. 1, a hermetic spray drying apparatus 1 consists of an upper cylindrical part 2 and a lower part 3 (generally conical). The upper part 2 is provided with a cover plate 4. A disk 5 attached to the end of the output shaft 6 of a high speed gearbox/motor assembly 7 is located near the top of the container. The disk 5 consists of two plates 8 and 9, and a blade 10 is attached between these plates. The drive shaft 6 is surrounded by a chamber 11 which reaches the upper plate 8 of the disc 5. A central opening 12 is bored in the plate 8. An air chamber 13 surrounding the chamber 11 is provided above the cover plate 4. The plenum chamber 13 communicates with the container 1 via an annular opening 14 between the central opening of the cover plate 4 and the lower extension of the chamber 11 . Attached to chamber 11 is a conduit 15 leading to a source (not shown) of a suspension containing a transition metal compound. A conduit 16 is provided in the filling chamber 13.
A conduit 16 is provided which communicates with a source of heated inert gas (not shown). A conduit 17 is disposed near the bottom of the container 1 and extends from the container 1 through the side wall of the conical portion 3 . Conduit 18 with pulp means 19
is provided at the bottom end of the conical portion 13 of the container and is connected to a hopper (not shown) for storing dry solids. During operation, the disk 5 is rotated at a high speed of 500 to 25,000 rpm. A suspension containing a transition metal compound and an inert liquid medium, for example a suspension of titanium trichloride in toluene, is introduced through conduit 15 and chamber 11 between plates 8 and 9 of disc 5. Due to the high speed rotation of the disk 5 and the blades 10, the suspension is blown off from the outer periphery of the disk 5 as mist droplets. Hot inert gas flows around the rotating disc 5 through the conduit 16, the plenum 13 and the annular opening 14.
The hot inert gas causes the liquid medium to evaporate from the suspension droplets. The inert gas containing the evaporated liquid medium and the accompanying spray-dried solids is discharged from the vessel 1 through conduit 17. The main part of the solids to be spray dried accumulates at the bottom of the cone 3 and is removed from the conduit 18 by actuation of the valve 19. The inert gas passing through conduit 17 is sent to a cyclone (not shown) to remove entrained solids therein, then to a condenser (not shown) to liquefy and recover the vapor, and finally to a reheater. (not shown). The reheated inert gas is then recycled to conduit 16. Spray dried solid material passing through conduit 18 is routed to a storage hopper (not shown). The inert gas supplied to conduit 16 is at a temperature of approximately
Preferably nitrogen at 130°C. The device shown in FIG. 2 is substantially similar to the device shown in FIG. 1, but a spray nozzle is used instead of a disc atomizer. In FIG. 2, parts corresponding to those in FIG. 1 are designated by the same reference numerals. The spray nozzle 20 is arranged within the plenum chamber 13 . The spray nozzle 20 includes an inner conduit 15A and an outer conduit 21. Inner conduit 15A leads to conduit 15, which leads to a source (not shown) of a suspension containing a transition metal compound. Outer conduit 21 is connected to an inert gas source (not shown). Conduits 15A and 21 are substantially coaxial and they taper downwardly. The nozzle 20 has a conduit 15 at its lower end.
It has an orifice 22 formed by both openings A and 21. In operation, the gas flow through conduit 21 flows through conduit 15.
and draw the suspension through 15A. The gas and suspension pass through the orifice 22 to form an atomized atom. The hot inert gas passing through conduit 16, plenum 13 and opening 14 passes through orifice 22 and causes the liquid medium to evaporate from the suspension droplets. The spray-dried solids are then recovered as described for the apparatus shown in FIG. The device shown in FIG. 3 differs from the device shown in FIG. 2 in the location of the spray nozzle. In FIG. 3, the spray nozzle 20 is arranged at the bottom of the container 1. The orifice 22 is directed upward. The container 1 comprises a conical cover plate 23, the central part of which is connected to the conduit 16.
It is connected to. During operation, gas and suspension are passed through orifice 22.
and the formed mist droplets rise first in the container 1 and then, under the influence of gravity and the action of the hot inert gas introduced countercurrently from the conduit 16, into the conical section. 3 and is collected in the same manner as in the apparatus described in connection with FIG. In FIG. 2, the thermally inert gas and the spray from the nozzle flow in the same direction, but in FIG. 3, the thermally inert gas and the spray from the nozzle flow countercurrently. In FIG. 4, the reservoir 24 is connected to the conduit 15. Conduit 18 is a storage tank 2 for solid material to be spray dried.
It is connected to 8. Conduit 17 leads to cyclone 25 which is provided with a bottom discharge conduit 26 and valve 27. Conduit 26 is connected to reservoir 28 . The cyclone 25 is connected through a steam conduit 29 to a scrubber condenser 30, in the upper part of which a spray head 31 is arranged. A conduit 32 extends from the bottom of the scrubber condenser 30 to a collection pot 33 which communicates with a liquid reservoir 35 through an overflow conduit 34. A conduit 36 extends from the bottom of the pot 33 to a pump 37, and then via a conduit 38 to a heat exchanger 39.
It is connected to. Conduit 40 connects heat exchanger 39 and spray head 31 . A recirculation conduit 41 connects scrubber condenser 30 to fan 42 .
From the fan 42, a conduit 43 reaches a heat exchanger 44,
Heat exchanger 44 is connected to spray dryer 1 through conduit 16 . The conduit 45 connects the conduit 43 and the storage tank 4.
6 is connected. In operation of the apparatus shown in FIG. 4, the suspension to be spray-dried is stored in a reservoir 24, and this suspension is passed through a conduit 15 in the desired proportions to a plenum provided at the top of the spray dryer 1. It is sent to the atomizing means in the chamber 13. Spray drying is carried out in the sprayer 1 in the same manner as described in connection with FIG. The solid material to be spray dried is collected at the bottom of the spray dryer 1 and sent via conduit 18 directly to storage tank 28 . The gas mixture passing through conduit 17 reaches cyclone 25 where entrained solids are separated from the gas.
Solids are collected at the bottom of cyclone 25 and removed through conduit 26 by operating valve 27. Solids from cyclone 25 is also sent to storage tank 28. The gas containing the still vaporized liquid medium is transferred to the vapor conduit 2.
9 to the scrubber condenser 30. A cold liquid identical to the liquid medium in the suspension is sprayed from the spray head 31 into the scrubber condenser 30 to condense the evaporated liquid medium and remove residual solid particles not removed in the previous step. From the bottom of the liquid scrubber condenser 30 is sent through conduit 32 to pot 33. Excess liquid is removed from overflow conduit 34. The remaining liquid passes through conduit 36, pump 37 and conduit 38 to heat exchanger 39 where it is cooled and sent through conduit 40 to spray head 31. The liquid in container 35 is subsequently used with or without purification to prepare a suspension for spray drying. Gas substantially free of liquid vapor is transferred from the scrubber condenser 30 to conduit 41, fan 42 and conduit 4.
3 to a heat exchanger 44 where the gas is heated and returned to the spray dryer 1 through conduit 16. Inert gas is supplied from reservoir 46 via conduit 45 into conduit 43 to compensate for gas losses from the system. It will be readily appreciated that if a spray nozzle is used as shown in FIGS. 2 or 3, a separate conduit will be required between the reservoir 46 and the spray nozzle. It will be readily understood that other modifications will be apparent to those skilled in the art and such modifications may be adopted without departing from the scope of the invention. Hereinafter, the present invention will be specifically described with reference to Examples. All operations in the Examples were performed under a nitrogen atmosphere unless otherwise specified. All glass equipment was also dried in an air oven for at least 1 hour at 120°C and further purged with nitrogen before use. Preparation of titanium trichloride suspension A Kneading process Contains 570 kg of steel balls with a diameter of 25.4 mm, total volume of approximately 165
A Jeep Technique SM50 Vibro mill with a 200 mm was sealed, evacuated to 0.2 mm of mercury, replaced with nitrogen, and filled the mill with nitrogen gas. A mixture of ethylene glycol and water at 0°C was passed through the jacket of the mill. Titanium trichloride (approximate formula TiCl ₃
Stouffer TiCl ₃ −AA expressed as 0.33AlCl ₃
12.01Kg was introduced into the mill as a free flowing powder,
Then 2.95 Kg of aluminum chloride (per ₃ moles of TiCl present in the Stouffer TiCl ₃ -AA above)
0.50 mol) was added. The mill was operated at a frequency of 1500/min and an amplitude of 2 mm while a mixture of ethylene glycol and water at 0°C was passed through the jacket of the mill.
I let it vibrate for 24 hours. After stopping the vibration of the mill,
Diphenyl sulfone 9.02Kg (Storfur above)
0.70 mol per ₃ mol of TiCl present in TiCl3 _- AA) was added and the mixture was kneaded for 5 minutes, after which kneading was stopped. Titanium tetrachloride 650cm ³ in the contents of the mill
(Present in the Stoffer- _TiCl3 -AA above)
0.10 moles per ₃ moles of TiCl) was added and milling was continued for a further 24 hours while the 0° C. ethylene glycol and water mixture was passed into the jacket of the mill. After the kneading was completed, the titanium trichloride product was removed from the mill by inverting the mill, vibrating it, and collecting the fallen solid product in nitrogen. B. Washing Step 1.1 kg of the kneaded product obtained in the above step A) was transferred to a 6-volume glass container equipped with a jacket and a stirrer. Add degassed toluene 5 to a glass container,
The mixture was stirred and the resulting suspension was heated to 100°C. This suspension was maintained at 100° C. for 1 hour, and then, after heating and stirring, the solid content was allowed to settle. The supernatant liquid was aspirated and separated from the settled solids. The above process was repeated four more times. Enough degassed toluene was used each time to fill the container to the 6 mark. A thick suspension was obtained after the final washing and removal of the washing liquid. Preparation of suspension (reference example) By adding degassed toluene to the concentrated suspension obtained in steps A) and B) above, the volume was again reduced to 6.
Diluted until. To this suspension was added 10 mol % of solid diphenyl sulfone based on the titanium trichloride contained in the suspension. Stir this suspension and
It was heated to 70°C for 40 minutes. The temperature was maintained at 70°C for 1 hour, after which stirring was stopped. Even after the stirring was stopped, the solid particles were finely dispersed and did not fold or settle. Repeat the above operation for several materials,
Finally, collect these materials and reduce the solid content to approximately 10% by weight.
A suspension 15 was obtained containing . This suspension will be hereinafter referred to as suspension. Preparation of Suspension (Reference Example) A large number of concentrated suspensions obtained by repeating the above steps A) and B) were collected and the solid content was approximately 30%.
A suspension containing 15% by weight was obtained. This suspension will be hereinafter referred to as a suspension. Preparation of Suspension (Reference Example) The above suspension preparation method was repeated to obtain a suspension (same content as the suspension). Preparation of suspension Repeat the suspension preparation method to obtain a concentrated suspension15
I got it. High molecular weight polystyrene (manufactured by BP Chemicals)
A toluene solution of polystyrene was prepared by adding 40 g to 250 cm ³ of toluene and heating the mixture in air to about 65° C. for a time sufficient to dissolve the polystyrene in the toluene (about 10 minutes). Nitrogen gas was bubbled through the solution to drive out dissolved air, and the solution was then maintained under a nitrogen atmosphere. A polystyrene solution is added to the above concentrated suspension, and polystyrene is 1% by weight based on the solid content in the concentrated suspension.
Added in proportions such that The obtained suspension will hereinafter be referred to as suspension. Examples 1 to 4 (Examples 1 to 3 are reference examples) The suspensions were spray dried using a spray drying apparatus similar to that shown in FIG. The diameter of the spray drying apparatus was 2.2 m, the height of the cylindrical part was 195 m, and the angle of the conical part was 60. Nitrogen gas, which was preheated to about 137° C., was circulated before entering the spray dryer. The nitrogen gas supply rate was approximately 600 kg/hour. The suspension was supplied to the spray dryer at room temperature without being preheated. The rotational speed of the spray disk and the time of feeding the suspension to the spray dryer were varied. Details of these conditions and the average particle size of the spray dried product are shown in Table 1 below.

EXAMPLE 5 The product obtained in Example 4 was used to polymerize liquid propylene without substantially using any other liquid. The propylene used in the polymerization was purified as follows. That is, propylene gas was first passed at 50-60°C through a column (7.6 cm diameter, 0.9 m length) containing 1.6 mm particles of Alcoa Fl alumina, and then a BTS catalyst (on a magnesium oxide support) was passed through a column (7.6 cm diameter, 0.9 m length) containing The evacuated gas is condensed by passing it through a column similar to the above containing copper (cupric oxide reduced to fine metallic copper) at 40-50°C, and the liquid propylene is passed through a Union Carbide 3A molecular sieve 1.6 mm pellet. 4 columns each containing (each with a diameter
7.6cm, two lengths are 0.9m and the other two are 1.8m)
at 25°C. By the above treatment, the water content in the monomer is reduced to 5-
Reduced from 10ppm (capacity) to less than 1ppm (capacity),
The oxygen content was reduced from 1-2 ppm (by volume) to less than 0.5 ppm (by volume). The content of inert compounds (nitrogen, ethane, etc.) remained unchanged at 0.3%, and the content of unsaturated hydrocarbons (alene, methylacetylene, etc.) remained unchanged at less than 1 ppm. Polymerizations were carried out using an 8 volume styrene steel autoclave equipped with a vertical anchor stirrer. The autoclave was heated to 70°C, evacuated and charged with propylene. The autoclave is then evacuated again and
The above procedure was repeated five times. A heptane solution of diethylaluminium chloride (20 gm mmol) was injected into the autoclave containing propylene gas described above at 35° C. and 0.14 Kg/cm ² gauge pressure. Boiling point 2 gm mmol of the product obtained in Example 4
The suspension in pentamethylheptane having a temperature of 170℃-180℃ was injected into an autoclave, and liquid propylene 5 was added while stirring with a stirrer at 150 rpm.
was added over 40 minutes. This addition of propylene was carried out by transferring 5.5 liters of liquid propylene from a room-temperature beer bottle to an autoclave under pressure with nitrogen. The autoclave was heated during the addition of liquid propylene and allowed to reach 70°C once the propylene addition was complete. Then hydrogen
200 gm mmol was added and the temperature of the autoclave contents was maintained at 70°C. The purity of the hydrogen used is
Column containing 99.99% commercially available hydrogen molecular sieve material (Union Carbide 3A) (8 inches x 4
The product was purified by passing it through a medium (feet) at 20°C. This hydrogen was stored in the sieve column and removed as needed. Polymerization was carried out at a temperature of 70° C. and a pressure of about 30 Kg/cm ² gauge. At 15, 30, 60, and 90 minutes after the initial hydrogen addition, 20 gm mmole of hydrogen was added. After completion of the polymerization, 2 hours after the completion of the addition of liquid propylene, the autoclave was degassed for 10 minutes to remove unpolymerized propylene and yield a free-flowing pink powder. The obtained polymer has a spherical particle morphology, a flexural modulus (see a below) of 1.47 GN/m ² and a melt flow index (see b below) of 18.1, with residual titanium present in the polymer. The amount of is 54ppm (weight)
It was hot. (a) Flexural modulus (FM) Flexural modulus is from Polymer Age, March 1970 issue.
Measurements were made using the cantilever beam apparatus described on pages 57 and 58. After holding the specimen at 23°C and 50% RH for 60 seconds, the deformation rate of the specimen was measured at 1% skin strain. The test piece used was approximately 150×
This test piece had a size of 19 x 1.6 mm, and was prepared as follows. 23 g of polymer was mixed with 0.1% by weight of an antioxidant (Topanol CA), and this mixture was added to a Brabender plasticizer and processed at 190° C., 30 rpm, and a load of 10 kg to prepare a crepe. The crepe was placed in a template, sandwiched between aluminum foils, and pressed using an electric Tansy press at a temperature of 250°C. The press was preheated for 6 minutes under sufficient pressure to cause the polymer to flow from the template, approximately 1 ton of force.
After preheating, the pressure was increased in 5 ton increments to a total of 15 ton, and the gas was vented (that is, the pressure was released) each time the pressure was increased in 5 ton increments. After 2 minutes, when the pressure reaches 15 tons, press with air and water for 10 minutes.
It was cooled down to room temperature for a minute. Next, the obtained plaque was cut into a size of 150 x 19 x 1.6 mm.
A test piece of each polymer was placed in an annealing furnace at 130°C.
After maintaining this temperature for 2 hours, the switch was turned off and the furnace was allowed to cool down to room temperature at a rate of 15°C per hour. (b) Melt Flow Index (MF1) Melt flow index was measured according to ASTM D1238/70, condition N (190°C and 10Kg). Example 6 35Kg of polypropylene powder was placed in a 91 volume stainless steel autoclave equipped with an agitator. The polypropylene used had a flexural modulus of 1.49 GN/m ² and was dissolved in hot heptane at 4.0% by weight as measured by weight loss after 24 hours of Soxhlet extraction.
The stirrer rotated at 60 rpm and was allowed to rotate continuously at this rate during the following procedure. The autoclave was purged with nitrogen at 70°C, then the pressure was reduced to mercury.
It was reduced to 0.1mm. Add liquid propylene to the autoclave, evaporate it, and reduce the pressure to 28Kg/
It was raised to cm ² gauge. Hydrogen was added separately in a proportion of 1.5% by weight relative to propylene. A solution of diethyl aluminum chloride in pentamethylheptane and a suspension of the product obtained in Example 4 (stored for several weeks) in pentamethylheptane (25% by weight) were added to the autoclave in a molar ratio of 8:1, respectively. , initiated polymerization. Liquid propylene was charged and gaseous propylene was degassed while the catalyst was added. When the polymerization has started, the degassing of the autoclave is stopped, liquid propylene is introduced into the autoclave at a rate of about 15 Kg/hour at 20°C, and the propylene-saturated polypropylene is intermittently pumped from the autoclave at a rate of about 10 to 12 Kg/hour. coalescence)/time. Temperature and pressure are 70℃ and
Maintained at 28Kg/ ^cm2 gauge. The above diethylaluminum chloride solution and the above suspension were mixed so that the molar ratio of diethylaluminium chloride to titanium trichloride was 8:1, and the polymer content was 10 to 12 kg/
Continuously introduced into the autoclave to produce at the desired rate of time. The properties of the polymer product taken out at various times during the polymerization are as shown in Table 2.

[Table] Example 7 (Reference Example) A. Preparation of titanium trichloride suspension The procedure described in Example 2 of GB 1485181 was repeated. However, Stoffer TiCl ₃
-AA and tri-n-butylphosphine were used in a molar ratio of 4.2:1. The kneaded titanium trichloride product was suspended in purified n-heptane to prepare a suspension containing 40% by weight of the kneaded titanium trichloride product based on the total amount of the suspension. B. Spray Drying of Titanium Trichloride Suspension The suspension obtained in step A) above was spray dried using a laboratory scale glass spray drying apparatus having a structure similar to that shown in FIG. The spray dryer had a diameter of 15 cm and a length of 0.7 m. conical part 3
was generally replaced by a hemispherical bottom part and the conduit 17 was omitted. The valve 19 of the conduit 18 is also omitted, and the conduit 18
was connected directly to the cyclone and collected the solid material into the cyclone's catch pot. The spray nozzle used was a 1/4JAU Automatic Air Spraying Systems Co., Ltd. in the United States with a diameter of 0.42mm.
It was an atomizing nozzle. For spraying, use nitrogen heated to 140 to 150℃ in advance.
A nitrogen atmosphere was applied while flowing through conduit 16 at a rate of 170-180 min. Approximately 2.3 Kg/cm ² (absolute pressure) of nitrogen was supplied to the spray nozzle. The suspension obtained in step A) above was fed from the stirred storage flask to the spray nozzle by applying excess nitrogen pressure (5 cm of mercury) to the storage flask. Example 8 (Reference Example) Polymerization was carried out using an 8 volume stainless steel autoclave. Consisting essentially of dodecane isomers 170-185℃
An aliphatic hydrocarbon diluent 3 having a boiling point range of 3 is placed in an autoclave at a pressure of 50 mm of mercury.
Degassed at 70°C for 15 minutes. Next, propylene was introduced into the reactor and the pressure was adjusted to 1.1 Kg/cm ² (absolute pressure).
The diluent was stirred and this stirring was continued during the following operations. Thirty millimoles of a 25% by weight solution of diethylaluminium chloride dissolved in the above hydrocarbon diluent was added to the autoclave. 2.5 mmol of the spray-dried titanium trichloride obtained in Example 7 were then added as the hydrocarbon diluent suspension. While maintaining the autoclave at 70°C, feed propylene into the autoclave to increase the pressure to 11.5
Kg/cm ² (absolute pressure) was maintained. Then hydrogen 200
Added mmol. Add propylene and apply pressure
The pressure was maintained at 11.5Kg/cm ² (absolute pressure). After 4 hours, the supply of propylene was stopped and the autoclave was evacuated to normal pressure. The polymer suspension was placed in a receiver and the polymer was separated in the atmosphere. A sample of the polymer was washed with petroleum ether (boiling point 60-80°C) and the polymer was dried at 100°C in a fluidized bed with nitrogen as diluent gas. For comparative purposes (Comparative Example A), Example 7 A)
Polymerization was carried out in the same manner using 3 mmol of the kneaded titanium trichloride product obtained in the step. When the particle size of the obtained polymer product was analyzed, the results shown in Table 3 were obtained.

[Table] The content of fine polymer in the polymer product of Example 8 (41.7% by weight) is lower than the content of fine polymer in the polymer product of Comparative Example A (70.7% by weight). it is obvious. Furthermore, the polymer product of Example 8 was free-flowing, non-powder, whereas the polymer product of Comparative Example A
The product has poor flowability. It was a completely powdery substance. Example 9 (Reference example) A. Preparation of titanium trichloride suspension Jieve Technique SM6 containing 180 stainless steel balls with a diameter of 25.4 mm and having an effective capacity of about 1.5
The Vibromil chamber was sealed, evacuated to 0.2 mm of mercury, and filled with hydrogen.
To this mill was added 17.7 g of dry phenoxatin (0.10 mol per mole of titanium trichloride present in Stouffer TiCl ₃ -AA) and additional titanium trichloride.
176.5 g (Storfer TiCl ₃ -AA) was added.
The mill was cooled to 0°C by passing a mixture of ethylene glycol and water at 0°C through the jacket of the mill. A mixture of ethylene glycol and water was passed through the jacket at a frequency of 1500/min and an amplitude of 2.
The mill was vibrated for 24 hours at mm. After 24 hours of milling, the titanium trichloride product was removed from the mill by inverting the mill, vibrating the mill, and collecting the solid product under a nitrogen atmosphere. 150 g of the kneaded product was suspended in 1500 cm ³ of diluent of the aliphatic hydrocarbon used in the polymerization of Example 8 at room temperature. stir the mixture
Heated to 100°C. When 100°C was reached, the stirrer and heater were switched off, the solids allowed to settle and the supernatant liquid was decanted at a temperature of about 75°C.
This procedure was repeated four more times. After the five treatments were completed, an additional aliphatic hydrocarbon diluent was added to give a titanium trichloride product suspension of 15% by weight. B Spray drying of titanium trichloride suspension The suspension obtained in step A) above was spray-dried using the apparatus used in step B) of Example 7. however,
The diameter of the spray nozzle used was 0.52 mm. The spraying conditions were similar to those described in step B) of Example 7, but the nitrogen was preheated to 170-180°C and its feed was at a rate of 185/min.
Further, nitrogen was supplied to the spray nozzle at a pressure of 1.7 to 2.0 Kg/cm ² . The resulting spray-dried product was a free-flowing powder. Example 10 (Comparative example) 1 Titanium tetrachloride-silica-magnesium chloride-
Preparation of the precursor component of tetrahydrofuran This method is generally used in EP-A-20818, page 28, 15
As stated in lines to page 29, line 8,
A product similar to that used in Example 3 was obtained using reduced amounts of reagents, as described below. a Magnesium chloride-tetrahydrofuran-
Preparation of the silica mixture The mixture was prepared in two three-necked glass flasks equipped with a stirrer, condenser, and connected to a nitrogen source. A nitrogen atmosphere was created inside the flask. Samples of tetrahydrofuran (THF) were first stored on molecular sieves and then stored on activated alumina and dried. This dry THF 410
^cm2 was placed in the flask. The flask was placed in a water bath at ambient temperature. 29.4 g of magnesium chloride was slowly added to the stirred THF. Upon completion of the magnesium chloride addition, 36.9 g of fuming silica (evacuated and then stored under nitrogen) was added.
Cabosil (M5 silica) was slowly added to the mixture with continued stirring. The mixture was then heated to reflux using a water bath and maintained at gentle reflux for 2 hours. The mixture was cooled with stirring. b Preparation of Magnesium Chloride-Titanium Tetrachloride-Tetrahydrofuran Composition This composition was prepared in one three-necked glass flask equipped with a magnetic stirrer and connected to a nitrogen source. A nitrogen atmosphere was created inside the flask. 328 cm ³ of THF (dried as in step (a)) was placed in the flask and 5.4 g of magnesium chloride was added. Stir this mixture without heating and make 3.6 (5) cm ³
of titanium tetrachloride was added dropwise. This occurred during the addition of titanium tetrachloride. The mixture was stirred for 1 hour without heating, then heated to 60°C and maintained at 60°C for 1 hour. Heating was then stopped and the mixture was allowed to cool to room temperature with stirring. c. Precursor Formation The composition obtained in step (b) is passed through a transfer tube containing the mixture obtained in step (a).
into a flask. The combined mixture was stirred for 30 minutes without heating. The combined mixture was heated to reflux temperature and maintained at gentle reflux for 2 hours. Heating was stopped and the mixture was cooled to room temperature with stirring. A small amount of this mixture was removed for analysis and testing in a polymerization system. 2 Preparation of precursor components of titanium chloride-magnesium chloride-silica-polystyrene-tetrahydrofuran This method is generally used in EP-A-20818, p. 28, 15
A product similar to that used in Example 6 was obtained using reduced amounts of reagents as described in lines to page 29, line 8, as described below. a Manufacture of magnesium chloride-titanium tetrachloride-tetrahydrofuran compositions This generally applies to 1b) with the exceptions noted below.
Prepared in the same manner. This composition was prepared in two flasks using 800 cm ³ of THF, 13.4 g of magnesium chloride, and 8.9 cm ³ of titanium chloride. After stirring for about 30 minutes at room temperature, the contents of the flask were heated to reflux temperature and maintained at gentle reflux for about 45 minutes. The mixture was then cooled to room temperature with stirring. b. Manufacture of silica-tetrahydrofuran-polystyrene mixtures. This generally applies to 1a) with the exceptions noted below.
Prepared in the same manner. This mixture consisted of 650 cm ³ of THF, 49.9 g of silica and 22.5 g of polystyrene (Dow Chemical Company).
It was prepared in 3 flasks using a "Styron" 686/7, commercially available from Chemical Company. This mixture was not heated. c. Precursor formation: Passing the composition obtained in step (a) through a transfer tube containing the mixture obtained in step (b).
I put it in a flask. The combined mixture was stirred for 30 minutes without heating. The combined mixture was heated to a temperature in the range of 60-650°C and maintained at that temperature for 2 hours. The mixture was then cooled to room temperature with continued stirring. A small amount of the resulting mixture was taken for analysis and testing in a polymerization system. 3. Spray Drying Precursor Components The main parts of the products of 1c) and 2c) were spray dried separately using the following conditions. Spray drying was carried out using a glass laboratory scale spray drying apparatus similar to that described with reference to FIG. 3 of the drawings of EP-A-37182.
The spray drying apparatus had a diameter of 18 cm, a length of 0.7 m and a roughly hemispherical bottom cross section. The conduit from the bottom section was connected directly to a cyclone with a catch pot where solid material could be collected. The spray nozzle is located at the top of the device and is manufactured by Spraying Systems, Inc.
1/4JAU Automatic Air Atomizing Nozzle (JAU Automatic Air Atomizing) obtained from
Nozzle) with a 0.72 mm diameter nozzle. Spraying was carried out under nitrogen by passing a nitrogen stream preheated to a temperature of 110° C. through the spray dryer at a rate of 190 dm ³ /min. Nitrogen at a pressure of approximately 0.6 Kg/cm ² gauge was introduced into the spray nozzle. Precursor mixture is 0.05Kg/cm ² from 2 or 3 flasks.
An excess nitrogen pressure of 100 ml was applied to the flask to feed the spray nozzle. The solids were collected, placed in a storage flask, and stored under nitrogen. The solid content obtained by spray drying the product of 1c) is designated by the reference number 1S, and the solid content obtained by spray drying the product of 2c) is designated by 2S. 4 Polymerization of Propylene Propylene was polymerized using the precursor components and the spray-dried derivative. 1 with efficient stirrer and water jacket
The polymerization flask was carefully dried and 500 cm ³ of isoparaffin fraction, substantially all of which had a boiling point in the range 117-135° C., was introduced. This isoparaffin fraction was purged with nitrogen for 1 hour and passed through a molecular sieve column before being charged into a polymerization flask. In the flask, the isoparaffin fraction is
It was evacuated at 60°C and then nitrogen was introduced. The water and oxygen content of the isoparaffin fraction is 10% by weight
It was less than ppm. Triethylaluminum is added to the isoparaffin fraction, which is stirred,
It was evacuated and then saturated to 1 atmosphere with purified propylene. Stirring was continued and then the precursor component of 1c) or 2c) or a suspension of the spray-dried material 1S or 2S in this isoparaffin fraction was added.
The pressure inside the reaction vessel was maintained at 1 atmosphere by supplying propylene from a cylinder. Approximately 30 minutes after introduction of the precursor component or spray-dried material,
The experiment was stopped by removing the propylene and passing nitrogen through the reaction vessel. Details of the polymerization conditions and the results obtained are shown in Table 4.

【table】

[Table] 5 Ethylene post-polymerization In propylene polymerization experiments 2 to 5, the polymerization flask was
The propylene was removed by evacuation to a pressure of 0.4 Kg/cm ² and then stopped by evacuation and at least one more addition of nitrogen. After evacuating the system once more, ethylene was introduced and a pressure of 1 atmosphere was established and maintained. The polymerization results are shown in Table 5.

[Table] 6 Ethylene Polymerization The method described in 4) was carried out in the same manner except that ethylene was used instead of propylene and the polymerization was continued for 1 hour. In polymerization experiments, hexene-
1 was added after the addition of triethylaluminum, but before the addition of the precursor components. The conditions used and the results obtained are shown in Table 6.

[Table] Example 11 Finely divided anhydrous magnesium chloride 134.4g
(1.41 mol) and ethyl benzoate 74 ml (70.6 g, 0.47
molar) in a ball mill to produce approximately 205g of product.
was placed in a 5-volume glass container with a jacket, titanium tetrachloride 2 (3.45 kg) was added, the mixture was stirred,
The temperature was raised to 100°C (30 minutes) and held at 100°C for 3 hours. The mixture was allowed to settle for 2 hours at 100°C, the supernatant liquid was decanted, and the residue was cooled. This treatment with titanium tetrachloride was repeated. The cooled solid residue was first diluted with 3 heptane (90% n-heptane).
The mixture was stirred and heated to about 100° C. (1 hour), allowed to settle (about 3 hours), the supernatant liquid was decanted, and the residue was cooled. Second, 3
of heptane, the mixture was stirred, heated to 10°C (40 minutes), and settled at 60°C (approximately 2 hours).
The supernatant was decanted and the residue was cooled. Further, washing with 2.5 heptane at room temperature, stirring the mixture (15 minutes), settling (about 2 hours), and decanting the supernatant were repeated three times. Heptane was added to the residue to form a slurry of 1, which was removed from the reaction vessel and the slurry was stored in a nitrogen atmosphere. A portion of this slurry containing approximately 200 g of solid product was allowed to settle and the supernatant liquid was decanted. solid content
Washed three times with 1.5 g of toluene, stirred (5 minutes), settled, and decanted the supernatant. Add 100ml of toluene to the residue (approx. 600ml) in one container.
and 2.5g of polystyrene to make a slurry,
This was transferred to a two-glass flask, stirred, and further 2 g of polystyrene was added. The slurry was spray dried in a glass spray dryer with a diameter of 15 cm and a length of 70 cm. This spray dryer differs from that shown in FIG. 2 in that the conical section 3 is replaced by a hemispherical section, a conduit 17 and a valve 19 are guided,
The difference is that conduit 18 is configured to be connected to a cyclone for product recovery. diameter
Using a 0.72mm spray nozzle, you can also use 140~145
Nitrogen heated to ℃ was used as the drying gas. The nitrogen pressure in the conduit 21 is 0.5Kg cm ^-2 (gauge pressure),
The overpressure in the second flask was 0.1 Kg·cm ^-2 . Polypropylene was prepared using the spray-dried product in the same autoclave as in Example 5 as follows. Aliphatic hydrocarbon fraction (mainly dodecane isomer, boiling point 170-185°C) 3 was placed in an autoclave and degassed at 70°C to 0.07 Kg·cm ^-2 (absolute pressure) (about 15 minutes). Gaseous propylene was charged to create an absolute pressure of 1.1 Kg·cm ^-2 . The mixture was stirred and 20 mmol of triisobutylaluminum dissolved in 40 ml of the above hydrocarbon fraction, methyl p-methylbenzoate dissolved in 40 ml of the above hydrocarbon fraction and 0.15 mmol of the catalyst prepared as above (as Ti) were added. (in the form of a suspension of spray-dried solids in heptane) was added. Furthermore, propylene was charged to make the absolute pressure 10Kg・cm ^-2 ,
10 mmol of hydrogen was added. Polymerization was continued while maintaining the pressure by adding propylene to the reaction system. After 30 minutes and after 1 hour, 10 mmol of hydrogen were added. After 2 hours, the propylene feed was stopped and the autoclave pressure was released. The polymer product was recovered by filtration using a diluent. The polymer was dried at 100°C in a nitrogen fluidized bed and the properties of the polymer were investigated. The results were as follows.

[Table] Measured.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a typical spray drying apparatus that can be used to carry out the method of the present invention;
3 is a sectional view of another device with a spray nozzle near the bottom of the device, and FIG. 4 is a sectional view of the entire device including the spray dryer. This is a flowchart. FIG. 5 is a flowchart showing the steps for preparing a catalyst component produced by the method of the present invention. The reference numbers are as follows. DESCRIPTION OF SYMBOLS 1... Airtight spray drying device, 2... Upper cylindrical part, 3... Lower cylindrical part, 4... Covering plate, 5...
... Disk, 6 ... Output shaft, 7 ... High speed gearbox/motor assembly, 8, 9 ... Plate, 10 ... Vane, 11 ... Chamber, 12 ... Center opening, 1
3... Air chamber, 14... Annular opening, 15, 16,
17, 18... Conduit, 19... Valve means, 20
... Nozzle, 21 ... Outer conduit, 22 ... Orifice, 23 ... Covering plate, 24 ... Storage tank, 25 ...
Cyclone, 26...Discharge conduit, 27...Valve, 28...Storage tank, 29...Steam conduit, 30...
Scrubber condenser, 31... Spray head, 32... Conduit, 33... Collection pot, 34... Conduit, 35...
...Storage tank, 36...Conduit, 37...Pump, 38...
... Conduit, 39 ... Heat exchanger, 40 ... Conduit, 41
... recirculation conduit, 42 ... fan, 43 ... conduit, 44 ... heat exchanger, 45 ... conduit, 46 ...
Storage tank.

Claims (1)

[Scope of Claims] 1. A method for preparing a catalyst component for polymerizing olefins containing solid particulate titanium halide, comprising: (1) particles of a solid substance in an inert liquid medium, which is an aliphatic, alicyclic or aromatic hydrocarbon; and a substance that promotes agglomeration of the solid particles, the suspension comprising a titanium halide, the titanium halide being dissolved in the inert liquid medium. (2) spray drying said suspension; and (3) ) recovering a spray-dried titanium halide-containing catalyst; 2. The method of claim 1, wherein the solid material is or comprises titanium trichloride. 3. The solid substance is a product obtained by contacting titanium tetrachloride with silica, alumina, magnesia, a mixture or complex of two or more of these compounds, or magnesium chloride. the method of. 4. The method of claim 1, wherein the suspension comprises titanium tetrachloride in a form dissolved in an inert liquid medium. 5. The method according to any one of claims 1 to 4, wherein the suspension comprises a Lewis base compound selected from among ethers, esters, organophosphorus compounds or sulfur-containing organic compounds. 6. The method of claim 5, wherein the Lewis base compound is blended with the titanium halide by grinding the solid titanium halide in the presence of the Lewis base compound. 7. The method according to claim 5, wherein the Lewis base compound is blended by grinding a solid particulate carrier in the presence of the Lewis base compound. 8. Claim 7, wherein the support is treated with titanium tetrachloride to form solid particles containing titanium halide.
The method described in section. 9 Claims 1 to 8, in which spray drying is performed using an inert gas at a temperature not exceeding 200°C.
The method described in any of the preceding sections. 10 The hot gas is removed from the spray drying zone, then passed through a cyclone to remove entrained solids in the gas stream, and then passed through a condenser to condense and remove the vapor of the inert liquid medium, before being recycled again. 10. The method of claim 9, wherein the method is heated and recycled to the spray drying process.