JP4966482B2 - Process for producing ion-exchangeable layered silicate particles, catalyst component for olefin polymerization using the same - Google Patents

Description

  The present invention relates to a method for producing ion-exchange layered silicate particles and an olefin polymerization catalyst component using the same. More specifically, by using the method for producing ion-exchangeable layered silicate particles having specific properties and the obtained ion-exchangeable layered silicate particles, the fluidity is good, and adhesion to the polymerization reactor wall surface or the like is achieved. The present invention relates to a catalyst component that enables the production of polyolefin polymer powder that is easy to handle and has a good shape.

It is known to produce an olefin polymer by polymerizing an olefin in the presence of a catalyst using clay or clay mineral as a catalyst component for olefin polymerization (see, for example, Patent Document 1). There are also known olefin polymerization catalysts containing, as a component, an ion-exchange layered compound subjected to acid treatment, salt treatment, or coexistence treatment of an acid and a salt (see, for example, Patent Documents 2 to 4).
Furthermore, in order to improve the particle properties of the polymer to be produced and prevent fouling, the properties are obtained by a preliminary polymerization method (for example, see Patent Documents 5 to 6) or by granulating clay or clay mineral. A method for obtaining a good polymerized powder is also known (for example, see Patent Document 7).
However, the current state of the art has not yet reached a level that satisfies both the catalytic activity and the particle properties of the polymer essential for the production of a stable polymer. Furthermore, the polymer obtained is designed on the premise that it is once melted and processed into a uniform pellet in the subsequent process. Are difficult to handle.
Japanese Patent Laid-Open No. 5-301917 Japanese Patent Laid-Open No. 7-309907 JP-A-8-127613 JP-A-10-168109 JP-A-5-295022 JP 10-168130 A JP-A-7-228621

  In view of the above-mentioned problems, the present invention provides a spherical, uniform ion-exchange layered shape that can obtain a polymer powder having good fluidity and excellent powder properties that can be handled in the same manner as pellets. Providing a method for producing silicate particles, and further using the ion-exchange layered silicate particles, having a large particle size, uniform shape, good fluidity, and powder properties that can be handled in the same way as pellets It is an object of the present invention to provide a catalyst component for olefin polymerization which can obtain an excellent polymerization powder with high activity and low cost.

  As a result of intensive studies to solve the above problems, the inventors of the present invention can control the particle shape and particle size by granulating the ion-exchangeable layered silicate through a granulation process in at least two stages. By using the ion-exchange layered silicate particles with controlled particle shape and particle size as the catalyst component for olefin polymerization, the shape is good while maintaining the polymerization of the olefin polymerization catalyst that is economically required. It was possible to produce a polyolefin polymer powder that was easy to handle with ease, and obtained knowledge that an industrially and economically excellent product could be obtained, leading to the completion of the present invention.

That is, according to the first invention of the present invention, the average particle diameter is 25 to 200 μm, and M / L ≧ 0.80 (where L is the value of the maximum particle diameter of the projected view and M is orthogonal to L This is a production method by spray granulation of ion-exchange layered silicate particles in which the number of particles satisfying 50% or more of the total number of particles is granulated in at least two stages. step only contains, in a first stage granulation process, using the average particle size of the ion-exchange layered silicate microparticles 0.01~5μm the raw material, the average particle size in the disk rotation speed 10000~30000rpm is 1~25μm And a method for producing ion-exchange layered silicate particles, characterized in that the rotational speed of the secondary granulation disk is 5,000 to 20000 rpm lower than the rotational speed of the primary granulation disk. .

According to the second invention of the present invention, in the first invention, the average particle size of the particles obtained in the first stage granulation step is from 1 to 15 μm. A method for producing silicate particles is provided.

According to a third aspect of the present invention, there is provided the method for producing ion-exchange layered silicate particles according to the first or second aspect , wherein the crushing strength is 3 to 15 MPa.

  According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the ion-exchangeable layered silicate is characterized in that the ion-exchangeable layered silicate particles are smectite group silicate particles. A method for producing salt particles is provided.

  According to a sixth aspect of the present invention, there is provided an olefin polymerization catalyst component comprising the ion-exchangeable layered silicate particles of any one of the first to fifth aspects.

  Since the ion-exchange layered silicate particles of the present invention are granulated in at least two stages of granulation processes, the average particle size is 25 to 200 μm, and the number of particles satisfying M / L ≧ 0.8 is the number of previous particles. Spherical shape of 50% or more of the number. Therefore, when this ion-exchange layered silicate particle is used as a catalyst component for olefin polymerization, it has high catalytic activity, large particle size, uniform shape, and can be handled in the same way as pellets with good fluidity. A polymer powder having excellent properties can be produced.

I. Ion Exchange Layered Silicate Particles The ion exchange layered silicate particles of the present invention are a first-stage granulation step obtained by granulating a raw material ion exchange layered silicate to obtain primary granulated particles, and a primary obtained. It is manufactured from a step of granulating in at least two stages comprising a step of granulating the granulated particles as constituent particles again. Details will be described below.

  In the present invention, the ion-exchange layered silicate used as a raw material has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other, and the contained ions can be exchanged. A silicate compound. Most ion-exchange layered silicates are naturally produced mainly as the main component of clay minerals, and therefore often contain other impurities (quartz, cristobalite, etc.). May be. Further, the ion-exchange layered silicate used in the present invention is not limited to a natural product, and may be an artificial synthetic product. Specific examples of the silicate include, for example, the following ones described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).

(A) A kaolin family such as dickite, nacrite, kaolinite, anorokite, metahalloysite, halloysite, etc., and a serpentine family such as chrysotile, lizardite, antigolite, etc., in which the 1: 1 layer is the main constituent layer.
(B) 2: 1 layer is the main constituent layer of montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite and other smectites, vermiculite such as vermiculite, mica, illite, sericite, sea Mica such as green stone, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group.

  The silicate used as a raw material in the present invention may be a layered silicate in which the mixed layers (a) and (b) are formed. However, in the present invention, the main component silicate is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

  The particle size of the raw material ion-exchangeable layered silicate has an average particle size of 0.01 to 5 μm and a particle fraction of less than 1 μm of 10% or more, preferably an average particle size of 0.1 to 3 μm. The particle fraction of less than 1 μm is preferably 40% or more. As a method of obtaining ion-exchange layered silicate particles having such a particle size, a dry fine particle formation method, for example, a fine particle formation by a jet mill, a ball mill, a vibration mill or the like, or a wet grinding method, polytron, etc. There are methods such as pulverization by forced agitation using dyno, dyno mill, pearl mill and the like. Preferably, it is a wet method using water as a medium utilizing the swellability of the ion-exchange layered silicate.

Examples of the granulation method used in the present invention include stirring granulation method, spray granulation method, rolling granulation method, briquetting, fluidized bed granulation method, and submerged granulation method. A preferable granulation method is a stirring granulation method, a spray granulation method, a rolling granulation method or a fluidized granulation method, and more preferably a spray granulation method. The particle strength will be described later, but it can also be controlled in this granulation step. In order to obtain a preferred range of crushing strength, it is preferable to use an ion-exchange layered silicate silicate having a particle size distribution as described above.
There is no limitation on the combination of granulation methods when granulating in at least two stages, but preferably, spray granulation method and spray granulation method, spray granulation method and rolling granulation method, spray granulation method And a fluidized granulation method.

The shape of the granulated particles obtained by the granulation method of the present invention is spherical. Specifically, the number of particles having an M / L value of 0.8 or more and 1.0 or less is 50% or more and 100% or less of all particles (where L is the maximum number of particles in the projected view) It is a shape that satisfies the diameter value, and M is the diameter value orthogonal to L.) Preferably, the number of particles having an M / L value of 0.8 or more and 1.0 or less is 85% or more and 100% or less of all particles.
M / L is obtained by observing 100 or more of arbitrary particles with an optical microscope and image-processing them.

The concentration of the silicate in the raw slurry in the spray granulation in which spherical ion-exchange layered silicate particles are obtained is 0.1 to 50% by weight, preferably 0.5 to 30% by weight, depending on the slurry viscosity. Particularly preferably, it is 5.0 to 20% by weight. The temperature at the inlet of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example. Any desired dispersion medium can be used. Water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene alone or in a mixed solvent is used. Of these, water is particularly preferred.
However, many of the raw material ion-exchange layered silicates have water swellability, and when dispersed in water, they are finely dispersed and have a small particle size, so that the slurry viscosity is high, and therefore the slurry concentration is increased. Is often difficult. If the slurry viscosity is too high, the spray path becomes clogged or the supply becomes unstable during spray granulation, and it is difficult to obtain particles having a good shape. Conversely, if the slurry concentration is lowered in order to lower the slurry viscosity, the drying temperature must be raised, and it becomes difficult to control the shape by rapid evaporation of water, and the ion exchange properties contained in the droplets Since the amount of the layered silicate is small, only particles having a small particle size can be produced even when the droplets are dried, and it is difficult to control the particle size.

  In order to obtain particles having a desired shape with a desired particle size, it is necessary to prepare the particle size of the raw material by at least two stages of granulation processes. That is, it is possible to control the particle shape and particle size by granulating to a particle size that can be granulated to some extent in the first-stage granulation step, and performing granulation again using the granulated particle size. In the first-stage granulation step, primary exchange particles are produced by granulating ion-exchange layered silicate fine particles as a raw material having an average particle diameter of 0.01 to 5 μm. The primary granulated particles preferably have a particle size of 1 to 25 μm. More preferably, it is 1-15 micrometers.

  The primary granulated particles thus granulated are further slurried to perform the next granulation. At that time, the slurry viscosity is relatively low, and the slurry concentration can be increased. By taking appropriate spray granulation conditions, it is possible to obtain a particle size and particle shape suitable for the olefin polymerization catalyst component. The particle size that can be produced is 25 to 200 μm, preferably 25 to 150 μm, although it depends on the type of raw material ion-exchangeable layered silicate.

  The granulation conditions can be selected appropriately so that particles having good properties can be obtained by the granulation method. For example, in the spray granulation method, the inlet temperature of hot air during spraying can be set in a wide temperature range of about 90 ° C to 300 ° C. The outlet temperature is defined by the flow rate of spray from the nozzle or disk, the flow rate of hot air, and the like, and is 80 ° C. to 150 ° C. As the spray format, a general spray drying method such as a disk type, a pressurized nozzle type, or a two-fluid nozzle type can be applied. In order to control the particle size, it is possible to set the flow rate of the spray liquid, the rotational speed or the disk size of the disk, the pressure of the pressure nozzle, the flow rate of the carrier gas, and the like. In the present invention, since the primary granulated particles are granulated again to produce secondary particles, the secondary granulated particles have a larger size. The particle size increase rate of the primary particles relative to the raw material particles is preferably 3 to 500%, more preferably 5 to 300%. Further, the particle size increase rate of the secondary particles relative to the primary particles is preferably 3 to 200%, more preferably 3 to 100%. Therefore, it is possible to obtain particles with better powder properties when the primary granulation condition and the secondary granulation condition are different. For example, it is possible to obtain particles in which secondary granulation is preferred to lower the rotational speed of the disc than primary granulation. The secondary granulation disk rotation speed is preferably 1000 to 30000 rpm lower than the primary granulation disk rotation speed, and more preferably 5000 to 20000 rpm. The drying temperature is preferably lower in the secondary granulation than in the primary granulation. The hot air inlet temperature of secondary granulation is preferably 10 to 80 ° C. lower than the hot air inlet temperature of primary granulation, and more preferably 20 to 50 ° C. lower. Specifically, depending on the disk size, in the primary granulation, the hot air inlet temperature is preferably 130 to 250 ° C, more preferably 150 to 200 ° C. The disk rotation speed is preferably 10,000 to 30,000 rpm. In secondary granulation, the hot air inlet temperature is preferably 90 ° C to 180 ° C, more preferably 100 to 150 ° C. The disk rotation speed is preferably 5000 to 20000 rpm.

  During granulation, organic substances, inorganic solvents, inorganic salts, and various binders may be used. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcelluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein, Examples thereof include latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, and sodium alginate.

  The ion-exchange layered silicate may be subjected to chemical treatment. This may be performed either before the granulation for forming the primary granulated particles, after the granulation for forming the primary granulated particles, or after the subsequent granulation of the secondary granulated particles. As the chemical treatment, acid treatment and salt treatment are performed with a washing operation interposed therebetween. The chemical treatment agent may be dissolved in an appropriate solvent and used as a treatment solution, or the treatment agent itself may be used as a solvent. Solvents that can be used include water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, dimethylformamide, carbon disulfide, nitrobenzene Pyridines and their halides. Further, the concentration of the treatment agent in the treatment agent solution is preferably about 0.1 to 100% by weight, more preferably about 5 to 50% by weight. If the concentration of the treatment agent is within this range, there is an advantage that the time required for the treatment is shortened and the production can be efficiently performed.

  In the above acid treatment, impurities on the surface of the ion-exchange layered silicate particles are removed or interlayer cations are exchanged, and some or all of cations such as Al, Fe, Mg, etc. in the crystal structure are eluted. Can do. Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. An inorganic acid is preferable, and sulfuric acid is particularly preferable. There are no particular limitations on the acid treatment conditions, but preferably the conditions are such that an aqueous solution of 5 to 50% by weight acid is reacted at a temperature of 60 to 100 ° C. for 1 to 24 hours, and the acid concentration is changed during the reaction. May be.

  The ion-exchanged layered silicate is washed after being acid-treated. Washing is an operation for separating and removing the acid contained in the treatment system from the ion-exchangeable layered silicate. The method for separating and removing the acid is not particularly limited, and examples thereof include a method of washing with a solvent, a method of removing with an adsorbent, and a method of removing with a gas. A method of washing with a solvent is preferred. Water is particularly preferable.

  Examples of the salt used in the salt treatment include various salts described in JP-A-8-127613. In the present invention, a salt containing a specific cation is selected and used. Is preferred. As for the type of cation, a monovalent to tetravalent metal cation is preferable, and a cation of Li, Ni, Zn, or Hf is particularly preferable. Specific examples of the salts include the following.

Examples of the cation with Li include LiCl, LiBr, Li ₂ SO ₄ , Li ₃ (PO ₄ ), Li (ClO ₄ ), Li ₂ (C ₂ O ₄ ), LiNO ₃ , Li (OOCCH ₃ ), Li ₂ (C ₄ H ₄ O ₄ ) and the like, and those whose cation is Ni include NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl _2. NiBr _{2 and the} like, and those whose cation is Zn include Zn (OOCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , _{Zn 3 (PO 4) 2,} ZnSO 4, ZnF 2, ZnCl 2, ZnBr 2, ZnI 2 , and the like, those cations of Hf, Hf _{(OOCCH 3 4, Hf (CO 3) 2} , Hf (NO 3) 4, Hf (SO 4) 2, HfOCl 2, HfF 4, HfCl 4, can be cited HfBr 4, HFI _4, and the like.

  Although there is no restriction | limiting in particular about the quantity of the cation to exist, Preferably it is preferable to process by making 0.001 mol or more exist per 1g of ion-exchange layered silicate. One kind of these cations may be used alone, or two or more kinds may be used in combination. When used in combination, it is preferable that the total amount to be present is 0.001 mol or more per gram of ion-exchangeable layered silicate.

  In the salt treatment, as a method for causing the above-described Li, Ni, Zn, and / or Hf cation to exist in another method, a method for causing a substance that generates such a cation by reaction to exist, a treatment agent It is also possible to adopt a method in which the ion exchange layered silicate itself contains these cations. Although there is no restriction | limiting in particular about the quantity of the cation to exist, Preferably it is preferable to process by making 0.001 mol or more exist per 1g of ion exchange layered silicate. When used in combination with salts, the total of the cations is preferably 0.001 mol or more per 1 g of ion-exchangeable layered silicate.

  Since the silicate treated by the method of the present invention changes in properties depending on the drying temperature even if it is not structurally destroyed, it is preferable and possible to change the drying temperature depending on the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. It does not specifically limit regarding a drying method, It can implement by various methods.

The ion-exchangeable layered silicate in a state used as a catalyst component for olefin polymerization after the treatment of the present invention preferably further has the following characteristics.
In the present invention, the crushing strength of the ion exchange layered silicate is preferably within a certain range. If the particle strength of the ion-exchange layered silicate is too low, the catalyst powder and polymer particles are likely to collapse, so that fine powder is generated, flowability and adhesion are deteriorated, and the bulk density is lowered. Therefore, in the present invention, the average crushing strength of the carrier is desirably 1 MPa or more, more preferably 3 MPa or more. On the other hand, if the crushing strength is too high, uniform catalyst activation may be hindered during pre-polymerization or polymerization, or particle growth may be uneven and fine powder may be generated. Therefore, the upper limit of the carrier strength is desirably an average crushing strength of 15 MPa or less, more preferably 10 MPa or less.

The pores of the ion-exchange layered silicate produced by the production method of the present invention are not only the pores generated as a result of elution of the constituent components by the silicate acid treatment, but also the pores of the primary granulated particles obtained by granulation. Generate. Intragranular pore distribution has a maximum pore diameter in a pore radius ¹⁰ 3 to 10 ⁵ Å, a pore volume of pore radius ¹⁰ 3 to 10 ⁵ Å is 0.2~0.8ml / g. The pore size distribution, particularly the control of relatively large pores, can be controlled by the particle size distribution of the primary granulated particles used, and is effective.

  Use of the ion-exchange layered silicate having the above-mentioned crushing strength and controlled pore distribution as a catalyst component (co-catalyst) for olefin polymerization for functioning as an activator of a transition metal complex such as metallocene. Thus, it can be considered that the action mechanism described below works. That is, the silicate of the present invention exhibits a specific range of pore sizes, but the size is sufficiently large relative to metallocene complexes, organoaluminum compounds, and monomers. Therefore, these compounds involved in the reaction can easily enter the pores at each stage of catalyst formation, activation, prepolymerization, and polymerization, and the complex is highly dispersed in the support, thereby allowing the metallocene catalyst It is considered that the active points are uniformly formed.

  Furthermore, for uniform growth of catalyst particles, it is important that the carrier is dispersed in the form of fine particles along with the growth of the polymer particles. In the carrier having pores as in the present invention, this is considered to promote this. . In such a catalyst, local heat generation on the catalyst is suppressed in the polymerization reaction as compared with the conventional catalyst. For this reason, particularly in the production of a polymer that is easy to melt or dissolve, for example, in the polymerization of propylene-based low-melting-point random polymerization or ethylene-propylene block polymer, a highly active and particulate form that could not be obtained conventionally. It is presumed that the polymerization can be allowed to proceed in a maintained state.

  In general, the ion-exchangeable layered silicate includes adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water before use. Usually, heat treatment is used to remove water. The method is not particularly limited, but it is necessary to select conditions so that adhering water and interlayer water do not remain and structural damage does not occur. The heating time is 0.1 hour or longer, preferably 0.2 hour or longer. At that time, the moisture content after removal is 3% by weight or less, preferably 1% by weight or less when the moisture content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. It is preferable that

II. Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention is a catalyst using the ion-exchange layered silicate particles described above as a catalyst component. Specifically, it is a catalyst prepared using (A) Periodic Table Group 4-6 metallocene compound, (B) the above-described ion-exchange layered silicate particles, and (C) an organoaluminum compound. Details of the components (A) and (C), the preparation method, the polymerization of olefins and the like are described below.

1. Catalyst Component (A) Periodic Table Group 4-6 Metallocene Compound Component (A) Periodic Table Group 4-6 metallocene compound used in the olefin polymerization catalyst of the present invention has at least one conjugated five-membered ring ligand. It is a transition metal compound of Groups 4-6 of the periodic table. Preferred as such a transition metal compound are compounds represented by the following general formulas (1), (2), (3) and (4).

  In the formula, A and A ′ represent a conjugated five-membered ring ligand (which may be the same or different in the same compound), and Q represents two conjugated five-membered ligands. Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, and Q ′ represents a conjugated five-membered ring coordination. An arbitrary position of a child and a bonding group that bridges Z; M represents a metal atom selected from groups 4 to 6 of the periodic table; X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, An amino group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group (in the same compound, X and X ′ may be the same or different).

Examples of A and A ′ include a cyclopentadienyl group. The cyclopentadienyl group may be one having five hydrogen atoms [C ₅ H _5- ], or a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with substituents. May be.
Examples of this substituent are hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, and when there are a plurality of these, two of them are bonded to the other end (ω-end) to form cyclopentadienyl. A ring may be formed together with a part of the enyl. Examples of the latter include those in which two substituents are each bonded at the ω-end to share two adjacent carbon atoms in the cyclopentadienyl group to form a condensed six-membered ring, That is, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and those forming a condensed seven-membered ring, that is, an azulenyl group and a tetrahydroazurenyl group can be mentioned.

  Preferable specific examples of the conjugated five-membered ring ligand represented by A and A ′ include a substituted or unsubstituted cyclopentadienyl group, indenyl group, fluorenyl group, or azulenyl group. Among these, an azulenyl group is particularly preferable.

As the substituent on the cyclopentadienyl group, in addition to the hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, halogen atom groups such as fluorine, chlorine and bromine, and alkoxy having 1 to 12 carbon atoms. A group, for example, a silicon-containing hydrocarbon group represented by -Si (R ¹ ) (R ² ) (R ³ ), a phosphorus-containing hydrocarbon group represented by -P (R ¹ ) (R ² ), or -B (R ¹ ) a boron-containing hydrocarbon group represented by (R ² ). When there are a plurality of these substituents, each substituent may be the same or different. R ¹ , R ² and R ³ described above may be the same or different and each represents an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.

Q is a binding group that bridges two conjugated five-membered ring ligands at any position, and Q ′ is a binding group that bridges any position of the conjugated five-membered ring ligand with a group represented by Z. Represents.
Specific examples of Q and Q ′ include
(A) alkylene groups such as methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group,
(B) Silylene groups such as dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisilylene group, etc. ,
(C) A hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, more specifically, (CH ₃ ) ₂ Ge, (C ₆ H ₅ ) ₂ Ge, (CH ₃ ) P, (C ₆ H _{5) P, (C 4 H} 9) N, (C 6 H 5) N, (C 4 H 9) B, (C 6 H 5) B, (C 6 H 5) Al (C 6 H 5 O) And a group represented by Al. Preference is given to alkylene groups and silylene groups.

  M is a metal atom transition metal selected from Groups 4 to 6 of the Periodic Table, preferably a Group 4 metal atom of the Periodic Table, specifically titanium, zirconium, hafnium and the like. In particular, zirconium and hafnium are preferable.

  Z represents a ligand, a hydrogen atom, a halogen atom or a hydrocarbon group containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom. Preferable specific examples include an oxygen atom, a sulfur atom, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and 1 to 1 carbon atoms. 40, preferably a nitrogen-containing hydrocarbon group having 1 to 18 carbon atoms, 1 to 40 carbon atoms, preferably a phosphorus-containing hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom, chlorine, bromine, or a hydrocarbon group having 1 to 20 carbon atoms. .

  X and Y are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, a diphenylphosphino group, etc. A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms such as a trimethylsilyl group or a bis (trimethylsilyl) methyl group. . X and Y may be the same or different. Of these, halogen atoms, hydrocarbon groups, particularly those having 1 to 8 carbon atoms, and amino groups are preferred.

(A) Examples of the compound represented by the general formula (1) include (1) bis (methylcyclopentadienyl) zirconium dichloride,
(2) bis (ethylcyclopentadienyl) zirconium dichloride,
(3) bis (propylcyclopentadienyl) zirconium dichloride,
(4) bis (n-butylcyclopentadienyl) zirconium dichloride,
(5) bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
(6) bis (1-ethyl-3-methylcyclopentadienyl) zirconium dichloride,
(7) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(8) bis (1-i-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(9) Bis (1-t-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(10) bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl,
(11) Bis (1,3-dimethylcyclopentadienyl) zirconium methyl chloride,
(12) Bis (1,3-dimethylcyclopentadienyl) zirconium diethyl,
(13) Bis (1,3-dimethylcyclopentadienyl) zirconium diisobutyl,
(14) bis (1,3-dimethylcyclopentadienyl) zirconium chloride monohydride,
(15) Bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium dihydride,
(16) bis (1,3-dimethylcyclopentadienyl) zirconium dimethoxide,
(17) Bis (1,3-dimethylcyclopentadienyl) zirconium bis (dimethylamide),
(18) bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium diethylamide monochloride,
(19) Bis (1-methyl-3-trifluoromethylcyclopentadienyl) zirconium dichloride,
(20) bis (1-methyl-3-trimethylsilylcyclopentadienyl) zirconium dichloride,
(21) bis (1-cyclohexyl-3-methylcyclopentadienyl) zirconium dichloride,
(22) bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride,
(23) bis (1-benzyl-3-methylcyclopentadienyl) zirconium dichloride,
(24) Bis (1-n-butyl-3-trifluoromethylcyclopentadienyl) zirconium dichloride,
(25) bis (indenyl) zirconium dichloride,
(26) bis (tetrahydroindenyl) zirconium dichloride,
(27) Bis (2-methyl-tetrahydroindenyl) zirconium dichloride is mentioned.

(B) Examples of the compound represented by the general formula (2) include:
(1) Dimethylsilylenebis {1- (2-methyl-4-isopropyl-4H-azurenyl)} zirconium dichloride,
(2) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(3) Dimethylsilylenebis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(4) Dimethylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium dichloride,
(5) Dimethylsilylenebis [1- {2-methyl-4- (3-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(6) Dimethylsilylenebis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azulenyl}] zirconium dichloride,
(7) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} zirconium dichloride,
(8) Diphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(9) methylphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(10) Dimethylphenylsilylenebis [1- {2-methyl-4- (1-naphthyl) -4H-azurenyl}] zirconium dichloride,
(11) methylphenylsilylenebis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(12) methylphenylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium dichloride,
(13) methylphenylsilylenebis [1- {2-methyl-4- (3-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(14) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(15) Dimethylsilylenebis [1- {2-ethyl-4- (1-naphthyl) -4H-azurenyl}] zirconium dichloride,
(16) Dimethylsilylenebis [1- {2-ethyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(17) Dimethylsilylenebis [1- {2-ethyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium dichloride,
(18) Dimethylsilylenebis [1- {2-ethyl-4- (3-chlorophenyl) -4H-azulenyl}] zirconium dichloride,
(19) Dimethylsilylenebis [1- {2-ethyl-4- (2-naphthyl) -4H-azurenyl}] zirconium dichloride,
(20) Dimethylsilylenebis [1- {2-ethyl-4- (1-anthracenyl) -4H-azulenyl}] zirconium dichloride,
(21) Dimethylsilylenebis [1- {2-ethyl-4- (2-anthracenyl) -4H-azurenyl}] zirconium dichloride,
(22) Dimethylsilylenebis [1- {2-ethyl-4- (9-anthracenyl) -4H-azurenyl}] zirconium dichloride,
(23) Dimethylsilylenebis [1- {2-ethyl-4- (1-phenanthryl) -4H-azurenyl}] zirconium dichloride,
(24) Dimethylsilylenebis [1- {2-ethyl-4- (9-phenanthryl) -4H-azurenyl}] zirconium dichloride,
(25) Dimethylmethylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(26) Dimethylgermylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azulenyl]} zirconium dichloride,
(27) ethylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(28) Dimethylsilylenebis {1- [2-i-propyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(29) Dimethylsilylenebis {1- [2-methyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(30) Dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(31) Dimethylsilylenebis {1- [2-methyl-4- (2 ′, 6′-dimethyl-4-biphenylyl) -4H-azulenyl]} zirconium dichloride,
(32) Dimethylsilylenebis {1- [2-methyl-4- (1-naphthyl) -4H-azurenyl]} zirconium dichloride,
(33) Dimethylsilylenebis {1- [2-i-propyl-4- (1-naphthyl) -4H-azurenyl]} zirconium dichloride,
(34) Dimethylsilylenebis {1- [2-i-propyl-4- (4-t-butylphenyl) -4H-azulenyl]} zirconium dichloride,
(35) Dimethylsilylene {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} {1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium dichloride,
(36) Dimethylsilylenebis {1- [2-ethyl-4- (4-biphenylyl) -4H-5,6,7,8-tetrahydroazulenyl]} zirconium dichloride,
(37) Dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azulenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(38) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-6-isopropyl-4H-azurenyl)} zirconium dichloride,
(39) Dimethylsilylenebis {1- (2-ethyl-4,6-diphenyl-4H-azurenyl)} zirconium dichloride,
(40) Dimethylsilylenebis [1- {2-methyl-4- (pentafluorophenyl) -4H-azurenyl}] zirconium dichloride,
(41) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoro-4H-azulenyl)} zirconium dichloride,
(42) Dimethylsilylenebis {1- (2-ethyl-4-indolyl-4H-azurenyl)} zirconium dichloride,
(43) Dimethylsilylenebis {1- (2-dimethylborano-4-indolyl-4H-azurenyl)} zirconium dichloride,
(44) Dimethylsilylenebis [1- {2-ethyl-4- (3,5-bistrifluoromethylphenyl) -4H-azurenyl}] zirconium dichloride,
(45) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dimethyl,
(46) Dimethylsilylene bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium bis (trifluoromethanesulfonic acid),
(47) Dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(48) Dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(49) Dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(50) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropylindenyl)} zirconium dichloride,
(51) Diphenylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(52) methylphenylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(53) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(54) Dimethylsilylenebis [1- {2-ethyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(55) Dimethylsilylenebis [1- {2-ethyl-4- (9-anthryl) indenyl}] zirconium dichloride,
(56) Dimethylsilylenebis [1- {2-ethyl-4- (9-phenanthryl) indenyl}] zirconium dichloride,
(57) Dimethylsilylene {1- (2-ethyl-4-phenylindenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(58) Dimethylsilylenebis [1- {2-methyl-4- (pentafluorophenyl) indenyl}] zirconium dichloride,
(59) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoroindenyl)} zirconium dichloride,
(60) ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(61) ethylene-1,2-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(62) ethylene-1,2-bis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(63) isopropylidenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(64) ethylene-1,2-bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(65) ethylene-1,2-bis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(66) ethylene-1,2-bis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(67) Ethylene-1,2-bis [1- {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride,
(68) isopropylidenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(69) ethylene-1,2-bis {1- (2-ethyl-4-indolyl-4H-azurenyl)} zirconium dichloride,
(70) Dimethylgermylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(71) Dimethylgermylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(72) methylaluminum bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(73) phenylphosphinobis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(74) Phenylaminobis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(75) Dimethylsilylenebis [3- (2-furyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(76) Dimethylsilylenebis [2- (2-furyl) -3,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(77) Dimethylsilylenebis [3- (2-furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(78) Dimethylsilylenebis [3- (2-thienyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(79) Dimethylsilylenebis [2- (2-thienyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(80) Dimethylsilylenebis [2- (2-furyl) -indenyl] zirconium dichloride,
(81) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(82) Dimethylsilylenebis [2- (2- (5-t-butyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(83) Dimethylsilylenebis [2- (2- (2- (5-trimethylsilyl) furyl) -4,5-dimethyl-cyclopentadienyl) zirconium dichloride,
(84) Dimethylsilylenebis [2- (2- (4,5-dimethyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(85) Dimethylsilylenebis [2- (2-benzofuryl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(86) Dimethylsilylenebis [2- (2-thienyl) -indenyl] zirconium dichloride,
(87) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -indenyl] zirconium dichloride,
(88) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -4-phenylindenyl] zirconium dichloride,
(89) Dimethylsilylene [2- (2- (5-methyl) furyl) -4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride,
(90) Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(91) Dimethylgermylbis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(92) Dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(93) Dimethylgermylbis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(94) Dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl) zirconium dichloride,
(95) Dimethylgermyl (2,5-dimethyl-3-phenylcyclopentadienyl) zirconium dichloride, and the like.

(C) As a compound represented by the general formula (3), for example,
(1) (tetramethylcyclopentadienyl) titanium (bis t-butylamide) dichloride,
(2) (tetramethylcyclopentadienyl) titanium (bisisopropylamide) dichloride,
(3) (tetramethylcyclopentadienyl) titanium (biscyclododecylamide) dichloride,
(4) (Tetramethylcyclopentadienyl) titanium {bis (trimethylsilyl) amide)} dichloride,
(5) (2-Methyl-4-phenyl-4H-azurenyl) titanium {bis (trimethylsilyl) amide} dichloride,
(6) (2-methyl-4-phenyl-4H-azurenyl) zirconium {bis (trimethylsilyl) amide} dichloride,
(7) (2-methylindenyl) titanium (bis t-butylamide) dichloride,
(8) (fluorenyl) titanium (bis t-butylamide) dichloride,
(9) (3,6-diisopropylfluorenyl) titanium (bis t-butylamide) dichloride,
(10) (Tetramethylcyclopentadienyl) titanium (phenoxide) dichloride,
(11) (Tetramethylcyclopentadienyl) titanium (2,6-diisopropylphenoxide) dichloride and the like.

(D) As a compound represented by the general formula (4), for example,
(1) Dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamido) titanium dichloride,
(2) Dimethylsilanediyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride,
(3) Dimethylsilanediyl (2-methylindenyl) (t-butylamido) titanium dichloride,
(4) Dimethylsilanediyl (fluorenyl) (t-butylamido) titanium dichloride, and the like.
The moiety [A] represented by the general formulas (1) to (4) can be used as a mixture of two or more compounds represented by the same general formula and / or compounds represented by different general formulas. .

(C) used in the olefin polymerization catalyst of the organoaluminum compound component (C) in the present invention the organoaluminum compound is a compound represented by the general formula AlR _{3 p} ^X 3-p is suitable. In the present invention, it goes without saying that the compounds represented by this formula can be used alone, in combination of two or more, or in combination. Moreover, this use is possible not only at the time of catalyst preparation but also at the time of preliminary polymerization or polymerization. In this formula, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group, or an amino group. p is in the range of 1 to 3. R ³ is preferably an alkyl group, and X is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 to 8 carbon atoms when it is an amino group. The amino group of is preferable.
Therefore, specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethyl Examples include aluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like. Of these, trialkylaluminum and dialkylaluminum hydride having p = 3 and q = 1 are preferable. More preferably, R ³ is a trialkylaluminum having 1 to 8 carbon atoms.

The catalyst of the present invention is formed by bringing the components (A), (B), and (C) into contact with each other outside or in the polymerization tank, simultaneously or continuously, or once or multiple times. Can be made. The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although a contact temperature is not specifically limited, It is preferable to carry out between -20 degreeC and 150 degreeC. As the contact order, any desired combination can be used. Particularly preferable components are shown as follows.
Usually, the component (B) and the component (A) are first contacted. Component (C) can be added to component (B) before, simultaneously with, or after component (A). A preferable contact order for improving the catalytic activity and polymer particle properties is a method in which the component (C) is added to the component (B) and then the component (A) is contacted. At this time, it is possible to use the same or different component (C) as the component (A) used in advance for the component (B).
After contacting each component, it can be washed with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of components (A), (B) and (C) used in the present invention is arbitrary. For example, the amount of component (A) used relative to component (B) is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component (B). The amount of component (C) used relative to component (B) is preferably such that the amount of transition metal is 0.001 to 100 μmol, particularly preferably 0.005 to 50 μmol, relative to 1 g of component (B). Therefore, the amount of component (C) relative to component (A) is preferably in the range of 10 ⁻⁵ to 50, particularly preferably 10 ^{−4 to} 5 in terms of the molar ratio of transition metal.

2. Prepolymerization The olefin polymerization catalyst of the present invention can be subjected to a prepolymerization treatment comprising bringing a polymerizable monomer into contact therewith and polymerizing the monomer in a small amount, and is preferable. The step of performing the prepolymerization is optional, and a method such as contacting the component (C) after contacting all the catalyst components of the present invention or after performing the prepolymerization is also possible. The polymerization conditions at that time are usually milder than those of the main polymerization. As the prepolymerized monomer, α-olefin can be used, and ethylene or propylene is preferable. The amount of prepolymerization is usually 0.01-100 g-PP / g-catalyst, preferably 0.1-50 g-PP / g-catalyst. Moreover, when superposing | polymerizing using a prepolymerization catalyst, an additional component (C) may be used and it is preferable.
At the time of or after the contact of each of the above components, a polymer such as polyethylene and polypropylene, and a solid of an inorganic oxide such as silica and titania may coexist or may be brought into contact.

3. Polymerization of Olefin An α-olefin can be polymerized or copolymerized using the olefin polymerization catalyst of the present invention. Preferred α-olefins that can be polymerized are those having about 2 to 20 carbon atoms, and specific examples include ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like. In the case of copolymerization, the type of comonomer used can be selected from α-olefins other than the main component among those listed as the α-olefin. The amount of comonomer can be carried out under any conditions in order to produce a polymer having desired physical properties (melting point, molecular weight, rigidity, etc.), but the catalyst of the present invention is usually difficult to produce due to deterioration of particle properties, for example. Suitable for the production of random polymers and the like, particularly suitable for the production of low melting point propylene random copolymers and so-called ethylene / propylene block copolymers having a high rubber content.
By using the catalyst of the present invention, a polymer having a uniform shape and a relatively large particle size can be produced. The obtained polymer has a particle size of 500 μm to 5 mm. Also, a polymer having a large pore volume and relatively large pores can be obtained. There is an effect of remarkably improving adhesion between polymers and fouling to the polymerization reaction layer.

  As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a solution polymerization method, a bulk method using propylene as a solvent that does not substantially use an inert solvent, or gasifying each monomer substantially without using a liquid solvent. A gas phase method can be used. Further, it is applied to continuous polymerization and batch polymerization. In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 ° C. to 200 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure can be carried out in the range of 0 to 200 MPa.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by these examples without departing from the gist thereof. In addition, the physical property measuring method is as follows.

(1) Particle size measurement of ion-exchange layered silicate particles The particle size was measured using a laser diffraction / scattering particle size distribution measuring device ("LA-920" manufactured by Horiba Ltd.). For the measurement of the ion-exchangeable layered silicate in the slurry before granulation, water was used as a dispersion medium, and the particle size distribution and average particle size (median diameter) were calculated with a refractive index of 1.32 and a shape factor of 1.0. The ion exchange layered silicate after granulation was measured in the same manner using ethanol as a dispersion medium.
(2) MFR measurement A polypropylene polymer shows a melt index value measured according to JIS-K-6758, and a polyethylene polymer shows a melt index value measured according to JIS-K-6760.
(3) Polymer BD
It shows the bulk density of the polymer according to ASTM D1895-69.
(4) Measurement of Crushing Strength Using a micro compression tester “MCTM-500” manufactured by Shimadzu Corporation, the crushing strength of 10 or more arbitrarily selected particles was measured, and the average value was taken as the crushing strength. .
(5) Measurement of powder particle size It measured using the particle size distribution measuring device camsizer by Lecce Technology.
(6) Melting point (Tm)
Using a Seiko Instruments DSC6200, the sheet-shaped sample piece was packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./minute, held for 5 minutes, and then 10 ° C./minute. After the temperature was lowered to 40 ° C. for crystallization, the maximum melting peak temperature (° C.) when the temperature was raised to 200 ° C. at 10 ° C./min was obtained.
(7) 23 ° C. xylene soluble amount (CXS)
The polymer is weighed with an electronic balance and placed in a 500 ml flat bottom flask and 300 ml of industrial xylene is added. Immerse in an oil bath adjusted to 140 ° C. in advance and dissolve for about 1 hour. Next, the flask was taken out and immersed in an oil bath adjusted to 23 ° C. for 1 hour, and then the supernatant was collected by filtration. Solvent removal / drying was carried out at 110 ° C. under reduced pressure for 4 hours to dissolve xylene. The amount was determined (unit:% by weight).
(8) Measurement of ratio of particles satisfying M / L ≧ 0.80 More than 100 arbitrary particles were observed with an optical microscope, and an image was obtained using a real-time image processing analyzer “LUZEX FS” manufactured by Nireco Corporation. Obtained by processing. Here, L represents the value of the maximum diameter of the particle in the projection, and M represents the value of the diameter orthogonal to L.

Example 1
(1) Granulation of fine particles (first stage granulation step)
Distilled water (2850 ml) and commercially available montmorillonite (Mizusawa Chemical Benclay SL) (150 g) were gradually added to a 4.5 liter metal container, stirred for several hours, and then homogenized using polytron for 10 minutes. . When the average particle size was measured, it was 0.63 μm for the montmorillonite water slurry. This slurry was subjected to spray granulation using a spray granulator (LT-8) manufactured by Okawara Chemical Corporation. The physical properties and operating conditions of the slurry are as follows.
Slurry properties: pH = 9.6, slurry viscosity = 3500 CP; operating conditions: atomizer rotation speed 30000 rpm, feed rate = 0.7 L / h, inlet temperature = 200 ° C., outlet temperature = 140 ° C., cyclone differential pressure = 80 mmH ₂ O
As a result, 90 g of granulated fine particles were recovered. The average particle size was 10.1 μm. The shape was spherical.
(2) Acid treatment To a glass flask equipped with a 1.0 liter stirring blade, 510 ml of distilled water and 150 g of concentrated sulfuric acid (96%) were slowly added, and 80 g of the granulated fine particles were dispersed. And heat treatment at 90 ° C. for 2 hours. After cooling, the slurry was filtered under reduced pressure to recover the cake. Distilled water was added to the cake in an amount of 0.5 to 0.6 liter, and the slurry was reslurried and then filtered. This washing operation was repeated 4 times.
The collected cake was dried at 110 ° C. overnight. The weight after drying was 67.5 g.
(3) Re-granulation The acid-treated fine particles 50 g thus obtained were gradually added to 150 ml of distilled water and stirred. This slurry was subjected to spray granulation using a spray granulator (LT-8) manufactured by Okawara Chemical Corporation. The physical properties and operating conditions of the slurry are as follows.
Slurry properties: pH = 5.7, slurry viscosity = 150 CP; operating conditions: atomizer rotation speed 10000 rpm, liquid supply amount = 0.7 L / h, inlet temperature = 130 ° C., outlet temperature = 110 ° C., cyclone differential pressure = 80 mmH ₂ O
As a result, 45 g of granulated particles were recovered. The average particle size was 69.3 μm. The shape was spherical, although the surface was rough. When the shape was measured, 92% of the particles had an M / L of 0.8 or more and 1.0 or less. The crushing strength was 3.6 MPa. The SEM observation figure of the obtained particle | grains is shown in FIG. It turns out that it is a spherical particle form.

(Example 2)
A slurry was prepared in the same manner as in the method described in Example 1 except that the slurry concentration was 3%, and spray granulation was performed in the same manner. As a result, 120 g of spherical fine particles having an average particle diameter of 4.6 μm were obtained.
This was subjected to acid treatment in the same manner as in Example 1 and then granulated. As a result, 37 g of spherical granulated particles were obtained. The average particle size was 57.2 μm. The number of particles having an M / L of 0.8 or more and 1.0 or less was 95%. The crushing strength was 4.5 MPa.

(Example 3)
Using the slurry prepared in the same manner as in Example 1, fine particles were granulated in the same manner as in Example 1 except that the atomizer rotation speed was set to 20000 rpm under spray granulation conditions. As a result, 83 g of spherical fine particles were obtained. The average particle size was 15.6 μm.
This was subjected to acid treatment in the same manner as in Example 1, and then re-granulation was carried out in the same manner as in Example 1 except that the atomizer speed was changed to 7000 rpm. As a result, spherical granulated particles having an average particle size of 93.6 μm were obtained. Some of the particles were flat, but 68% of the particles had an M / L of 0.8 or more and 1.0 or less. The crushing strength was 3.2 MPa.

(Comparative Example 1)
In Example 1 (granulation of fine particles), granulation was performed by changing the spray granulation conditions. The operating conditions are as follows.
Operating conditions: atomizer rotation speed 7000 rpm, liquid supply amount = 1.5 L / h, inlet temperature = 200 ° C., outlet temperature = 140 ° C., cyclone differential pressure = 80 mmH ₂ O
As a result, 75 g of granulated particles were recovered. The average particle size was 44.5 μm. The shape was a flat body. The number of particles having an M / L of 0.8 or more and 1.0 or less was 42%. In addition, the spray granulator was often attached to the drying chamber. The SEM observation figure of the obtained particle | grains is shown in FIG. It can be seen that the shape is flat.

Example 4
(1) Preparation of catalyst The following operations were carried out under inert gas using deoxygenated and dehydrated solvents and monomers. The granulated product of the ion exchange layered silicate was dried at 200 ° C. under reduced pressure for 2 hours.
10 g of the granulated particles obtained in Example 1 were introduced into a glass reactor equipped with a stirring blade having an internal volume of 1 liter, normal heptane and further a heptane solution (25 mmol) of triisobutylaluminum were added, and the mixture was stirred at room temperature. After 1 hour, the slurry was thoroughly washed with heptane to prepare a slurry of 100 ml.
Next, 43 ml of mixed toluene was added to 0.30 mmol of (r) -dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl]} hafnium dichloride in advance for 1 hour or more. After stirring, a mixed solution in which 1.5 mmol of triisobutylaluminum (heptane solution, 2.13 ml) was allowed to react at room temperature for 1 hour was added to the granulated particle slurry and stirred for 1 hour.
(2) Preliminary polymerization Subsequently, 105 ml of mixed heptane was introduced into a stirring autoclave having an internal volume of 1.0 liter sufficiently substituted with nitrogen and maintained at 40 ° C. The previously prepared granulated particle / complex slurry was introduced there. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 2 hours, the propylene feed was stopped and maintained for another 2 hours. The prepolymerized catalyst slurry was recovered with a siphon, and about 100 ml of the supernatant was removed, followed by drying at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.
(3) Polymerization After the inside of a stirred autoclave with an internal volume of 3 liters was sufficiently substituted with propylene, 2.76 ml (2.02 mmol) of a triisobutylaluminum / n-heptane solution was added, and 30 g of ethylene, 100 cc of hydrogen, Subsequently, 1500 ml of liquid propylene was introduced and the temperature was raised to 70 ° C. to maintain the temperature. The preliminarily preliminarily polymerized catalyst was slurried in normal heptane, and 10 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate the polymerization. The bath temperature was maintained at 70 ° C. After 60 minutes, 5 ml of ethanol was added, and the polymer obtained by purging the residual gas was dried. As a result, 220 g of a polymer was obtained. The catalytic activity was 22000 g-PP / g-catalyst · hour. Polymer BD = 0.41 (g / cc), MFR = 22.8 (dg / min), and melting point was 135.1 ° C. The particle size of the polymer powder was 2.3 mm, was spherical, and there was no fine powder.

(Example 5)
(1) Block polymerization of ethylene-propylene After the inside of a stirred autoclave having an internal volume of 3 liters was sufficiently substituted with propylene, 2.76 ml (2.02 mmol) of a triisobutylaluminum / n-heptane solution was added and hydrogen was added. 150 cc and then 1500 ml of liquid propylene were introduced, and the temperature was raised to 65 ° C. to maintain the temperature. The prepolymerized catalyst prepared in Example 4 was slurried in normal heptane, and 30 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The tank temperature was maintained at 65 ° C. After introducing the catalyst, 150 ml of hydrogen was injected. One hour after the catalyst was added, the remaining monomer was purged and the internal temperature was lowered to 40 ° C. Thereafter, 0.92 MPa of propylene and then 1.38 MPa of ethylene were introduced, and the internal temperature was raised to 80 ° C. Thereafter, a previously prepared mixed gas of propylene and ethylene was introduced, and the polymerization reaction was controlled for 40 minutes while adjusting the internal pressure to be 2.5 MPa so that the monomer composition ratio did not change during the polymerization. As a result, 250 g of an ethylene-propylene block polymer having no particle adhesion and having good particle properties was obtained. The catalytic activity was 8300 g-PP / g-catalyst. Polymer BD = 0.43 (g / cc), MFR = 18.2 (dg / min), and the average particle size of the polymer was 1.8 mm. The amount of CXS solubles was 37.5%. It has been found that a polymer with good particle properties can be obtained despite the very high rubber content.

(Comparative Example 2)
Using the granulated particles prepared in Comparative Example 1, catalyst preparation, preliminary polymerization, and polymerization evaluation were performed in the same manner as in Example 4. As a result, 180 g of a polymer was obtained. The catalytic activity was 18000 g-PP / g-catalyst · hour. Polymer BD = 0.34 (g / cc), MFR = 36.5 (dg / min), and melting point was 136.1 ° C. The particle size of the polymer powder was 2.4 mm, but it was irregular and had many aggregates and many fine powders were generated.

  According to the present invention, a catalyst component for olefin polymerization having excellent particle properties can be produced. By using the catalyst component for olefin polymerization of the present invention, it is possible to produce a polymerized powder that can be handled in the same manner as a pellet having high catalytic activity, large particle size, uniform shape, and good fluidity.

SEM observation diagram of particles produced in Example 1 SEM observation diagram of particles produced in Comparative Example 1

Claims (5)

  The number of particles satisfying an average particle size of 25 to 200 μm and satisfying M / L ≧ 0.80 (where L is the maximum particle size value in the projected view and M is the diameter value perpendicular to L). It is a production method by spray granulation of ion-exchange layered silicate particles occupying 50% or more of the total number of particles, including a step of granulating in at least two stages, in the first-stage granulation step, Using ion-exchange layered silicate fine particles having an average particle diameter of 0.01 to 5 μm as raw materials, producing particles having an average particle diameter of 1 to 25 μm at a disk rotation speed of 10,000 to 30000 rpm, and secondary granulation disks A method for producing ion-exchangeable layered silicate particles, characterized in that the rotational speed is 5,000 to 20,000 rpm lower than the primary granulation disk rotational speed.   The method for producing ion-exchangeable layered silicate particles according to claim 1, wherein the average particle size of the particles obtained in the first stage granulation step is 1 to 15 µm. The method for producing ion-exchangeable layered silicate particles according to claim 1 or 2 , wherein the crushing strength is 3 to 15 MPa. The method for producing ion-exchange layered silicate particles according to any one of claims 1 to 3 , wherein the ion-exchange layered silicate particles are smectite group silicate particles. A catalyst component for olefin polymerization, comprising the ion-exchangeable layered silicate particles according to any one of claims 1 to 4 .

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