JP2018095862A - Polyethylene powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyethylene powder capable of stably and homogeneously producing molded bodies obtained.SOLUTION: Polyethylene powder of the present invention is polyethylene powder of a homopolymer of ethylene, or a copolymer of ethylene and alpha-olefin having 3 or more and 15 or less carbons, and the polyethylene powder has a viscosity average molecular weight of 100,000 or larger and 10,000,000 or smaller, the density of 920 kg/mor larger and 960 kg/mor smaller, and a flow energy when a quantity of airflow is 4 mm/s of 30% or larger of the flow energy while no aeration.SELECTED DRAWING: None

Description

  The present invention relates to polyethylene powder.

  Polyethylene is used in a wide variety of applications such as films, sheets, microporous membranes, fibers, foams, pipes and the like. In particular, ultra-high molecular weight polyethylene has properties such as high strength and chemical stability and excellent long-term reliability. Therefore, it is a microporous material for separators of secondary batteries represented by lead-acid batteries and lithium-ion batteries. It can be used as a raw material for products that require high performance such as membranes and high-strength fibers.

JP 2008-36885 A JP2015-3442 JP2015-93908A Japanese Patent No. 2657434 JP-A-8-34873 JP 2003-192822 A

  Here, polyethylene including ultra-high molecular weight is generally obtained in the form of powder (powder) after polymerization, and the ultra-high molecular weight polyethylene powder obtained after polymerization is used as a base material (for example, a predetermined conveying device). ) After being spread and transported, it may be thermoformed in a state of being spread on the substrate to produce, for example, a porous sheet or a porous sintered body. In such a molding method, the ultrahigh molecular weight polyethylene powder has a fixed state maintenance property (polyethylene powder spread on the substrate) when the polyethylene powder is spread on the substrate and when the polyethylene powder is conveyed. There is a case where the maintenance of the filling state of each particle in the powder layer is highly demanded. Specifically, for example, an ultra-high molecular weight polyethylene powder is formed on a base material (for example, a predetermined apparatus) by applying a solid-phase stretch molding that is heat-rolled and then heat-rolled to obtain a highly strengthened sheet (porous sheet). Or after superimposing the ultra-high molecular weight polyethylene powder on a base material (for example, a predetermined apparatus) and then heating and fusing the powders together (sinter molding), a sintered body (porous sintered body) (See, for example, Patent Documents 1 to 3). In such solid-phase stretch molding and sintering molding, a process of heating the polyolefin powder spread on the base material in a pressurized or non-pressurized state is essential, for example, vibration of the base material itself or ambient airflow There is a risk that the filling state of the spread polyolefin powder and the like may change due to the influence of the above. And if changes such as the filling state of the polyolefin powder occur, it may be difficult to produce a molded body having high accuracy and stable and uniform characteristics, which may greatly affect the physical properties of the product. there were.

  Therefore, even when a disturbance occurs, it is desired to maintain a fixed state in which the state of the ultrahigh molecular weight polyethylene powder spread on the substrate can be maintained.

  Further, when processing ultra-high molecular weight polyethylene powder obtained after polymerization, one or more types of polyethylene powder are often blended and used together with ultra-high molecular weight polyethylene powder to give desired properties (for example, patents). References 4-6). For example, in microporous membranes for lithium ion secondary battery separators, blending one or more polyethylene powders together with ultra-high molecular weight polyethylene powders enables a variety of properties such as processability and strength of the resulting microporous membranes. Can be improved.

  However, the polyethylene powders to be blended often have different particle characteristics (particle size, bulk density, etc.), and the polyethylene powder may be unevenly distributed due to the particle characteristics during transportation or blending. When the blended polyethylene powder is unevenly distributed and the polyethylene powder is discharged as a raw material from a blender, silo, etc., the blend ratio and particle size of each polyethylene powder are non-uniform when introduced into the extruder. There was a case. Such non-uniformity of the polyethylene powder may have a great influence particularly in the production of a microporous membrane and the like that require stability during production and high precision.

  Therefore, when polyethylene powder is blended and used, there is a demand for ultrahigh molecular weight polyethylene powder having characteristics that can sufficiently prevent powder from being unevenly distributed during transportation or blending.

  The present invention has been made in view of the above problems, and a molded sheet obtained by a porous sheet molded by a method such as solid-phase stretching and sintering, a microporous film produced by blending polyethylene powder, and the like. An object of the present invention is to provide a polyethylene powder capable of stably and uniformly producing a body.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that the above-mentioned problems can be solved with a predetermined polyethylene powder, and has completed the present invention.

That is, the present invention is as follows.
(1) A polyethylene powder which is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms,
The viscosity average molecular weight is 100,000 or more and 10 million or less,
The density is 920 kg / m ³ or more and 960 kg / m ³ or less,
A polyethylene powder characterized in that the flow energy when the air flow rate is 4 mm / s is 30% or more of the flow energy when there is no air flow.
(2) The polyethylene powder according to (1), wherein the average particle size is 50 μm or more and 300 μm or less.
(3) When the particle diameters corresponding to 10% cumulative and 90% cumulative from the smaller diameter side of the cumulative particle size distribution are D10 and D90, respectively, the D90 / D10 ratio is 1.0 or more and 6.0 or less, (1 Or polyethylene powder according to (2).
(4) The polyethylene powder according to any one of (1) to (3), wherein the content of particles having a particle diameter of 75 μm or less is 3.0% by mass or more and 30.0% by mass or less.
(5) The polyethylene powder according to any one of (1) to (4) above, wherein the bulk density of particles having a particle diameter of 53 μm or less is 0.25 g / cm ³ or more and 0.40 g / cm ³ or less.
(6) The polyethylene powder according to any one of the above (1) to (5), wherein the flow energy at the time of no ventilation is 100 mJ or more.

  ADVANTAGE OF THE INVENTION According to this invention, the polyethylene powder which can produce a molded object stably and uniformly can be provided.

  Hereinafter, although the form for implementing this invention (henceforth "this embodiment") is demonstrated in detail, this invention is not limited to this. Various modifications are possible without departing from the scope of the invention.

[Polyethylene powder]
The polyethylene powder according to the present embodiment is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 15 carbon atoms, and has a viscosity average molecular weight of 100,000 to 10 million. When the density is 920 kg / m ³ or more and 960 kg / m ³ or less and the air flow rate is 4 mm / s, the flow energy during ventilation is 30% or more of the flow energy when there is no ventilation.

  Although it does not specifically limit as polyethylene used by this embodiment, Specifically, the copolymer of an ethylene homopolymer and ethylene and the olefin copolymerizable with ethylene is mentioned.

The ethylenically copolymerizable with olefins, but are not limited to, specifically, the number of 3 to 15 carbon α- olefins, cyclic olefins having 3 to 15 carbon atoms, wherein _CH 2 = CHR ¹ (wherein, R ¹ is an aryl group having 6 to 12 carbon atoms.) And at least one olefin selected from the group consisting of linear, branched or cyclic dienes having 3 to 15 carbon atoms. It is done. Although it does not specifically limit as said alpha-olefin, For example, propylene, 1-butene, 4-methyl-1- pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Examples include dodecene, 1-tridecene, and 1-tetradecene.

[Viscosity average molecular weight]
The polyethylene powder according to this embodiment has a viscosity average molecular weight (Mv) of 100,000 or more, preferably 300,000 or more. Moreover, the viscosity average molecular weight (Mv) of this polyethylene powder is 10 million or less, and 99.5 million or less is preferable. When the viscosity average molecular weight (Mv) is 100,000 or more, the wear resistance and strength are further improved. Moreover, a moldability improves more because a viscosity average molecular weight (Mv) is 10 million or less. Furthermore, when the viscosity average molecular weight is in the above range, it is excellent in productivity, and when molded, it becomes a polyethylene powder excellent in wear resistance. Polyethylene powder having such properties can be suitably used for solid phase stretching, sintering molding, press molding, ram extrusion, and the like, and the resulting molded product can be suitably used for a wide range of applications.

  As a method for controlling the viscosity average molecular weight within the above range, there may be mentioned changing the polymerization temperature of the reactor when polymerizing ultrahigh molecular weight polyethylene. The viscosity average molecular weight tends to decrease as the polymerization temperature is increased, and tends to increase as the polymerization temperature is decreased. Another method for setting the viscosity average molecular weight in the above range is to change the organometallic compound species as a co-catalyst used when polymerizing ultrahigh molecular weight polyethylene. A chain transfer agent may be added when polymerizing ultrahigh molecular weight polyethylene. Thus, by adding a chain transfer agent, the viscosity average molecular weight of the ultrahigh molecular weight polyethylene produced even at the same polymerization temperature tends to be low.

[density]
The density of polyethylene powder according to the present embodiment is 920 kg / ^{m 3} or more 960 kg / ^{m 3} or less, preferably 920 kg / ^{m 3} or more 945 kg / ^{m 3} or less. When the density of the polyethylene powder is 920 kg / m ³ or more and 960 kg / m ³ or less, the powder shape tends to hardly change due to the pressure at the time of deposition of the polyethylene powder or the impact at the time of transportation, and the powder characteristics are also maintained. be able to. The density of the polyethylene powder can be adjusted by adjusting the amount and molecular weight of the α-olefin in the polyethylene. The density can be measured by the method described in the examples.

[Flow energy]
The flow energy of the polyethylene powder according to the present embodiment when the air flow rate is 4 mm / s is 30% or more, preferably 35% or more of the flow energy when no ventilation is performed.
Here, in this embodiment, the flow energy means that a predetermined container (bottom perforated plate) is filled with polyethylene powder, and then air is sent from the bottom of the container (below the powder layer) (while being ventilated), or Measure the rotational torque and vertical load that occur when moving the polyethylene powder from top to bottom while rotating the blade at a predetermined speed without feeding it, and the amount of energy derived from the integrated value (specific measurement) The method will be described later). That is, the flow energy is an energy amount when the blade advances while pushing through the powder under a predetermined condition.

  And in this invention, in order to solve the subject of the above-mentioned this invention, it is important to evaluate the ease of maintaining the fixed state of polyethylene powder, the easiness of air inclusion, and jet property. Specifically, conventionally, it has been evaluated by using a polyethylene powder that is stationary in measurement of an angle of repose or a difference angle, but since the polyethylene powder is flowing, for example, when the polyethylene powder is molded, the present inventor Focused on evaluating the behavior of polyethylene powder when it flowed. Then, the present inventor found that the ratio of the flow energy during no ventilation and the ventilation is fluidization of the powder, in other words, the ease of maintaining the fixed state as a whole of the powder during no ventilation and ventilation. It has been found that it can be used as an index for evaluating the ease of embedding and the jet property of powder. Specifically, the smaller the amount of change in the ratio of the flow energy during ventilation to the flow energy during non-ventilation, the smaller the change in the flow rate of the powder even if the polyethylene powder in a stationary state is sufficiently filled with air. It has been found that it does not occur easily (low fluidity when it is ventilated), it is easy to maintain the fixed state as a whole, the powder is difficult to embed air, and it means that the powder has low jet properties . Based on the above findings, the present inventor has found that the problem of the present invention can be solved by defining the ratio of the flow energy.

  That is, the polyethylene powder of this embodiment in which the flow energy when the air flow rate is 4 mm / s is 30% or more of the flow energy when there is no air flow is less concrete and the gas is not contained in the deposited polyethylene powder. Therefore, the fluidization of the polyethylene powder hardly occurs, and the fixed state of the polyethylene powder is easily maintained even when vibration is applied. Therefore, even in sintering molding in which polyethylene powder is fused while deposited on a base material, and solid-phase stretch molding in which polyethylene powder is deposited and then rolled, the deposited state is difficult to change. Can be processed uniformly. In addition, since the polyethylene powder is easy to maintain its fixed state, it can be used as a uniform powder raw material without uneven distribution of the polyethylene powder, for example, during stirring and transportation. That is, variation in physical properties of the obtained molded body can be reduced, and the molded body can be produced stably and uniformly. Furthermore, since the powder can be prevented from being scattered, the risk of dust explosion and the like can be reduced.

  In the present embodiment, as described above, the reason why the polyethylene powder having a flow energy within a predetermined range is difficult to be unevenly distributed is not clear, but is considered as follows. In general, if gas is supplied (vented) into the powder and exceeds a certain amount of air flow, the fixed state of the powder as a whole cannot be maintained, and it is known that it becomes a suspended suspension that exhibits a fluidization phenomenon similar to liquid. It has been. And when the powder which became a floating state returns to a fixed state, since the quality of fluidization changes with particle | grain characteristics (a particle size, bulk density, etc.) of each powder, uneven distribution will arise in powder. However, as in the present embodiment, the polyethylene powder having a flow energy within a predetermined range is a state in which gas is not easily contained in the deposited polyethylene powder, in other words, a powder that does not easily enter a suspended suspension state. It is possible to effectively prevent uneven powder distribution that may occur when returning from the floating state to the fixed state.

  In the present embodiment, the flow energy at the time of air ventilation of 4 mm / s is used as the flow energy at the time of air ventilation. In polyethylene powder, the flow energy at the time of no air ventilation and the air ventilation rate of 4 mm / s are used. The amount of change tends to be large with the flow energy at the time of fluidization, and the amount of change in the flow energy is fluidization of the powder (fluidity when trying to contain air (when vented)) It is because it can specify suitably.

  Here, the flow energy can be measured by the following method. For the measurement, a powder fluidity analyzer “Powder Rheometer FT4” (Spectris Co., Ltd.) is used. Then, after 53 g of polyethylene powder is filled in a dedicated split container, polyethylene powder is rotated while rotating the blade at a rotation speed at which the blade tip speed is 100 mm / s without allowing air to flow from below the container. The inside is moved from top to bottom at a speed of 30 mm / s, the rotational torque and vertical load at that time are measured, and the integrated value is taken as the energy amount. Further, this energy amount is referred to as flow energy at the time of no ventilation as referred to in the present invention. After measuring the flow energy during non-aeration, the blade is raised at a speed of 30 mm / s and returned to its original position while rotating backward at a speed of 40 mm / s. After that, air is fed from the lower part of the container (lower part of the powder layer) at a linear speed of 2 mm / s, and the blade is moved at a speed of 30 mm / s from above to below while rotating the blade at a rotational speed of 100 mm / s. Then, the blade is raised at a speed of 30 mm / s while rotating backward at a rotational speed of 40 mm / s, and returned to its original position. The same operation is performed at a linear velocity of 4 mm / s, and the energy required at that time is measured. This is the flow energy when the air flow rate is 4 mm / s in the present invention.

  As a method for controlling the flow energy of polyethylene powder when the air flow rate is 4 mm / s to 30% or more of the flow energy when there is no air flow, ethylene gas, solvent, catalyst, etc. are continuously polymerized during polyethylene polymerization. Supply to the system and continuously discharge with the produced ethylene polymer, or introduce the catalyst solution into the upper part of the polymerization system while being heated to a polymerization temperature of ± 5 ° C., or After the polymerization, the polymerization slurry is continuously introduced into a flash drum (a drum for mainly removing unreacted ethylene after the polymerization vessel) having a pressure of 0.05 MPa or less and a temperature of 40 ° C. or more and 50 ° C. or less. And adjusting the water content of the flash drum to 200 ppm or more and 500 ppm or less. By these methods, the particle characteristics of polyethylene powder are not limited. For example, the average particle size, cumulative particle size distribution (D90 / D10 ratio) described below, and the inclusion of particles having a particle size of 75 μm or less (polyethylene powder) The bulk density of particles having a particle size of 53 μm or less is adjusted, and the polyethylene powder having the predetermined flow energy of the present embodiment can be effectively obtained.

[Average particle size]
The average particle diameter of the polyethylene powder according to this embodiment is preferably 50 μm or more, and more preferably 55 μm or more. The average particle size is preferably 300 μm or less, and more preferably 150 μm or less. This is because, when the average particle diameter is in the above range, the predetermined flow energy relationship of the present embodiment is more easily satisfied. Specifically, when the average particle diameter is 50 μm or more, the proportion of powder scattered by airflow or vibration can be reduced. On the other hand, when the average particle size is 300 μm or less, the fluidity of the polyethylene powder can be made sufficiently high, and thereby, for example, handling properties such as charging into a hopper and weighing from the hopper tend to be better. It is in. Further, it is possible to increase the flow energy at the time of non-ventilation and tend to be more excellent in processing applicability such as productivity and / or stretchability when processing a microporous membrane. The average particle diameter of polyethylene can be controlled by the particle diameter of the catalyst used, and can also be controlled by the productivity of polyethylene per unit catalyst amount. In addition, the average particle diameter of polyethylene can be measured by the method as described in the Example mentioned later.

[D90 / D10 ratio]
The polyethylene powder according to the present embodiment may have a D90 / D10 ratio of 1.0 or more, where D10 and D90 are the particle diameters corresponding to 10% cumulative and 90% cumulative from the smaller diameter side of the cumulative particle size distribution, respectively. Preferably, it is 1.5 or more. Moreover, it is preferable that D90 / D10 ratio is 6.0 or less, and it is more preferable that it is 4.5 or less. This is because when D90 / D10 is within the above range, the relationship of the flow energy of the present embodiment is more easily satisfied. In addition, when D90 / D10 is within the above range, powder fluidization hardly occurs (the fluidity is relatively low when aerated), the molded article has good mechanical strength, small physical property variation, and stable. A molded product having the above characteristics can be obtained. The D90 / D10 ratio of the present embodiment can be adjusted to the above range by keeping the conditions (hydrogen concentration, temperature, ethylene pressure, etc.) in the polymerization system described later constant.

  The particle size distribution can be measured by a general laser diffraction type particle size distribution measuring apparatus. The particle size distribution measuring apparatus includes a wet method and a dry method, and any of them may be used. In the case of a wet method, methanol can be used as a dispersion medium. It is also possible to use an ultrasonic bus as the dispersing device. Although the measurement range of the particle size distribution depends on the performance of the apparatus, it is desirable to measure a range from a minimum of 0.1 μm to a maximum of 500 μm. More desirably, a range from a minimum of 0.05 μm to a maximum of 700 μm is measured. The particle sizes corresponding to 10% cumulative and 90% cumulative from the small diameter side of the particle size cumulative distribution data analyzed by the laser diffraction particle size distribution measuring device can be set to D10 and D90, respectively.

[Content of particles (polyethylene powder) having a particle diameter of 75 μm or less]
In the polyethylene powder according to this embodiment, the content of polyethylene powder having a particle size of 75 μm or less in the powder is preferably 3.0% by mass or more, and more preferably 10.0% by mass or more. Moreover, it is preferable that the said content is 30.0 mass% or less, and it is more preferable that it is 28.0 mass% or less. Usually, such fine particles are likely to be unevenly distributed when the powder contains a gas and thus are removed from the viewpoint of uniformity. However, the polyethylene powder in the present embodiment preferably contains a fine particle component. This is because when the content of the polyethylene powder having a particle diameter of 75 μm or less is within the above range, the relationship of the flow energy of the present embodiment is more easily satisfied. In addition, it is possible to keep the flow energy at the time of non-ventilation to some extent, and not only can suppress the scattering of the powder, but also makes the powder less fluidized (when in the aerated state) and also contains a gas when it contains gas It is possible to suppress a state in which the overall fluidity is rapidly increased.

  The content of polyethylene powder having a particle diameter of 75 μm or less can be controlled by using a catalyst having a small particle diameter as a catalyst used for polymerization of polyethylene. Moreover, it is possible to control by the conditions at the time of polymerizing polyethylene. For example, the content of polyethylene powder having a particle diameter of 75 μm or less is controlled by lowering the polymerization pressure or shortening the residence time of the reactor. be able to. Further, the content of particles having a particle diameter of 75 μm or less can be controlled by adding the solid catalyst component and the cocatalyst after bringing them into contact with the polymerization system. The content of polyethylene powder having a particle diameter of 75 μm or less can be obtained as a ratio of particles that have passed through a sieve having an opening of 75 μm. The content of polyethylene powder having a particle diameter of 75 μm or less can be measured by the method described in the examples described later.

[Bulk density of particles having a particle size of 53 μm or less]
In the polyethylene powder according to the present embodiment, the bulk density of polyethylene powder having a particle size of 53 μm or less is preferably 0.25 g / cm ³ or more, and more preferably 0.30 g / cm ³ or more. In addition, the bulk density is preferably 0.40 g / cm ³ or less, and more preferably 0.38 g / cm ³ or less. This is because, when the bulk density is in the above range, the relationship of the flow energy of the present embodiment is more easily satisfied. In addition, since the bulk density of particles having a particle diameter of 53 μm or less of polyethylene powder is 0.25 g / cm ³ or more, fluidization of the powder (when in an aerated state) is less likely to occur, and when gas is included A state in which the fluidity of the entire powder is rapidly increased can be suppressed. Moreover, powder scattering can be suppressed. Further, when the bulk density of particles having a particle diameter of 53 μm or less of polyethylene powder is 0.40 g / cm ³ or less, the flow energy during no ventilation can be kept high to some extent.

  The bulk density of the particles having a particle size of 53 μm or less can be controlled by introducing into the reactor a catalyst having a small particle size and adjusted to 80 ° C. or more and 90 ° C. or less during polymerization as a catalyst used for the polymerization of polyethylene. Is possible. The bulk density of particles having a particle size of 53 μm or less can be obtained as the bulk density of particles that have passed through a sieve having an opening of 75 μm. In addition, the measurement of the bulk density of the particle | grains whose particle diameter is 53 micrometers or less can be performed by the method as described in the Example mentioned later.

[Polyethylene polymerization method]
Although it does not specifically limit as a catalyst component used for manufacture of the polyethylene which concerns on this embodiment, It is possible to manufacture using a general Ziegler-Natta catalyst and a metallocene catalyst.

(Ziegler-Natta catalyst)
The Ziegler-Natta catalyst is a catalyst comprising a solid catalyst component [A] and an organometallic compound component [B], and the solid catalyst component [A] can be used as an inert hydrocarbon solvent represented by the following formula 1. What is a catalyst for olefin polymerization manufactured by making the organomagnesium compound (A-1) which is soluble and the titanium compound (A-2) represented by following formula 2 react is preferable.

(A-1): (M ¹ ) _α (Mg) _β (R ² ) a (R ³ ) _b (Y ¹ ) _c Formula 1
(In the formula, M ¹ is a metal atom belonging to the group consisting of Groups 12, 13 and 14 of the periodic table, R ₂ and R ₃ are hydrocarbon groups having 2 to 20 carbon atoms, Y ₁ is alkoxy, siloxy, allyloxy, amino, amide, —N═C—R ⁴ , R ⁵ , —SR ⁶ (where R ⁴ , R ^5, and R ⁶ are hydrocarbon groups having 1 to 20 carbon atoms. In the case where c is 2, Y ¹ may be different from each other.), A β-keto acid residue, and α, β, a, b, and c satisfy the following relationship: Real number 0 ≦ α, 0 <β, 0 ≦ a, 0 ≦ b, 0 ≦ c, 0 <a + b, 0 ≦ c / (α + β) ≦ 2, nα + 2β = a + b + c (where n is M ¹ Represents the valence.))

(A-2): Ti (OR ⁷ ) _d X ¹ _(4-d) Formula 2
(In the formula, d is a real number of 0 or more and 4 or less, R ⁷ is a hydrocarbon group of 1 to 20 carbon atoms, and X ¹ is a halogen atom.)

  In addition, although it does not specifically limit as an inert hydrocarbon solvent used for reaction of (A-1) and (A-2), Specifically, aliphatic hydrocarbons, such as pentane, hexane, heptane; benzene, Aromatic hydrocarbons such as toluene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane.

  First, (A-1) will be described. (A-1) is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds. Is. The relational expression nα + 2β = a + b + c of the symbols α, β, a, b, c indicates the stoichiometry between the valence of the metal atom and the substituent.

In the formula 1, the hydrocarbon group having 2 to 20 carbon atoms represented by R ² and R ³ is not particularly limited, and is specifically an alkyl group, a cycloalkyl group or an aryl group, for example, ethyl Propyl, butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl group and the like. Of these, an alkyl group is preferable. When α> 0, as the metal atom M ¹ , a metal atom belonging to the group consisting of Groups 12, 13, and 14 of the periodic table can be used, and examples thereof include zinc, boron, and aluminum. Of these, aluminum and zinc are preferable.

The ratio β / α of magnesium to the metal atom M ¹ is not particularly limited, but is preferably 0.1 or more and 30 or less, and more preferably 0.5 or more and 10 or less. When a predetermined organomagnesium compound with α = 0 is used, for example, when R ² is 1-methylpropyl or the like, it is soluble in an inert hydrocarbon solvent, and such a compound is also included in this embodiment. Gives favorable results. In Formula 1, when α = 0, R ² and R ³ are recommended to satisfy any one of the following three groups (1), (2), and (3): .

Group (1): At least one of R ² and R ³ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R ² and R ³ have 4 to 6 carbon atoms. The following alkyl groups, at least one of which is a secondary or tertiary alkyl group.
Group (2): R ² and R ³ are alkyl groups having different carbon atoms, preferably R 2 is an alkyl group having 2 or 3 carbon atoms, and R ³ is 4 or more carbon atoms. Must be an alkyl group.
Group (3): At least one of R ² and R ³ is a hydrocarbon group having 6 or more carbon atoms, preferably an alkyl group that becomes 12 or more when the number of carbon atoms contained in R ² and R ³ is added. There is.

  These groups are specifically shown below. Specific examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms in the group (1) include 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2-methylbutyl. , 2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl group and the like. Of these, a 1-methylpropyl group is particularly preferable.

  In the group (2), specific examples of the alkyl group having 2 or 3 carbon atoms include ethyl, 1-methylethyl, and propyl groups. Of these, an ethyl group is particularly preferred. Further, the alkyl group having 4 or more carbon atoms is not particularly limited, and specific examples include butyl, pentyl, hexyl, heptyl, octyl group and the like. Of these, butyl and hexyl groups are particularly preferable.

  Furthermore, in the group (3), the hydrocarbon group having 6 or more carbon atoms is not particularly limited, and specific examples include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl group and the like. Among the hydrocarbon groups, an alkyl group is preferable, and among the alkyl groups, hexyl and octyl groups are particularly preferable.

  In general, when the number of carbon atoms contained in an alkyl group increases, it tends to be soluble in an inert hydrocarbon solvent, and the viscosity of the solution tends to increase. Therefore, it is preferable in handling to use an appropriate long-chain alkyl group. The organomagnesium compound can be used by diluting with an inert hydrocarbon solvent, although a small amount of Lewis basic compound such as ether, ester, amine or the like may be contained or remain in the solution. It can be used without any problem.

It will now be described ^{Y 1.} In Formula 1, Y ¹ is alkoxy, siloxy, allyloxy, amino, amide, —N═C—R ⁴ , R ⁵ , —SR ⁶ (wherein R ⁴ , R ⁵ and R ⁶ are each independently 2 or more carbon atoms) Represents a hydrocarbon group of 20 or less), or a β-keto acid residue.

In the formula 1, the hydrocarbon group represented by R ⁴ , R ⁵ and R ⁶ is preferably an alkyl group or aryl group having 1 to 12 carbon atoms, particularly preferably an alkyl group or aryl group having 3 to 10 carbon atoms. . Although not particularly limited, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 2-methylpentyl, 2-ethylbutyl, 2-ethylpentyl, Examples include 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, octyl, nonyl, decyl, phenyl, naphthyl group and the like. Of these, butyl, 1-methylpropyl, 2-methylpentyl and 2-ethylhexyl groups are particularly preferable.

In Formula 1, Y ¹ is preferably an alkoxy group or a siloxy group. Although it does not specifically limit as an alkoxy group, Specifically, methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 1,1-dimethylethoxy, pentoxy, hexoxy, 2-methylpentoxy, 2-ethylbutoxy, 2-ethylpentoxy, 2-ethylhexoxy, 2-ethyl-4-methylpentoxy, 2-propylheptoxy, 2-ethyl-5-methyloctoxy, octoxy, phenoxy, naphthoxy group Is preferred. Of these, butoxy, 1-methylpropoxy, 2-methylpentoxy and 2-ethylhexoxy groups are more preferable. The siloxy group is not particularly limited. Specifically, hydrodimethylsiloxy, ethylhydromethylsiloxy, diethylhydrosiloxy, trimethylsiloxy, ethyldimethylsiloxy, diethylmethylsiloxy, triethylsiloxy groups and the like are preferable. Of these, hydrodimethylsiloxy, ethylhydromethylsiloxy, diethylhydrosiloxy, and trimethylsiloxy groups are more preferable.

In the present embodiment, the synthesis method (A-1) is not particularly limited, and includes the formula R ² MgX ¹ and the formula R ² Mg (R ² has the above-mentioned meaning and X ¹ is halogen). An organomagnesium compound belonging to the group, and the formulas M ¹ R ³ _n and M ¹ R ³ _(n-1) H (M ¹ and R ³ are as defined above, and n represents the valence of M ¹ ). An organometallic compound belonging to the group consisting of is reacted in an inert hydrocarbon solvent at 25 ° C. or higher and 150 ° C. or lower, and if necessary, the formula Y ¹ -H (Y ¹ is as defined above). It is possible to synthesize by reacting a compound represented by the formula ( ¹⁾ or reacting an organomagnesium compound and / or an organoaluminum compound having a functional group represented by Y1. Among these, when the organomagnesium compound soluble in the inert hydrocarbon solvent is reacted with the compound represented by the formula Y ¹ -H, the order of the reaction is not particularly limited, and the formula Y ^{1 is} contained in the organomagnesium compound. Either a method of adding a compound represented by —H, a method of adding an organomagnesium compound to a compound represented by the formula Y ¹ —H, or a method of adding both at the same time can be used. it can.

In this embodiment, the molar composition ratio c / (α + β) of Y ¹ with respect to all metal atoms in (A-1) is 0 ≦ c / (α + β) ≦ 2, and 0 ≦ c / (α + β) <1. It is preferable. When the molar composition ratio of Y ^{1 to} all metal atoms is 2 or less, the reactivity of (A-1) to (A-2) tends to be improved.

Next, (A-2) will be described. (A-2) is a titanium compound represented by Formula 2.
(A-2): Ti (OR ⁷ ) _d X ¹ _(4-d) Formula 2
(In the formula, d is a real number of 0 or more and 4 or less, R ⁷ is a hydrocarbon group of 1 to 20 carbon atoms, and X ¹ is a halogen atom.)

In the above formula 2, d is preferably 0 or more and 1 or less, and more preferably 0. Further, the hydrocarbon group represented by R ⁷ in Formula 2 is not particularly limited, and specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl, allyl An aliphatic hydrocarbon group such as a group; an alicyclic hydrocarbon group such as a cyclohexyl, 2-methylcyclohexyl, or cyclopentyl group; an aromatic hydrocarbon group such as a phenyl or naphthyl group; Among these, an aliphatic hydrocarbon group is preferable. The halogen represented by X ^1, chlorine, bromine, and iodine. Of these, chlorine is preferred. In this embodiment, (A-2) is most preferably titanium tetrachloride. In this embodiment, it is possible to use a mixture of two or more compounds selected from the above.

  Next, the reaction between (A-1) and (A-2) will be described. The reaction is preferably performed in an inert hydrocarbon solvent, more preferably in an aliphatic hydrocarbon solvent such as hexane or heptane. The molar ratio of (A-1) to (A-2) in the reaction is not particularly limited, but the molar ratio of Ti atoms contained in (A-2) to Mg atoms contained in (A-1) ( Ti / Mg) is preferably 0.1 or more and 10 or less, and more preferably 0.3 or more and 3 or less. Although it does not specifically limit about reaction temperature, It is preferable to carry out in the range of -80 degreeC or more and 150 degrees C or less, and it is more preferable to carry out in the range of -40 degreeC-100 degreeC. There is no restriction | limiting in particular in the addition order of (A-1) and (A-2), (A-2) is added following (A-1), (A-1) following (A-2) Any method of adding (A-1) and (A-2) at the same time is possible, but the method of simultaneously adding (A-1) and (A-2) is preferred. In the present embodiment, the solid catalyst component [A] obtained by the above reaction is used as a slurry solution using an inert hydrocarbon solvent.

  Another example of the Ziegler-Natta catalyst component used in the present embodiment includes a solid catalyst component [C] and an organometallic compound component [B], and the solid catalyst component [C] is represented by Formula 3. A carrier (C-3) prepared by reacting an organomagnesium compound (C-1) that is soluble in an inert hydrocarbon solvent with a chlorinating agent (C-2) represented by formula 4 contains Preferred is an olefin polymerization catalyst produced by supporting an organomagnesium compound (C-4) that is soluble in an inert hydrocarbon solvent represented by formula (6) and a titanium compound (C-5) represented by formula (6). .

(C-1): (M ² ) _γ (Mg) _δ (R ⁸ ) _e (R ⁹ ) _f (OR ¹⁰ ) _g ... Formula 3
(In the formula, M ² is a metal atom belonging to the group consisting of Groups 12, 13 and 14 of the periodic table, and R ⁸ , R ⁹ and R ¹⁰ are each a hydrocarbon having 2 to 20 carbon atoms. Γ, δ, e, f, and g are real numbers that satisfy the following relationships: 0 ≦ γ, 0 <δ, 0 ≦ e, 0 ≦ f, 0 ≦ g, 0 <e + f, 0 ≦ g / (Γ + δ) ≦ 2, kγ + 2δ = e + f + g (where k represents the valence of M ² ))

(C-2): H _h SiCl _i R ¹¹ _{(4- (h + i))} Formula 4
(Wherein R ¹¹ is a hydrocarbon group having 1 to 12 carbon atoms, and h and i are real numbers satisfying the following relationship: 0 <h, 0 <i, 0 <h + i ≦ 4)

(C-4): (M ¹ ) _α (Mg) _β (R ² ) _a (R ³ ) _B Y ¹ _C Formula 5
(In the formula, M ¹ is a metal atom belonging to the group consisting of Groups 12, 13 and 14 of the periodic table, R ² and R ³ are hydrocarbon groups having 2 to 20 carbon atoms, Y ¹ is alkoxy, siloxy, allyloxy, amino, amide, —N═C—R ⁴ , R ⁵ , —SR ⁶ (where R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups having 1 to 20 carbon atoms. In the case where c is 2, Y ¹ may be different from each other.), A β-keto acid residue, and α, β, a, b, and c satisfy the following relationship: Real number 0 ≦ α, 0 <β, 0 ≦ a, 0 ≦ b, 0 ≦ c, 0 <a + b, 0 ≦ c / (α + β) ≦ 2, nα + 2β = a + b + c (where n is M ¹ Represents the valence.))

(C-5): Ti (OR ⁷ ) _d X ¹ _(4-d) Formula 6
(In the formula, d is a real number of 0 or more and 4 or less, R ⁷ is a hydrocarbon group of 1 to 20 carbon atoms, and X ¹ is a halogen atom.)

  First, (C-1) will be described. (C-1) is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds Is. The relational expression kγ + 2δ = e + f + g of the symbols γ, δ, e, f, and g in Formula 3 indicates the stoichiometry between the valence of the metal atom and the substituent.

In the above formula, the hydrocarbon group represented by R ⁸ to R ⁹ is not particularly limited, but specifically, it is an alkyl group, a cycloalkyl group or an aryl group, for example, methyl, ethyl, propyl, butyl. , Pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl group and the like. Of these, preferably R ⁸ and R ⁹ are each an alkyl group. When α> 0, the metal atom M ² can be a metal atom belonging to the group consisting of Group 12, Group 13, and Group 14 of the Periodic Table, and examples thereof include zinc, boron, and aluminum. Among these, aluminum and zinc are particularly preferable.

The ratio δ / γ of magnesium to metal atom M ² is not particularly limited, but is preferably 0.1 or more and 30 or less, and more preferably 0.5 or more and 10 or less. When a predetermined organomagnesium compound with γ = 0 is used, for example, when R ⁸ is 1-methylpropyl or the like, it is soluble in an inert hydrocarbon solvent, and such a compound is also included in this embodiment. Gives favorable results. In Equation 3, it is recommended that R ⁸ and R ⁹ when γ = 0 be one of the following three groups (1), (2), and (3).

Group (1): At least one of R ⁸ and R ⁹ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R ⁸ and R ⁹ have 4 to 6 carbon atoms. Yes, at least one of which is a secondary or tertiary alkyl group.
Group (2): R ⁸ and R ⁹ are alkyl groups different from each other in carbon number, preferably R ⁸ is an alkyl group having 2 or 3 carbon atoms, and R ⁹ is an alkyl group having 4 or more carbon atoms. Be.
Group (3): At least one of R ⁸ and R ⁹ is a hydrocarbon group having 6 or more carbon atoms, preferably an alkyl group in which the sum of carbon atoms contained in R ⁸ and R ⁹ is 12 or more. .

  Hereinafter, these groups are specifically shown. Specific examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms in the group (1) include 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2-methylbutyl, 2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl group and the like are used. Among these, a 1-methylpropyl group is particularly preferable.

  In group (2), examples of the alkyl group having 2 or 3 carbon atoms include ethyl, 1-methylethyl, and propyl groups. Among these, an ethyl group is particularly preferable. Further, the alkyl group having 4 or more carbon atoms is not particularly limited, and specific examples thereof include butyl, pentyl, hexyl, heptyl, octyl group and the like. Of these, butyl and hexyl groups are particularly preferable.

  Furthermore, in the group (3), the hydrocarbon group having 6 or more carbon atoms is not particularly limited, and specific examples include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl group and the like. Among the hydrocarbon groups, an alkyl group is preferable, and among the alkyl groups, hexyl and octyl groups are particularly preferable.

  In general, when the number of carbon atoms contained in the alkyl group increases, it tends to be soluble in an inert hydrocarbon solvent, and the viscosity of the solution tends to increase. Therefore, it is preferable in handling to use an appropriate long-chain alkyl group. In addition, although the said organomagnesium compound is used as an inert hydrocarbon solution, even if trace amount of Lewis basic compounds, such as ether, ester, an amine, are contained in this solution, it can be used without any problem.

Next, the alkoxy group (OR ¹⁰ ) will be described. The hydrocarbon group represented by R ¹⁰ is preferably an alkyl group or aryl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group or aryl group having 3 to 10 carbon atoms. R ¹⁰ is not particularly limited, and specifically, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 2-methylpentyl, 2 -Ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, octyl, nonyl, decyl, phenyl, naphthyl groups and the like can be mentioned. Of these, butyl, 1-methylpropyl, 2-methylpentyl and 2-ethylhexyl groups are particularly preferable.

In this embodiment, the (C-1) is not particularly limited to the synthesis method, wherein ^R 8 MgX ¹ and wherein ^{R 8} Mg ^(R 8 have the meaning described above, ^{X 1} is a halogen atom.) An organomagnesium compound belonging to the group consisting of: and an organometallic compound belonging to the group consisting of formula M ² R ⁹ _k and formula M ² R ⁹ _(k-1) H (where M ² , R ⁹ and k are as defined above) Is reacted at a temperature of 25 ° C. or higher and 150 ° C. or lower in an inert hydrocarbon solvent, and if necessary, an alcohol having a hydrocarbon group represented by R ⁹ (R ⁹ has the above-mentioned meaning). Alternatively, a method of reacting with an alkoxymagnesium compound having a hydrocarbon group represented by R ⁹ and / or an alkoxyaluminum compound soluble in an inert hydrocarbon solvent is preferred.

  Among these, when reacting an organomagnesium compound soluble in an inert hydrocarbon solvent with an alcohol, the order of the reaction is not particularly limited, and a method of adding alcohol to the organomagnesium compound, organomagnesium in the alcohol. Either a method of adding a compound or a method of adding both at the same time can be used. In the present embodiment, the reaction ratio between the organomagnesium compound soluble in the inert hydrocarbon solvent and the alcohol is not particularly limited. However, as a result of the reaction, the alkoxy group-containing organomagnesium compound has an alkoxy group with respect to all metal atoms. The molar composition ratio g / (γ + δ) is 0 ≦ g / (γ + δ) ≦ 2, and preferably 0 ≦ g / (γ + δ) <1.

  Next, (C-2) will be described. (C-2) is represented by Formula 4, and at least one is a silicon chloride compound having a Si—H bond.

(C-2): H _h SiCl _i R ¹¹ _{(4- (h + i))} Formula 4
(Wherein R ¹¹ is a hydrocarbon group having 1 to 12 carbon atoms, and h and i are real numbers satisfying the following relationship: 0 <h, 0 <i, 0 <h + i ≦ 4)

The hydrocarbon group represented by R ¹¹ in Formula 4 is not particularly limited, and specific examples include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group such as methyl, ethyl, and the like. Propyl, 1-methylethyl, butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl group and the like. Among these, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and 1-methylethyl group is more preferable. H and i are numbers greater than 0 satisfying the relationship of h + i ≦ 4, and i is preferably 2 or more and 3 or less.

These compounds are not particularly limited, _{specifically, HSiCl 3, HSiCl 2 CH 3} , HSiCl 2 C 2 H 5, HSiCl 2 (C 3 H 7), HSiCl 2 (2-C 3 H 7) , HSiCl ₂ (C ₄ H ₉ ), HSiCl ₂ (C ₆ H ₅ ), HSiCl ₂ (4-Cl—C ₆ H ₄ ), HSiCl ₂ (CH═CH ₂ ), HSiCl ₂ (CH ₂ C ₆ H ₅₎ ), HSiCl ₂ (1-C ₁₀ H ₇ ), HSiCl ₂ (CH ₂ CH═CH ₂ ), H ₂ SiCl (CH ₃ ), H ₂ SiCl (C ₂ H ₅ ), HSiCl (CH ₃ ) ₂ , HSiCl _{(C 2 H 5) 2,} HSiCl (CH 3) (2-C 3 H 7), HSiCl (CH 3) (C 6 H 5), HSiCl (C 6 H 5) 2 and the like. A silicon chloride compound comprising these compounds or a mixture of two or more selected from these compounds is used. Among these, HSiCl ₃ , HSiCl ₂ CH ₃ , HSiCl (CH ₃ ) ₂ and HSiCl ₂ (C ₃ H ₇ ) are preferable, and HSiCl ₃ and HSiCl ₂ CH ₃ are more preferable.

  Next, the reaction between (C-1) and (C-2) will be described. In the reaction, (C-2) is preliminarily used as an inert hydrocarbon solvent, chlorinated hydrocarbon such as 1,2-dichloroethane, o-dichlorobenzene and dichloromethane; ether-based medium such as diethyl ether and tetrahydrofuran; It is preferable to use after diluting with a mixed medium. Among these, an inert hydrocarbon solvent is more preferable in terms of catalyst performance. Although the reaction ratio of (C-1) and (C-2) is not particularly limited, the silicon atom contained in (C-2) with respect to 1 mol of magnesium atom contained in (C-1) is 0.01 mol or more and 100 mol. Or less, more preferably 0.1 mol or more and 10 mol or less.

  There is no restriction | limiting in particular about the reaction method of (C-1) and (C-2), The method of simultaneous addition made to react, introducing (C-1) and (C-2) into a reactor simultaneously, ( A method in which (C-1) is introduced into the reactor after C-2) is charged to the reactor in advance, or (C-2) is charged into the reactor after (C-1) is charged in the reactor in advance. Any of the methods of introduction can be used. Among these, the method of introducing (C-1) into the reactor after charging (C-2) into the reactor in advance is preferable. The carrier (C-3) obtained by the above reaction is preferably separated by filtration or decantation, and then thoroughly washed with an inert hydrocarbon solvent to remove unreacted products or by-products. .

  Although it does not specifically limit about the reaction temperature of (C-1) and (C-2), It is preferable that it is 25 to 150 degreeC, It is more preferable that it is 30 to 120 degreeC, 40 degreeC or more More preferably, it is 100 ° C. or lower. In the method of simultaneous addition in which (C-1) and (C-2) are simultaneously introduced into the reactor and reacted, the temperature of the reactor is adjusted to a predetermined temperature in advance, It is preferable to adjust the reaction temperature to the predetermined temperature by adjusting the temperature to the predetermined temperature. In the method in which (C-1) is introduced into the reactor after (C-2) is charged into the reactor in advance, the temperature of the reactor charged with the silicon chloride compound is adjusted to a predetermined temperature, and the organomagnesium It is preferable to adjust the reaction temperature to a predetermined temperature by adjusting the temperature in the reactor to a predetermined temperature while introducing the compound into the reactor. In the method of introducing (C-2) into the reactor after charging (C-1) into the reactor in advance, the temperature of the reactor charged with (C-1) is adjusted to a predetermined temperature, It is preferable to adjust the reaction temperature to a predetermined temperature by adjusting the temperature in the reactor to a predetermined temperature while introducing -2) into the reactor.

  Next, the organomagnesium compound (C-4) will be described. As (C-4), what is represented by the above-mentioned Formula 5 (C-4) is preferable.

(C-4): (M ¹ ) _α (Mg) _β (R ² ) _a (R ³ ) _b Y ¹ _c Formula 5
(In the formula, M ¹ is a metal atom belonging to the group consisting of Groups 12, 13 and 14 of the periodic table, R ² and R ³ are hydrocarbon groups having 2 to 20 carbon atoms, Y ¹ is alkoxy, siloxy, allyloxy, amino, amide, —N═C—R ⁴ , R ⁵ , —SR ⁶ (where R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups having 1 to 20 carbon atoms. In the case where c is 2, Y ¹ may be different from each other.), A β-keto acid residue, and α, β, a, b, and c satisfy the following relationship: Real number 0 ≦ α, 0 <β, 0 ≦ a, 0 ≦ b, 0 <a + b, 0 ≦ c / (α + β) ≦ 2, nα + 2β = a + b + c (where n represents the valence of M ¹ .))

  The amount of (C-4) used is preferably 0.1 or more and 10 or less in terms of a molar ratio of magnesium atoms contained in (C-4) to titanium atoms contained in (C-5). More preferably, it is 5 or less.

  The temperature of the reaction between (C-4) and (C-5) is not particularly limited, but is preferably −80 ° C. or higher and 150 ° C. or lower, and more preferably −40 ° C. or higher and 100 ° C. or lower. preferable.

  The concentration at the time of using (C-4) is not particularly limited, but is preferably 0.1 mol / L or more and 2 mol / L or less based on the titanium atom contained in (C-4), 0.5 mol / L More preferably, it is 1.5 mol / L or less. In addition, it is preferable to use an inert hydrocarbon solvent for the dilution of (C-4).

  The order of addition of (C-4) and (C-5) to (C-3) is not particularly limited, and (C-5) is added following (C-4), following (C-5). (C-4) and (C-4) and (C-5) can be added at the same time. Among these, the method of adding (C-4) and (C-5) simultaneously is preferable. The reaction between (C-4) and (C-5) is carried out in an inert hydrocarbon solvent, but it is preferable to use an aliphatic hydrocarbon solvent such as hexane or heptane. The catalyst thus obtained is used as a slurry solution using an inert hydrocarbon solvent.

  Next, (C-5) will be described. In the present embodiment, (C-5) is a titanium compound represented by Formula 6 described above.

(C-5): Ti (OR ⁷ ) _d X ¹ _(4-d) Formula 6
(In the formula, d is a real number of 0 or more and 4 or less, R ⁷ is a hydrocarbon group of 1 to 20 carbon atoms, and X ¹ is a halogen atom.)
The hydrocarbon group represented by R ⁷ in Formula 6 is not particularly limited, and specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl, allyl group, and the like An aliphatic hydrocarbon group such as cyclohexyl, 2-methylcyclohexyl and cyclopentyl groups; and an aromatic hydrocarbon group such as phenyl and naphthyl groups. Among these, an aliphatic hydrocarbon group is preferable. The halogen represented by X ¹ is not particularly limited, and specific examples include chlorine, bromine and iodine. Of these, chlorine is preferred. (C-5) selected from the above may be used singly or in combination of two or more.

Although it does not specifically limit as the usage-amount of (C-5), 0.01-20 is preferable by molar ratio with respect to the magnesium atom contained in a support | carrier (C-3), and 0.05-10 is especially preferable.
The reaction temperature of (C-5) is not particularly limited, but is preferably -80 ° C or higher and 150 ° C or lower, and more preferably -40 ° C or higher and 100 ° C or lower.

  In the present embodiment, the method of supporting (C-5) with respect to (C-3) is not particularly limited, and a method of reacting excess (C-5) with (C-3), or a third method A method of efficiently supporting (C-5) by using components may be used, but a method of supporting by (C-5) and an organomagnesium compound (C-4) is preferable.

  Next, the organometallic compound component [B] in the present embodiment will be described. The solid catalyst component of this embodiment becomes a highly active polymerization catalyst by combining with the organometallic compound component [B]. The organometallic compound component [B] is sometimes called a “promoter”. The organometallic compound component [B] is preferably a compound containing a metal belonging to the group consisting of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, particularly organoaluminum compounds and / or Or an organomagnesium compound is preferable.

  As the organoaluminum compound, a compound represented by the following formula 7 is preferably used alone or in combination.

AlR ¹² _j Z ¹ _(3-j) Equation 7
Wherein R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, Z ¹ is a group belonging to the group consisting of hydrogen, halogen, alkoxy, allyloxy and siloxy groups, and j is a number of 2 to 3 .)

In the above formula 7, the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² is not particularly limited. Specifically, the hydrocarbon group is an aliphatic hydrocarbon, an aromatic hydrocarbon, or an alicyclic hydrocarbon. For example, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tri (2-methylpropyl) aluminum (or triisobutylaluminum), tripentylaluminum, tri (3-methylbutyl) aluminum, trihexyl Trialkylaluminum such as aluminum, trioctylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, bis (2-methylpropyl) aluminum chloride, ethylaluminum sesquichloride, die Aluminum halide compounds such as tilaluminum bromide, alkoxyaluminum compounds such as diethylaluminum ethoxide, bis (2-methylpropyl) aluminum butoxide, dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, ethyldimethylsiloxyaluminum diethyl Siloxyaluminum compounds and mixtures thereof are preferred. Among these, a trialkylaluminum compound is particularly preferable.

  As the organomagnesium compound, an organomagnesium compound that is soluble in the inert hydrocarbon solvent represented by the above formula 3 is preferable.

(M ² ) _γ (Mg) _δ (R ⁸ ) _e (R ⁹ ) _f (OR ¹⁰ ) _g Expression 3
(In the formula, M ² is a metal atom belonging to the group consisting of Groups 12, 13 and 14 of the periodic table, and R ⁸ , R ⁹ and R ¹⁰ are each a hydrocarbon having 2 to 20 carbon atoms. Γ, δ, e, f, and g are real numbers that satisfy the following relationships: 0 ≦ γ, 0 <δ, 0 ≦ e, 0 ≦ f, 0 ≦ g, 0 <e + f, 0 ≦ g / (Γ + δ) ≦ 2, kγ + 2δ = e + f + g (where k represents the valence of M ² ))

This organomagnesium compound is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but encompasses all dialkylmagnesium compounds and complexes of this compound with other metal compounds. is there. γ, δ, e, f, g, M ² , R ⁸ , R ⁹ , and OR ¹⁰ are as described above. However, since this organomagnesium compound preferably has higher solubility in an inert hydrocarbon solvent, δ / γ is preferably in the range of 0.5 to 10, and more preferably a compound in which M ² is aluminum.

  Regarding the method of adding the solid catalyst component and the organometallic compound component [B] to the polymerization system under the polymerization conditions, both may be added separately to the polymerization system, or the polymerization is performed after reacting both in advance. Although it may be added to the system, it is preferably added from the upper part in the polymerization system. This is because by adding the catalyst component from the upper part of the polymerization system, the bulk density of polyethylene powder of 53 μm or less tends to be low, and the above flow energy relationship of the present embodiment is more easily satisfied. . The ratio of the two to be combined is not particularly limited, but the organometallic compound component [B] is preferably 1 mmol or more and 3,000 mmol or less with respect to 1 g of the solid catalyst component.

(Metallocene catalyst)
On the other hand, as an example using a metallocene catalyst, a general transition metal compound is used. For example, the production method described in Japanese Patent No. 4868853 can be mentioned. Such metallocene catalysts include two catalysts: a) a transition metal compound having a cyclic η-bonding anion ligand and b) an activator capable of reacting with the transition metal compound to form a complex that exhibits catalytic activity. Consists of ingredients.

  The transition metal compound having a cyclic η-bonding anion ligand used in the present embodiment can be represented by, for example, the following formula 8.

L ¹ _j W _k M ³ X ² _p X ³ _q Expression 8
In Formula 8, L ¹ is each independently η selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. Represents a binding cyclic anionic ligand, and the ligand optionally has 1 to 8 substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, C1-C12 halogen-substituted hydrocarbon group, C1-C12 aminohydrocarbyl group, C1-C12 hydrocarbyloxy group, C1-C12 dihydrocarbylamino group, C1-C12 hydrocarbyl Selected from the group consisting of a phosphino group, a silyl group, an aminosilyl group, a hydrocarbyloxysilyl group having 1 to 12 carbon atoms, and a halosilyl group, 20 It is a substituent having a non-hydrogen atoms up.

In Formula 8, M ³ is a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and is bonded to at least one ligand L ¹ by η ^5. Represents a transition metal.

In Formula 8, W is a divalent substituent having up to 50 non-hydrogen atoms, and is bonded to L ¹ and M ³ with a valence of 1 each, whereby L ¹ and M ³ Represents a divalent substituent that forms a metallocycle in cooperation with each other, and each X ² independently represents a monovalent anionic σ-bonded ligand, a divalent bond that binds to M ³ in a divalent manner. Up to 60 non-ionic σ-bonded ligands selected from the group consisting of an anionic σ-bonded ligand and a divalent anionic σ-bonded ligand that binds to L ¹ and M ³ each with a monovalent valence. An anionic σ-bonded ligand having a hydrogen atom is represented.

In Formula 8, each X ² independently represents a neutral Lewis base coordinating compound having up to 40 non-hydrogen atoms, and X ³ represents a neutral Lewis base coordinating compound.

j is 1 or 2, provided that when j is 2, in some cases two ligands L ¹ are bonded to each other through a divalent group having up to 20 non-hydrogen atoms, The divalent group includes a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, and a hydrocarbyleneamino group having 1 to 12 carbon atoms. A group selected from the group consisting of a group, a silanediyl group, a halosilanediyl group, and a silyleneamino group.

k is 0 or 1, p is 0, 1 or 2, provided that X ² is a monovalent anionic σ-bonded ligand, or a divalent bond bonded to L ¹ and M ³ If an anionic σ-bound ligand, p is 1 or more integer smaller than form oxidation number of M ^3, also divalent anionic σ-bound coordination which X ² is bonded only to M ³ When it is a child, p is an integer that is (j + 1) or more smaller than the formal oxidation number of M ³ , and q is 0, 1 or 2.

Examples of ligands X ² in the compound of Formula 8, halides, hydrocarbon group of 1 to 60 carbon atoms, hydrocarbyloxy group of 1 to 60 carbon atoms, hydrocarbyl amido group of 1 to 60 carbon atoms, carbon Examples thereof include a hydrocarbyl phosphido group having 1 to 60 carbon atoms, a hydrocarbyl sulfide group having 1 to 60 carbon atoms, a silyl group, and a composite group thereof.
Examples of neutral Lewis base coordination compound X ³ in the compound of formula 8 is derived phosphine, ether, amine, olefin having 2 to 40 carbon atoms, dienes having 1 to 40 carbon atoms, these compounds And divalent groups.

  In the present embodiment, the transition metal compound having a cyclic η-bonding anion ligand is preferably a transition metal compound represented by the formula 8 (where j = 1). Preferable examples of the compound represented by Formula 8 (where j = 1) include compounds represented by Formula 9 below.

In Formula 9, M ⁴ represents a transition metal selected from the group consisting of titanium, zirconium, nickel, and hafnium, and represents a transition metal having a formal oxidation number of +2, +3, or +4, and R ¹³ is independently selected. A substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom and a composite group thereof. Wherein, when the substituent R ¹³ is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group or a germyl group, in some cases, two adjacent substituents R ¹³ are bonded to each other to form a divalent group. And thereby can form a ring by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring that is bonded to each of the two adjacent substituents R ¹³ .

In Formula 9, each X ⁴ independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or a carbon number. Substitution having up to 20 non-hydrogen atoms selected from the group consisting of 1 to 18 hydrocarbyl amide groups, 1 to 18 hydrocarbyl phosphide groups, 1 to 18 hydrocarbyl sulfide groups, and complex groups thereof Represents a group, but in some cases, two substituents X ⁴ can cooperate to form a neutral conjugated diene having 4 to 30 carbon atoms or a divalent group.

In Formula 9, Y ² represents —O—, —S—, —NR ^* — or —PR ^* —, where R ^* is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or 1 carbon atom. Represents a hydrocarbyloxy group having -8, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, or a composite group thereof.

In Formula 9, Z ² represents SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^{* 2} , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ , where R ^* is as defined above and n is 1, 2 or 3.

  Examples of the transition metal compound having a cyclic η-binding anion ligand used in the present embodiment include the following compounds. Although it does not specifically limit as a zirconium type compound, Specifically, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (1 , 3-Dimethylcyclopentadienyl) zirconium dimethyl, (pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl Bis (fluorenyl) zirconium dimethyl, ethylene bis (indenyl) zirconium dimethyl, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylene bis (4 Methyl-1-indenyl) zirconium dimethyl, ethylenebis (5-methyl-1-indenyl) zirconium dimethyl, ethylenebis (6-methyl-1-indenyl) zirconium dimethyl, ethylenebis (7-methyl-1-indenyl) zirconium dimethyl Ethylene bis (5-methoxy-1-indenyl) zirconium dimethyl, ethylene bis (2,3-dimethyl-1-indenyl) zirconium dimethyl, ethylene bis (4,7-dimethyl-1-indenyl) zirconium dimethyl, ethylene bis- (4,7-dimethoxy-1-indenyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclope Tajieniru - fluorenyl) zirconium dimethyl, Shirirenbisu (cyclopentadienyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) zirconium dimethyl, and the like.

Although it does not specifically limit as a titanium-type compound, Specifically, [(Nt-butyramide) (tetramethyl- (eta) ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(N- t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N- Phenylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-benzylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N- t- butylamido) (eta ⁵ - cyclopentadienyl) -1,2-ethane Yl] Titanium Dimethyl, [(N-t- butylamido) (eta ⁵ - cyclopentadienyl) dimethyl silane] titanium dimethyl, [(N-methylamide) (eta ⁵ - cyclopentadienyl) -1,2-ethanediyl] Titanium dimethyl, [(N-methylamide) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamide) (η ⁵ -indenyl) dimethylsilane] titanium dimethyl, [(N-benzylamide ) (Η ⁵ -indenyl) dimethylsilane] titanium dimethyl and the like.

  Although it does not specifically limit as a nickel-type compound, Specifically, Dibromobistriphenylphosphine nickel, Dichlorobistriphenylphosphine nickel, Dibromodiacetonitrile nickel, Dibromodibenzonitrile nickel, Dibromo (1,2-bisdiphenylphosphinoethane) Nickel, dibromo (1,3-bisdiphenylphosphinopropane) nickel, dibromo (1,1′-diphenylbisphosphinoferrocene) nickel, dimethylbisdiphenylphosphinenickel, dimethyl (1,2-bisdiphenylphosphinoethane) nickel Methyl (1,2-bisdiphenylphosphinoethane) nickel tetrafluoroborate, (2-diphenylphosphino-1-phenylethyleneoxy) phenylpyridine nickel, Chlorobistriphenylphosphine palladium, dichlorodibenzonitrile palladium, dichlorodiacetonitrile palladium, dichloro (1,2-bisdiphenylphosphinoethane) palladium, bistriphenylphosphine palladium bistetrafluoroborate, bis (2,2'-bipyridine) methyliron Examples thereof include tetrafluoroborate etherate.

  Although it does not specifically limit as a hafnium type compound, Specifically, [(Nt-butyramide) (tetramethyl- (eta) 5-cyclopentadienyl) -1,2-ethanediyl] hafnium dimethyl, [(N-t -Butylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(N-methylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(N-phenylamide) (Tetramethyl-η5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(N-benzylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(Nt-butylamide) ( η5-cyclopentadienyl) -1,2-ethanediyl] Funium dimethyl, [(Nt-butylamide) (η5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(N-methylamido) (η5-cyclopentadienyl) -1,2-ethanediyl] hafnium dimethyl, [(N-methylamide) (η5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(Nt-butylamide) (η5-indenyl) dimethylsilane] hafnium dimethyl, [(N-benzylamide) (η5-indenyl ) Dimethylsilane] hafnium dimethyl and the like.

Specific examples of the transition metal compound having a cyclic η-bonding anion ligand used in the present embodiment further include “dimethyl” in the names of the above-mentioned zirconium-based compounds and titanium-based compounds (this is , The last part of the name of each compound, that is, the part that appears immediately after the part of “zirconium” or “titanium”, and the name corresponding to the part of X ^{4 in} the formula 9) , “Dibromo”, “diiodo”, “diethyl”, “dibutyl”, “diphenyl”, “dibenzyl”, “2- (N, N-dimethylamino) benzyl”, “2-butene-1,4-diyl” , "s- trans -η4-1,4- diphenyl-1,3-butadiene,""s- trans eta ^{4-3-methyl-1,3-pentadiene",} "s- trans eta ⁴ - , 4-dibenzyl-1,3-butadiene, "" s- trans eta ^{4-2,4-hexadiene,} "" s- trans eta ⁴ -1,3-pentadiene "," s- trans eta ⁴ - 1,4-ditolyl-1,3-butadiene ”,“ s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene ”,“ s-cis-η ⁴ -1,4-diphenyl ” -1,3-butadiene ”,“ s-cis-η ⁴ -3-methyl-1,3-pentadiene ”,“ s-cis-η ⁴ -1,4-dibenzyl-1,3-butadiene ”,“ s -Cis-η ⁴ -2,4-hexadiene "," s-cis-η ⁴ -1,3-pentadiene "," s-cis-η ⁴ -1,4-ditolyl-1,3-butadiene "," s- cis eta ^4-1,4-bis (trimethylsilyl) -1,3-butadiene Compounds having a name that can be in place of any of the like may be mentioned.

  The transition metal compound having a cyclic η-bonding anion ligand used in this embodiment can be synthesized by a generally known method. In this embodiment, these transition metal compounds may be used alone or in combination.

Next, b) an activator (hereinafter, also simply referred to as “activator”) that can form a complex that reacts with a transition metal compound and exhibits catalytic activity, used in the present embodiment will be described.
Examples of the activator in the present embodiment include compounds defined by the following formula 10.

[L ² −H] ^{d +} [M ⁵ _m Q _p ] ^d− Formula 10
(Wherein [L ² -H] ^{d +} represents a proton-donating Bronsted acid, wherein L ² represents a neutral Lewis base, d is an integer of 1 to 7; [M ⁵ _m Q _p ] ^d- represents a compatible non-coordinating anion, where M ⁵ represents a metal or metalloid belonging to any of Groups 5 to 15 of the periodic table, and Q each independently , Hydride, halide, dihydrocarbyl amide group having 2 to 20 carbon atoms, hydrocarbyloxy group having 1 to 30 carbon atoms, hydrocarbon group having 1 to 30 carbon atoms, and substituted hydrocarbon group having 1 to 40 carbon atoms Wherein the number of halides Q is 1 or less, m is an integer from 1 to 7, p is an integer from 2 to 14, and d is as defined above. , Pm = d.)

  Although it does not specifically limit as a non-coordinating anion, Specifically, a tetrakis phenyl borate, a tri (p-tolyl) (phenyl) borate, a tris (pentafluorophenyl) (phenyl) borate, a tris (2,4- Dimethylphenyl) (hydrphenyl) borate, tris (3,5-dimethylphenyl) (phenyl) borate, tris (3,5-di-trifluoromethylphenyl) (phenyl) borate, tris (pentafluorophenyl) (cyclohexyl) borate , Tris (pentafluorophenyl) (naphthyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) volley , Tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) ( Hydroxyphenyl) borate, tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) Borate, tris (pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydride) Carboxymethyl-2-naphthyl) borate, and the like.

  Examples of other preferable non-coordinating anions include borates in which the hydroxy group of the borate exemplified above is replaced with an NHR group. Here, R is preferably a methyl group, an ethyl group or a tert-butyl group.

  Further, the proton-providing Bronsted acid is not particularly limited, and specifically, triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium and tri (n-octyl) ammonium. Trialkyl group-substituted ammonium cation such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzylanilinium, etc. N, N-dialkylanilinium cations; dialkylammonium cations such as di- (i-propyl) ammonium and dicyclohexylammonium; triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) Phosphonium triaryl phosphonium cations such as, or dimethyl sulfonium, diethyl full sulfonium include diphenyl sulfonium and the like.

  In this embodiment, an organometallic oxy compound having a unit represented by the following formula 11 can also be used as an activator.

(Here, M ⁶ is a metal or metalloid of Groups 13 to 15 of the periodic table, R ¹⁴ is each independently a hydrocarbon group or substituted hydrocarbon group having 1 to 12 carbon atoms, and n is a metal. M is a valence of ⁶ and m is an integer of 2 or more.)

  A preferred example of the activator of the present embodiment is an organoaluminum oxy compound containing a unit represented by the following formula 12, for example.

(Here, R ¹⁵ is an alkyl group having 1 to 8 carbon atoms, and m is an integer of 2 to 60.)
A more preferable example of the activator of the present embodiment is methylalumoxane including a unit represented by the following formula 13, for example.

(Here, m is an integer from 2 to 60.)

  In the present embodiment, the activator components may be used alone or in combination.

  In the present embodiment, these catalyst components can be supported on a solid component and used as a supported catalyst. Such a solid component is not particularly limited, and specifically, a porous polymer material such as polyethylene, polypropylene or a copolymer of styrene divinylbenzene; silica, alumina, magnesia, magnesium chloride, zirconia, titania, boron oxide Inorganic solid materials of Group 2, 3, 4, 13 and 14 elements of the periodic table such as calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, chromium oxide and thorium oxide, and mixtures thereof; Examples include at least one inorganic solid material selected from oxides.

  The composite oxide of silica is not particularly limited, and specific examples include composite oxides of silica such as silica magnesia, silica alumina and the like, and Group 2 or Group 13 elements of the periodic table. In the present embodiment, in addition to the above two catalyst components, an organoaluminum compound can be used as a catalyst component as necessary. The organoaluminum compound that can be used in the present embodiment is a compound represented by the following formula 14, for example.

(Wherein R ¹⁶ is an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 20 carbon atoms, X ⁵ is a halogen, hydrogen or alkoxyl group, and the alkyl group is linear, branched or And n is an integer of 1 to 3.)

Here, the organoaluminum compound may be a mixture of compounds represented by the above formula 14. Examples of the organoaluminum compound that can be used in this embodiment include the above formula, wherein R ¹⁶ is a methyl group, an ethyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, a tolyl group, or the like. Examples of X ⁵ include a methoxy group, an ethoxy group, a butoxy group, and chloro.

  The organoaluminum compound that can be used in the present embodiment is not particularly limited, and specifically, trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. Or reaction products of these organic aluminums with alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, such as dimethylmethoxyaluminum, diethylethoxyaluminum, dibutylbutoxyaluminum, etc. Can be mentioned.

[Production method of polyethylene powder]
Examples of the method for polymerizing polyethylene in the method for producing polyethylene powder of the present embodiment include a method of (co) polymerizing ethylene or a monomer containing ethylene by a suspension polymerization method or a gas phase polymerization method. Among these, the suspension polymerization method that can efficiently remove the heat of polymerization is preferable. In the suspension polymerization method, an inert hydrocarbon medium can be used as a medium, and the olefin itself can also be used as a solvent.

  Such an inert hydrocarbon medium is not particularly limited, and specifically, propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons; cyclopentane, And alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane; or a mixture thereof.

  The polymerization temperature in the polyethylene powder production method is usually 30 ° C. or higher and 100 ° C. or lower. The polymerization temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher, and preferably 95 ° C or lower, more preferably 90 ° C or lower. When the polymerization temperature is 30 ° C. or higher, industrially more efficient production tends to be possible. On the other hand, when the polymerization temperature is 100 ° C. or lower, there is a tendency that continuous and more stable operation can be performed.

  The polymerization pressure in the method for producing polyethylene powder is usually from normal pressure to 2 MPa. The polymerization pressure is preferably 0.1 MPa or more, more preferably 0.12 MPa or more, and preferably 1.5 MPa or less, more preferably 1.0 MPa or less. When the polymerization pressure is higher than normal pressure, industrially more efficient production tends to be possible, and when the polymerization pressure is 2 MPa or less, partial heat generation due to rapid polymerization reaction at the time of catalyst introduction is suppressed. It tends to be able to produce polyethylene stably.

  The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods, but it is preferable to perform polymerization in a continuous manner. By continuously supplying ethylene gas, solvent, catalyst, etc. into the polymerization system and continuously discharging it together with the generated polyethylene, it becomes possible to suppress partial high-temperature conditions due to rapid ethylene reaction. The system becomes more stable. When ethylene reacts in a uniform state in the system, the formation of branches, double bonds, etc. in the polymer chain is suppressed, and it is difficult for low molecular weight and cross-linking of polyethylene to occur. Unmelted material remaining at the time of dissolution is reduced, coloring is suppressed, and problems such as deterioration of mechanical properties are less likely to occur. Therefore, a continuous system in which the inside of the polymerization system becomes more uniform is preferable.

  It is also possible to carry out the polymerization in two or more stages having different reaction conditions. Furthermore, the intrinsic viscosity of the resulting polyethylene can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature, as described, for example, in DE-A-3127133. You can also. By adding hydrogen as a chain transfer agent in the polymerization system, the intrinsic viscosity can be controlled within an appropriate range. When hydrogen is added into the polymerization system, the molar fraction of hydrogen is preferably 0 mol% or more and 30 mol% or less, more preferably 0 mol% or more and 25 mol% or less, and 0 mol% or more and 20 mol% or less. More preferably. In addition, in this embodiment, the other well-known component useful for manufacture of polyethylene other than each above components can be included.

  When polymerizing polyethylene, it is also possible to use an antistatic agent such as Stadis 450 manufactured by The Associated Octel Company (manufactured by the agency Maruwa product) in order to suppress polymer adhesion to the polymerization reactor. Stadis 450 can also be diluted with an inert hydrocarbon medium and added to the polymerization reactor by a pump or the like. In this case, the addition amount is preferably in the range of 0.10 ppm to 20 ppm, more preferably in the range of 0.20 ppm to 10 ppm, with respect to the polyethylene production amount per unit time.

  As described above, the polyethylene powder according to the present embodiment is characterized in that the flow energy when the air flow rate of polyethylene powder is 4 mm / s is 30% or more of the flow energy when there is no air flow. And, as an effective method for setting the flow energy in such a specific range, the average particle size, the particle size distribution, the content of particles having a particle size of 75 μm or less, and / or the bulk density of 53 μm or less are set as the specific range. And so on.

[Additive]
If necessary, additives such as a slip agent, a neutralizing agent, an antioxidant, a light-resistant stabilizer, an antistatic agent, and a pigment can be added to the polyethylene powder of this embodiment.
The slipping agent or neutralizing agent is not particularly limited, and examples thereof include aliphatic hydrocarbons, higher fatty acids, higher fatty acid metal salts, fatty acid esters of alcohols, waxes, higher fatty acid amides, silicone oils, and rosins. Although content of a slip agent or a neutralizing agent is not specifically limited, It is 5000 ppm or less, Preferably it is 4000 ppm or less, More preferably, it is 3000 ppm or less.

  Although it does not specifically limit as antioxidant, For example, a phenol type compound or a phenol phosphate type compound is preferable. Specifically, 2,6-di-t-butyl-4-methylphenol (dibutylhydroxytoluene), n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis (Methylene (3,5-di-tert-butyl-4-histaloxyhydrocinnamate)) phenolic antioxidants such as methane; 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) Phenyl) propoxy] -2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine and other phenol phosphorus antioxidants; tetrakis (2,4 -Di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetra Bis (2, 4-t-butylphenyl phosphite) phosphorus-based antioxidants and the like.

  The amount of antioxidant in the polyethylene powder according to this embodiment is 100 ppm to 5000 ppm, preferably 100 ppm to 4000 ppm, and more preferably 100 ppm to 3000 ppm. When the antioxidant is 100 ppm or more, the deterioration of the polyethylene is suppressed, and embrittlement, discoloration, deterioration of mechanical properties and the like hardly occur, and the long-term stability is improved. Moreover, when antioxidant is 5000 ppm or less, coloring by antioxidant itself and the modified body of antioxidant, or coloring by reaction of antioxidant and a metal component can be suppressed.

  The light-resistant stabilizer is not particularly limited, and examples thereof include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro. Benzotriazole-based light stabilizers such as benzotriazole; bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4- Hindered amine light stabilizers such as piperidyl) imino}]. Although content of a light-resistant stabilizer is not specifically limited, It is 5000 ppm or less, Preferably it is 3000 ppm or less, More preferably, it is 2000 ppm or less.

  The antistatic agent is not particularly limited, and examples thereof include aluminosilicate, kaolin, clay, natural silica, synthetic silica, silicates, talc, diatomaceous earth, and glycerin fatty acid ester.

  The content of the organic additive contained in the fiber made of polyethylene powder can be determined by extraction with tetrahydrofuran (THF) for 6 hours by Soxhlet extraction, and separation and quantification of the extract by liquid chromatography. The content of the inorganic additive can be quantified from the weight of ash by burning polyethylene resin in an electric furnace.

[Molded body]
The polyethylene powder of the present embodiment can be processed by various methods. Moreover, the molded object obtained using this polyethylene powder can be used for various uses. Although it is not limited as a molded object, for example, it is suitable as a microporous film for secondary battery separators, among them, a microporous film for lithium ion secondary battery separators, a sintered body, high-strength fibers, gel spinning, etc. is there. Examples of the method for producing the microporous membrane include a processing method in which a wet process using a solvent is performed by extrusion, stretching, extraction, and drying in an extruder equipped with a T die.
In addition, by taking advantage of the characteristics of high molecular weight ethylene polymers such as wear resistance, high slidability, high strength, and high impact properties, compacts, filters and dusts obtained by sintering ethylene polymers. It can also be used as a trap material.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example and a comparative example, this invention is not limited at all by the following examples.

[Measurement method and conditions]
The physical properties of the polyethylene powders of Examples and Comparative Examples were measured by the following methods.
(1) Viscosity average molecular weight (Mv)
1) 10 mg of polyethylene powder was weighed and put into a test tube. 2) 20 mL of decalin (decahydronaphthalene) was added to the test tube.
3) The mixture was stirred at 150 ° C. for 2 hours to dissolve the polyethylene.
4) The dropping time (ts) between the marked lines was measured using a Ubbelohde type viscometer for the solution in a thermostatic bath at 135 ° C.
5) Similarly, for the case of 5 mg of polyethylene powder, the drop time (ts) between the marked lines was measured.
6) The fall time (tb) of only decalin without polyethylene as a blank was measured.
7) The reduced viscosity (ηsp / C) of the polyethylene powder obtained according to the following equation is plotted to derive a linear expression of the concentration (C) and the reduced viscosity (ηsp / C) of the polyethylene powder. And the intrinsic viscosity (η) was determined.
.eta.sp / C = (ts / tb-1) /0.1
8) The viscosity average molecular weight (Mv) was determined from the intrinsic viscosity (η) according to the following formula.
Mv = (5.34 × 10 ⁴ ) × [η] ^1.49

(2) Density 1) 180 g of polyethylene powder was put into a 200 mm × 200 mm × 4 mm thick mold.
2) With a press machine at a set temperature of 200 ° C., preheating was performed at 10 kg / cm ² for 5 minutes, defoaming operation was performed 3 times, and pressing was performed at 150 kg / cm ² for 15 minutes.
3) The mold was cooled to room temperature with a cooling press.
4) A section of 2 cm × 2 cm × thickness 4 mm was cut out from the obtained press sheet.
5) Using a density gradient tube according to JIS K7112, the density of the molded body was measured, and the obtained value was used as the density of the powder.

(3) Fluid energy A powder fluidity analyzer, powder rheometer FT4 (Spectris Co., Ltd.) was used.
1) 53 g of powder was filled in a dedicated split container (capacity was 260 ml, and the bottom plate of the container was a mesh-shaped cylindrical container).
2) Powder is produced while rotating the blade (attached blade corresponding to the dedicated split container) at a rotational speed at which the blade tip speed is 100 mm / s without allowing air to flow from below the container. The inside was moved from above to below at a speed of 30 mm / s, and the rotational torque and vertical load at that time were measured. The integrated value of the measured rotational torque and vertical load was defined as the flow energy during no ventilation.
3) While rotating the blade in the opposite direction to 2) at a rotation speed at which the tip speed of the blade is 40 mm / s, the powder is raised from below to above at a speed of 30 mm / s to the original position. Returned. Thereafter, air is fed from below the container (lower part of the powder layer) at a linear speed of 2 mm / s, and the blade is rotated at a rotational speed at which the speed of the tip of the blade is 100 mm / s (the rotational direction is 2). The same), and moved from above to below at a speed of 30 mm / s. Next, while rotating the blade in the direction opposite to 2) at the rotation speed at which the blade tip speed is 40 mm / s, the powder is raised from below to above at a speed of 30 mm / s until the original position. Returned.
4) The same operation as 3) is performed at a linear velocity of 4 mm / s for the air fed from the lower part of the powder layer, and the rotational torque and the vertical load when the air fed at a linear velocity of 4 mm / s is 2) The measurement was performed in the same manner. The flow energy calculated in the same manner as 2) was defined as the flow energy when the air flow rate was 4 mm / s.

(4) Average particle size The average particle size of the polyethylene powder is 10 types of sieves (openings: 710 μm, 500 μm, 425 μm, 355 μm, 300 μm, 212 μm, 150 μm, 106 μm, 75 μm, 53 μm) defined in JIS Z8801. Then, in the integral curve obtained by integrating the weight of the particles remaining on each sieve obtained when classifying 100 g of particles from the side having a large mesh opening, the particle size at 50% weight was defined as the average particle size.

(5) D90 / D10 ratio The particle size distribution was measured using a laser diffraction particle size distribution measuring device SALD-2300 (manufactured by Shimadzu Corporation). Methanol was used as the dispersion medium, and an ultrasonic bath was used as the dispersion apparatus. In the particle size cumulative distribution data analyzed by this apparatus, the D90 / D10 ratio was calculated as D10 and D90, respectively, by adding the particles in the distribution from the small diameter side to become 10% cumulative or 90% cumulative. .

(6) Content of particles having a particle size of 75 μm or less The content of particles having a particle size of 75 μm or less is determined by measuring the average particle size in the following (7), with an opening of 75 μm relative to the weight of all particles (polyethylene powder) It was determined as the sum of the weights of the particles that passed through the sieve having the opening.

(7) Bulk density of particles having a particle size of 53 μm or less 1) Polyethylene powder was classified with a sieve having an opening of 53 μm in accordance with JIS Z8801 standard.
2) The polyethylene powder that passed through a sieve having an opening of 53 μm was collected.
3) Each powder was allowed to flow down into a 100 cc cylindrical container through a calibrated funnel orifice of standard dimensions according to JIS K 6891.
4) To prevent compaction and overflow of powder from the cup, move the blade such as a spatula vertically while keeping it in contact with the top surface of the container, and carefully scour excess powder from the top surface of the container. Dropped.
5) Remove all samples from the side of the container, measure the mass of the powder together with the container, and subtract the mass of the empty measurement container previously measured to reduce the mass (g) of the powder to 0 Calculated up to 1 g.
6) The bulk density (g / cc) was calculated by the following formula.
Bulk density (g / cc) = Mass of powder (g) / Volume of cylindrical container (cc)
7) The above measurement was performed three times, and the average value was recorded.
8) This average value was taken as the bulk density of particles having a particle size of 53 μm or less.

〔Evaluation method〕
The polyethylene powders of Examples and Comparative Examples were evaluated by the following methods.
(8) Variation in thickness of microporous membrane Three samples of microporous membranes ((A) to (C) samples, each sample obtained by forming the polyethylene powder of Examples and Comparative Examples by the method described later) About 5 sheets), the thickness variation of the microporous film between 3 samples was evaluated by measuring the thickness of each microporous film. The thickness of each microporous membrane is measured using a contact-type continuous thickness measuring device (ANRITSU K310D manufactured by Anritsu Electric Co., Ltd.) in the width direction of the film, and the thickness of the microporous membrane of each sample is measured. The thicknesses of five films formed from the above were averaged. About thickness variation, the difference of the thickness average value of the microporous film between three samples was evaluated on the following evaluation criteria.

(Evaluation criteria)
◎ (very good): Difference in thickness average value between 3 samples is less than 0.1 μm ○ (No problem): Difference in thickness average value between 3 samples is 0.1 μm or more and less than 0.3 μm × (Poor): The difference in thickness average value among the three samples was 0.3 μm or more. The better the evaluation of the variation in the thickness of the microporous film between the three samples, the more the samples were used for the production of the three microporous films (A) to (C). This means that there is no uneven distribution between the polyethylene powder blends in the sample. Specifically, in order to produce a microporous membrane, the polyethylene of each example and comparative example, low molecular weight polyethylene, etc. are stirred with a Henschel mixer. When mixed, it means that the powder blend is not unevenly distributed in the mixer.

(9) TD direction tensile strength (MPa), TD direction tensile elongation (%) variation of microporous membrane 3 samples of each obtained by film formation by the method described later using polyethylene powder of Examples and Comparative Examples By measuring the TD-direction tensile strength (MPa) and TD-direction tensile elongation (%) of each microporous membrane (referred to here) for the porous membranes ((A) to (C) samples, 5 for each sample). The “TD direction” means the TD direction at the time of producing the microporous membrane), and the variation in the physical properties of the microporous membrane between the three samples was evaluated. About each microporous film, TD direction (vertical direction) tensile strength (MPa) and TD direction tensile elongation (%) are based on JIS K7127, Shimadzu Corporation tensile tester, Autograph AG-A type (trademark) Was used to measure a TD sample (shape; width 10 mm × length 100 mm) prepared from each microporous membrane. In this measurement, the TD sample had a 50 mm gap between the chucks, and cellophane tape (product name: N.29, manufactured by Nitto Denko Packaging System Co., Ltd.) was attached to one side of both ends (25 mm each) of the sample. Was used. Furthermore, in order to prevent sample slippage during the test, 1 mm-thick fluororubber was affixed inside the chuck of the tensile tester.

The tensile elongation (%) in the TD direction was obtained by dividing the amount of elongation (mm) until rupture by the distance between chucks (50 mm) and multiplying by 100.
The TD direction tensile strength (MPa) was determined by dividing the strength at break by the sample cross-sectional area before the test. The TD tensile strength (MPa) and TD tensile elongation (%) were measured at a temperature of 23 ± 2 ° C., a chuck pressure of 0.30 MPa, and a tensile speed of 200 mm / min.
The TD direction (vertical direction) tensile strength (MPa) and TD direction tensile elongation (%) of the microporous membrane (samples (A) to (C)) of each sample were five films ( The tensile strength (MPa) and the tensile elongation (%) of the TD sample were averaged.

Regarding the variation in TD direction tensile strength (MPa) and TD direction tensile elongation (%), the difference between the three samples in the TD direction tensile strength (MPa) and TD direction tensile elongation (%) was evaluated as follows. Evaluated by criteria.
(Evaluation criteria)
A (good): Both the difference in tensile strength and the difference in elongation between samples are less than 2%.
○ (no problem): Not applicable to “◎”, and both the difference in tensile strength and the difference in elongation between samples are less than 5%.
X (Poor): At least one of the difference in tensile strength and the difference in elongation between samples is 5% or more.
The better the evaluation of the TD direction tensile strength (MPa) and TD direction tensile elongation (%) variation of the microporous membrane between the three samples, the more the microporous membranes used in the production of the three samples (A) to (C) ) Means no uneven distribution between the polyethylene powder blends of the sample.

(10) Surface roughness (Ra) variation of porous sheet For porous sheets molded using the polyethylene powders of Examples and Comparative Examples, the surface roughness (Ra) of each porous sheet was measured, thereby measuring the sheet. The roughness of the surface roughness (surface uniformity) was evaluated. The surface roughness (Ra) of the sheet was measured using a stylus type surface roughness meter (“Handy Surf E-35B” manufactured by Tokyo Seimitsu Co., Ltd.), tip diameter R: 5 μm, speed: 0.6 mm / s, measurement. Measurement was performed under the conditions of length: 12.5 mm and cut-off value λc: 2.5 mm. The measurement position was measured at a total of five locations, one at the center of the surface of the object to be measured and one at the center of the four equally divided surfaces when the surface was equally divided into four as much as possible.

For the surface roughness (Ra) variation, the difference in surface roughness (Ra) between the five locations was evaluated based on the following criteria.
(Evaluation criteria)
○ (No problem): All the differences between the five locations are within 5 μm.
X (bad): The difference exceeds 5 μm at one or more of the five locations.
The better the evaluation of the variation in the surface roughness (Ra) of the porous sheet, the better the surface uniformity of the sheet, that is, the sheet is stably and uniformly produced from polyethylene powder. Specifically, in the production of a porous sheet, there is a step in which polyethylene powder is spread and transported on a metal flat plate. This means that the polyethylene powder maintains its fixed state (maintains the accumulated state), and the sheet is stably and uniformly manufactured.

[Catalyst synthesis method]
[Reference Example 1: Catalyst Synthesis Example 1: Preparation of Solid Catalyst Component [A]]
1,600 mL of hexane was added to an 8 L stainless steel autoclave purged with nitrogen. While stirring at 10 ° C., 800 mL of 1 mol / L titanium tetrachloride hexane solution and 800 mL of hexane solution of organomagnesium compound represented by 1 mol / L composition formula AlMg ₅ (C ₄ H ₉ ) ₁₁ (OSiH) ₂ Added simultaneously over time. After the addition, the temperature was slowly raised and the reaction was continued at 10 ° C. for 1 hour. After completion of the reaction, 1,600 mL of the supernatant was removed, and the solid catalyst component [A] was prepared by washing 10 times with 1,600 mL of hexane. The amount of titanium contained in 1 g of this solid catalyst component was 3.05 mmol.

[Reference Example 2: Catalyst Synthesis Example 2: Preparation of supported metallocene catalyst component [B]]
Spherical silica having an average particle diameter of 15 μm, a surface area of 700 m ² / g, and an intraparticle pore volume of 1.8 mL / g was calcined at 500 ° C. for 5 hours in a nitrogen atmosphere and dehydrated. The amount of surface hydroxyl groups of dehydrated silica was 1.85 mmol / g per gram of SiO ₂ . Under a nitrogen atmosphere, 40 g of this dehydrated silica was dispersed in 800 mL of hexane in a 1.8 L autoclave to obtain a slurry. While maintaining the obtained slurry at 50 ° C. with stirring, 80 mL of a hexane solution of triethylaluminum (concentration 1 mol / L) was added, and then stirred for 2 hours to react triethylaluminum with the surface hydroxyl group of silica to be treated with triethylaluminum. A component [a] containing silica and a supernatant liquid and having the surface hydroxyl group of the silica treated with triethylaluminum capped with triethylaluminum was obtained. Thereafter, the supernatant liquid in the obtained reaction mixture was removed by decantation to remove unreacted triethylaluminum in the supernatant liquid. Thereafter, an appropriate amount of hexane was added to obtain 880 mL of silica hexane slurry treated with triethylaluminum.

On the other hand, 200 mmol of [(Nt-butyramide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) was added to Isopar E (exon). 1 mol / of the formula AlMg ₆ (C ₂ H ₅ ) ₃ (nC ₄ H ₉ ) ₁₂ dissolved in 1000 mL and previously synthesized from triethylaluminum and dibutylmagnesium. 20 mL of L hexane solution was added, and further hexane was added to adjust the titanium complex concentration to 0.1 mol / L to obtain component [b].

  Further, 5.7 g of bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter referred to as “borate”) was added to 50 mL of toluene and dissolved, and borate Of 100 mmol / L in toluene was obtained. To this borate toluene solution, 5 mL of a 1 mol / L hexane solution of ethoxydiethylaluminum was added at room temperature, and further hexane was added so that the borate concentration in the solution was 70 mmol / L. Then, it stirred at room temperature for 1 hour and obtained the reaction mixture containing a borate.

46 mL of this reaction mixture containing borate was added to 800 mL of the slurry of component [a] obtained above with stirring at 15 to 20 ° C., and the borate was supported on silica. Thus, a slurry of silica carrying borate was obtained. Further, 32 mL of the component [b] obtained above was added and stirred for 3 hours to react the titanium complex with borate. Thus, a supported metallocene catalyst [B] containing silica and a supernatant liquid and having catalytically active species formed on the silica was obtained.
Thereafter, the supernatant liquid in the obtained reaction mixture was removed by decantation to remove unreacted triethylaluminum in the supernatant liquid.

[Comparative Example 1]
(Polyethylene polymerization process)
Hexane, ethylene, hydrogen, and supported metallocene catalyst component [B] were continuously fed to a Bessel type polymerization reactor equipped with a stirrer to produce polyethylene (ethylene homopolymer) at a rate of 10 kg / Hr. Hydrogen having a purity of 99.99 mol% or more purified by contact with molecular sieves was used. The supported metallocene catalyst component [B] was prepared so that the above-mentioned solvent hexane was used as the transfer liquid, and the hydrogen was added to 10 NL / Hr (NL is Normal Liter (volume converted to the standard state)), and the production rate was set to 10 kg / Hr. The addition was carried out at a rate of 1 mmol / L from the middle between the liquid surface and the bottom of the polymerization reactor. The supported metallocene catalyst component [B] is adjusted to 10 ° C. and added from the bottom of the polymerization vessel at a rate of 0.2 g / Hr, and triisobutylaluminum is adjusted to 20 ° C. at a rate of 5 mmol / Hr. Added from the middle of the polymerization vessel. The catalytic activity was 11,000 g-PE / g-supported metallocene catalyst component [B]. The polymerization temperature was kept at 75 ° C. by jacket cooling. The humidity in the polymerization reactor was kept at 0 ppm. Hexane was adjusted to 20 ° C. and fed from the bottom of the polymerization vessel at 60 L / Hr. Ethylene was supplied from the bottom of the polymerization reactor to keep the polymerization pressure at 0.8 MPa. The polymerization slurry was continuously drawn into a flash drum having a pressure of 0.05 MPa so that the level of the polymerization reactor was kept constant, and unreacted ethylene was separated. The polymerization slurry was continuously sent to a centrifuge so that the level of the flash drum was kept constant, and the polymer and other solvents were separated. At that time, the content of the solvent and the like with respect to the polymer was 45%. The separated polyethylene powder was dried at 95 ° C. while blowing nitrogen. In this drying step, the catalyst and the cocatalyst were deactivated by spraying steam on the polymerized powder. A polyethylene powder PE9 of Comparative Example 1 was obtained by removing the obtained polyethylene powder using a sieve having an aperture of 425 μm and removing the polyethylene powder that did not pass through the sieve. Table 1 shows the physical properties of the obtained polyethylene powder PE9.

(Method for producing microporous membrane)
The polyethylene of Comparative Example 1 (viscosity average molecular weight: 280,000) and the polyethylene having a viscosity average molecular weight of 100,000 were mixed in a weight ratio of 70:30, and a total weight of 1500 g was stirred and mixed at 2000 rpm with a 10 L Henschel mixer. Thereafter, 0.5 wt% of 2,6-di-t-butyl-4-methylphenol (dibutylhydroxytoluene) was added to the mixture as an antioxidant with respect to the total amount of polyethylene, and the mixture was stirred and mixed in the same manner. The polyethylene having a viscosity average molecular weight of 100,000 was obtained by increasing the hydrogen supply amount and adjusting the viscosity average molecular weight in the same manner as in Comparative Example 1.

  500 g of this mixture was collected in order from the bottom of the Henschel mixer, and each sample was (A) sample, (B) sample, and (C) sample, a twin-screw type melt-kneader Labo Plast Mill (Toyo Seiki Seisakusho) : Model 20R200) to obtain a uniform molten mixture. Five of this mixture were made for each sample. The conditions at this time were a melt kneading temperature of 190 ° C., a screw rotation speed of 50 revolutions / minute, and a kneading time of 5 minutes.

  Further, in each sample, liquid paraffin (P-350 (trademark) manufactured by Matsumura Oil Co., Ltd.) was injected into a 50 wt% extruder with respect to the total amount of polyethylene, and kneaded at a set temperature of 200 ° C. and a screw rotation speed of 240 rpm. . The melt-kneaded material is passed through a Gnois disk filter type continuous screen exchanger equipped with a screen equivalent to 350 mesh, and then discharged from a T-die and cast with a roll to obtain a gel having a thickness of 1,250 μm. A shaped sheet was formed.

  After preparing five gel sheets of each of these (A) to (C) samples and stretching them at 124 ° C. using a simultaneous biaxial stretching machine at an MD magnification of 7.0 times and a TD magnification of 6.4 times, This stretched film was immersed in methyl ethyl ketone, liquid paraffin was extracted and removed, and then dried. Next, the stretched film was guided to a TD tenter and heat-fixed to obtain 3 samples (5 samples each) of the microporous membrane of Comparative Example 1. The stretching temperature during heat setting was 128 ° C., the magnification was 2.0 times, the temperature during subsequent relaxation was 133 ° C., and the relaxation rate was 0.80. For the obtained microporous membrane, the evaluation of “(8) Variation in thickness of microporous membrane” and “(9) Variation in tensile strength (MPa) and tensile elongation (%) in TD direction of microporous membrane” described above. The results are shown in Table 1.

(Method for producing porous sheet)
The polyethylene described in Comparative Example 1 (viscosity average molecular weight: 280,000) was deposited on a metal flat plate with a thickness of 2.1 mm or more, and passed through a scraping portion provided with a 2.1 mm clearance from the flat plate to obtain polyethylene. I spread the powder. Polyethylene powder uniformly deposited with a thickness of 2.1 mm is put into a heating furnace set at 180 ° C., allowed to stand for 10 minutes, then taken out of the heating furnace and cooled at room temperature to a thickness of 2.0 mm. Was obtained as a porous resin body (a). A polyolefin hot melt adhesive was spray-coated on the porous resin body in a fibrous form at 20 g / m ² using a hot melt applicator set at 160 ° C. As sheet (b), fabric (warp / weft: polyethylene terephthalate monofilament) L-screen165-027 / 420PW subjected to antistatic treatment AS L-screen165-027 / 420PW (manufactured by NBC Meshtec Co., Ltd.) The porous sheet of Comparative Example 1 was obtained by laminating this on the resin porous body (a). The obtained porous sheet was evaluated for “(10) variation in surface roughness (Ra) of porous sheet” described above, and the results are shown in Table 1.

[Example 1]
The supported metallocene catalyst component [B] was pre-warmed to 75 ° C. and then added from the top in the polymerization system of the polymerization reactor at a rate of 0.2 g / Hr, and the water content of the flash drum was 400 ppm. A polyethylene powder PE1 of Example 1 was obtained in the same manner as in Comparative Example 1 except that it was maintained. Table 1 shows the physical properties of the obtained polyethylene powder PE1.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Example 2]
The polymerization temperature was kept at 70 ° C., and the supported metallocene catalyst component [B] was pre-warmed to 75 ° C. and then added from the top in the polymerization system of the polymerization reactor at a rate of 0.2 g / Hr; The tube reagent was added to the inside of the polymerization reactor at 5 μmol / L through a line different from the supported metallocene catalyst component [B], the water content of the flash drum was kept at 300 ppm, and hexane was added. A polyethylene powder PE2 of Example 2 was obtained in the same manner as in Comparative Example 1 except that the temperature was adjusted to 20 ° C. and supplied from the bottom of the polymerization vessel at 40 L / hr. Table 1 shows the physical properties of the obtained polyethylene powder PE2.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Example 3]
The supported metallocene catalyst component [B] was preheated to 75 ° C. and then added from the top in the polymerization system of the polymerization reactor at a rate of 0.2 g / Hr, and the Teve reagent was added to the supported metallocene catalyst component [B]. Was added to the inside of the polymerization reactor at 1.15 μmol / L, and the water content of the flash drum was kept at 400 ppm, and hexane was adjusted to 20 ° C. and 80 L / hr. The polyethylene powder PE3 of Example 3 was obtained in the same manner as in Comparative Example 1 except that the polymer was supplied from the bottom of the polymerization vessel and that propylene was introduced from the gas phase at 0.38 mol% relative to ethylene. Table 1 shows the physical properties of the obtained polyethylene powder PE3.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Example 4]
The supported metallocene catalyst component [B] was preheated to 75 ° C. and then added from the top in the polymerization system of the polymerization reactor at a rate of 0.2 g / Hr, and the Teve reagent was added to the supported metallocene catalyst component [B]. Was added to the inside of the polymerization reactor at 3.59 μmol / L, the water content of the flash drum was kept at 500 ppm, and hexane was adjusted to 20 ° C. and 80 L / hr. The polyethylene powder PE4 of Example 4 was obtained in the same manner as in Comparative Example 1 except that it was supplied from the bottom of the polymerization vessel. Table 1 shows the physical properties of the obtained polyethylene powder PE4.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Example 5]
The polymerization temperature was maintained at 70 ° C., the polymerization pressure was maintained at 0.9 MPa, and the supported metallocene catalyst component [B] was preheated to 78 ° C., and then polymerization in the polymerization reactor was conducted at a rate of 0.2 g / Hr. The addition of the tube reagent from the top of the system, the addition of the Tebbe reagent to the inside of the polymerization reactor at 1.75 μmol / L through a line different from the supported metallocene catalyst component [B], and the moisture content of the flash drum A polyethylene powder PE5 of Example 5 was obtained in the same manner as in Comparative Example 1 except that it was kept at 350 ppm and hexane was adjusted to 20 ° C. and supplied from the bottom of the polymerization vessel at 80 L / hr. It was. Table 1 shows the physical properties of the obtained polyethylene powder PE5.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Example 6]
The polymerization temperature was kept at 80 ° C., the polymerization pressure was kept at 0.9 MPa, the solid metal catalyst component [A] was used instead of the supported metallocene catalyst component [B], and the mixture was preheated to 78 ° C. It was added from the upper part of the polymerization system of the polymerization reactor at a rate of 2 g / Hr, the water content of the flash drum was kept at 500 ppm, and hexane was adjusted to 20 ° C. and polymerized at 80 L / hr. Except having supplied from the bottom part of the container, it carried out similarly to the comparative example 1, and obtained polyethylene powder PE6 of Example 6. Table 1 shows the physical properties of the obtained polyethylene powder PE6.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Example 7]
The pre-warmed metallocene catalyst component [B] was added to the bottom of the polymerizer at a rate of 0.2 g / hr after preheating to 75 ° C, and the bottom of the polymerizer at 60 L / hr by adjusting hexane to 20 ° C. A polyethylene powder PE7 of Example 7 was obtained in the same manner as in Comparative Example 1 except that it was supplied from Table 1 shows the physical properties of the obtained polyethylene powder PE7.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Example 8]
Except that the supported metallocene catalyst component [B] was preheated to 75 ° C. and added from the bottom of the polymerization vessel at a rate of 0.2 g / hr, and that the water content of the flash drum was kept at 200 ppm. In the same manner as in Comparative Example 1, polyethylene powder PE8 of Example 8 was obtained. Table 1 shows the physical properties of the obtained polyethylene powder PE8.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Comparative Example 2]
A polyethylene powder PE10 of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that the water content of the flash drum was kept at 400 ppm. Table 1 shows the physical properties of the obtained polyethylene powder PE10.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Comparative Example 3]
The polymerization temperature was maintained at 48 ° C., and the polymerization reactor was heated at 50 ° C. in advance using the solid catalyst component [A] instead of the supported metallocene catalyst component [B] and then at a rate of 0.2 g / Hr. Comparative Example, except that it was added from the upper part in the polymerization system, the water content of the flash drum was kept at 500 ppm, and 1-butene was introduced from a gas phase of 6.5 mol% with respect to ethylene. 1 was performed to obtain polyethylene powder PE11 of Comparative Example 3. Table 1 shows the physical properties of the obtained polyethylene powder PE11.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

[Comparative Example 4]
The polymerization temperature was maintained at 70 ° C., the supported metallocene catalyst component [B] was added at a temperature of 15 ° C. at a rate of 0.2 g / Hr from the middle between the liquid surface and the bottom of the polymerization reactor, A polyethylene powder PE12 of Comparative Example 4 was obtained in the same manner as Comparative Example 1 except that the water content was kept at 550 ppm. Table 1 shows the physical properties of the obtained polyethylene powder PE12.
In addition, a micro-thick film and a porous sheet were obtained by the same operation as in Comparative Example 1. Evaluation similar to the comparative example 1 was performed using the obtained micro-thick film and the porous sheet. The results are shown in Table 1.

  From the above results, the polyethylene powders of the examples have a high ratio of the flow energy when the air flow rate is 4 mm / s to the flow energy when there is no air flow, so the physical properties do not vary in the raw polyethylene powder until molding. It can be seen that a molded body having stable and uniform physical properties can be produced stably. In the comparative example, the flow energy ratio is low and the jet property is high (the flow energy when the air flow rate is 4 mm / s is relatively low), so the thickness and strength of the micro-thick film vary, It affects the physical properties of the molded body, such as variations in the surface roughness of the porous sheet.

  According to the polyethylene powder of the present invention, a molded product produced from the polyethylene powder can be stably and uniformly produced. The polyethylene powder of the present invention is not limited to the above-mentioned micro-thick film and porous sheet, but also high-performance textiles such as various sports clothing, bulletproof clothing, protective clothing / protective gloves and various safety goods, tag rope / mooring rope, yacht rope Various rope products such as construction ropes, various braided products such as fishing lines and blind cables, net products such as fishing nets and ball nets, reinforcement materials such as chemical filters and battery separators, various nonwoven fabrics, curtain materials such as tents, etc. In addition, the present invention has industrial applicability, such as reinforcing fibers for sports such as helmets and skis, speaker cones, prepregs, and composites such as concrete reinforcement.

Claims (6)

A polyethylene powder which is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 to 15 carbon atoms,
The viscosity average molecular weight is 100,000 or more and 10 million or less,
The density is 920 kg / m ³ or more and 960 kg / m ³ or less,
A polyethylene powder characterized in that the flow energy when the air flow rate is 4 mm / s is 30% or more of the flow energy when there is no air flow.   The polyethylene powder according to claim 1, wherein the average particle size is 50 µm or more and 300 µm or less.   The D90 / D10 ratio is 1.0 or more and 6.0 or less, where D10 and D90 are the particle sizes corresponding to 10% cumulative and 90% cumulative from the smaller diameter side of the cumulative particle size distribution, respectively. The polyethylene powder described.   The polyethylene powder according to any one of claims 1 to 3, wherein the content of particles having a particle diameter of 75 µm or less is 3.0 mass% or more and 30.0 mass% or less. The polyethylene powder according to any one of claims 1 to 4, wherein a particle having a particle diameter of 53 µm or less has a bulk density of 0.25 g / cm ³ or more and 0.40 g / cm ³ or less.   The polyethylene powder according to any one of claims 1 to 5, wherein the flow energy at the time of no ventilation is 100 mJ or more.