JP2023118376A - Method for producing olefinic polymer particle - Google Patents

Abstract

To provide a large-scale fouling prevention method to solve a problem in which, when producing olefinic polymer particulates on a large scale in the presence of aliphatic or alicyclic hydrocarbon media, the produced olefinic polymer particles tend to cause fouling.SOLUTION: Controlling surface roughness of a reactor in a specific range can prevent or suppress occurrence of fouling.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing olefin polymer particles using an olefin polymerization catalyst containing an olefin polymerization catalyst component with a specific particle size.

Ultra-high molecular weight olefin polymers, represented by so-called ultra-high molecular weight ethylene polymers, are excellent in impact resistance, wear resistance, chemical resistance, strength, etc., and have excellent characteristics as engineering plastics. .

However, it is said that ultra-high molecular weight olefin polymers are difficult to perform melt molding, which is a general resin molding method, because of their high molecular weight. For this reason, for example, as a method of molding an ultra-high molecular weight ethylene polymer, an ultra-high molecular weight ethylene-based polymer is melted under specific conditions using a specific solvent, a low-molecular weight olefin polymer (wax), etc., and molded. After that, a method of removing the solvent, etc., a method of compressing the ultra-high molecular weight ethylene polymer particles at a temperature below the melting point and molding them into a desired shape, a solid phase stretching molding method of stretching after the compression step, etc. special molding methods are known.

Patent Document 1 describes a postmetallocene catalyst ([3-t-Bu-2-O-C ₆ H ₃ CH=N(C ₆ F ₅ )] ₂ TiCl ₂ ) described in Patent Document 2. It is disclosed that the strength of a molded article obtained by molding ultra-high molecular weight polyethylene by a solid phase stretching molding method is 3 GPa or more. However, since the polymerization method described in Patent Document 1 does not use a support such as an inorganic solid component for supporting the catalyst component described above, the polymer is deposited on the walls of the polymerization vessel, the stirring blades, etc. during the polymerization reaction. A phenomenon of adhesion, that is, the occurrence of so-called fouling is expected. For this reason, it is assumed that stable industrial production is extremely difficult with the method for producing an ethylene polymer described in Patent Document 1. Furthermore, this method requires a large amount of an expensive organoaluminum oxy compound as a co-catalyst in order to develop catalytic activity, and therefore requires a separate deashing step for removing inorganic components contained in the polymer. , is expected to be very expensive for industrial production.

On the other hand, in the production of ultra-high molecular weight ethylene-based polymers, titanium-based supported catalysts using magnesium compounds as carriers such as those described in Patent Documents 3 and 4, and organic aluminum catalysts described in Patent Document 5, etc. It is known that the use of a supported catalyst in which a transition metal compound is supported on a carrier such as an inorganic solid component made of SiO ₂ treated with an oxy compound can suppress fouling, making industrial production possible. ing.
The present applicant has disclosed a production method for ultra-high molecular weight ethylene polymerization using a catalyst containing a special carrier (Patent Document 6).

International publication 2009/007045 pamphlet JP-A-11-315109 JP-A-3-130116 JP-A-7-156173 Japanese Patent Application Laid-Open No. 2000-297114 Japanese Patent No. 5689473

According to the studies of the present inventors, olefin polymerization is carried out on a relatively large scale such as 30 L or more in the presence of a liquid with extremely low polarity such as an aliphatic hydrocarbon or an alicyclic hydrocarbon. It has been found that the process for producing ultra-high molecular weight olefin polymers tends to cause fouling. It is obvious that the occurrence of such fouling can be a factor that makes long-term stable production of ultra-high molecular weight olefin polymers impossible.

As a result of studies to solve the above problems, the present inventors found that slurry polymerization using an aliphatic hydrocarbon or an alicyclic hydrocarbon as a medium can be performed by using a production apparatus having a surface roughness within a specific range. The inventors have found that fouling is unlikely to occur even if there is, and completed the present invention. That is, the present invention can be specified by the following requirements.

[1] A method for producing olefin polymer particles that satisfies the following requirement (E),
In a reactor that satisfies the following requirements (α),
a liquid containing 95% by volume or more of a hydrocarbon selected from aliphatic hydrocarbons and alicyclic hydrocarbons;
A method for producing olefin polymer particles, comprising a step of polymerizing an olefin in the presence of a particulate olefin polymerization catalyst component containing a transition metal element and having an average particle size of 1 nm or more and 300 nm or less:
(E) the intrinsic viscosity [η] measured at 135°C in a decalin solvent is 5 to 50 dl/g;
(α) The internal volume is 30 liters or more, and the surface roughness Ra of the reactor surface determined by a method according to the JIS B 0601 standard is 0.15 μm or less.

[2] the reactor has a reaction vessel, a baffle, and a stirring blade;
the reactor surface comprises a reaction vessel inner wall surface, a baffle surface, and a stirring blade surface;
A method for producing olefin polymer particles according to item [1].

[3] The method for producing olefin polymer particles according to item [2], wherein the surface of the stirring blade has an Ra of 0.05 µm or less.

[4] The catalyst component for olefin polymerization is
(A) fine particles having an average particle size of 1 nm or more and 300 nm or less, which are obtained through at least steps 1 and 2 below;
(B) The method for producing olefin polymer particles according to item [1], which contains a transition metal compound having a structure represented by the following general formula (I).
(Step 1) A step of contacting a metal halide and an alcohol in a hydrocarbon solvent (Step 2) Contacting the component obtained in (Step 1) with an organoaluminum compound and/or an organoaluminumoxy compound process

（式（Ｉ）中、Ｍは周期表第４、５族の遷移金属原子を示し、
ｍは１～４の整数を示し、
Ｒ¹～Ｒ⁵は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよく、
Ｒ⁶は、水素原子、１級または２級炭素のみからなる炭素数１～４の炭化水素基、炭素数４以上の脂肪族炭化水素基、アリール基置換アルキル基、単環性または二環性の脂環族炭化水素基、芳香族炭化水素基、およびハロゲン原子から選ばれ、
ｎは、Ｍの価数を満たす数であり、
Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合は、Ｘで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）

(In formula (I), M represents a transition metal atom of groups 4 and 5 of the periodic table,
m represents an integer of 1 to 4,
R ¹ to R ⁵ may be the same or different, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus a containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked together to form a ring;
R ⁶ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting only of primary or secondary carbon atoms, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, monocyclic or bicyclic selected from alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and halogen atoms of
n is a number that satisfies the valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different, and the multiple groups represented by X may be bonded to each other. may form a ring. )

[5] Item [4], wherein the alcohol is a combination of two alcohols selected from alcohols having 1 to 25 carbon atoms, and the difference in the number of carbon atoms between the two alcohols is 4 or more. A method for producing the described olefin polymer particles.

[6] The method for producing olefin polymer particles according to item [5], wherein the two alcohols are a combination of an alcohol having 2 to 12 carbon atoms and an alcohol having 13 to 25 carbon atoms.

[7] The method for producing olefin polymer particles according to item [5], wherein the two alcohols are a combination of two alcohols selected from alcohols having 2 to 12 carbon atoms.

[8] In the general formula (I), M is titanium, zirconium or hafnium,
m is 2,
R ¹ is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. indicating the group to be selected,
R ² to R ⁵ , which may be the same or different, each represent a hydrogen atom, a halogen atom, or a hydrocarbon group;
R ⁶ is selected from an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group;
The method for producing olefin polymer particles according to item [5], wherein X represents a hydrogen atom, a halogen atom, or a hydrocarbon group.

[9] The method for producing olefin polymer particles according to item [1], wherein the olefin contains ethylene.

Since the method for producing olefin polymer particles according to the present invention uses a reactor having a specific shape, it is possible to minimize the fouling of the ethylene polymer particles on the walls of the polymerization vessel, stirring blades, and the like. .

It is an example of a reactor used in the method for producing olefin polymer particles of the present invention.

Hereinafter, the method for producing olefin polymer particles according to the present invention will be described in more detail. In the present invention, the olefin polymer particles refer to homopolymer particles such as ethylene homopolymer particles as well as copolymer particles such as copolymer particles of ethylene and α-olefin.

(Reactor)
The reactor used in the present invention has a characteristic surface. That is, the surface roughness Ra of the surface of the reactor is 0.15 μm or less. It is more preferably 0.13 μm or less, still more preferably 0.11 μm or less, and particularly preferably 0.10 μm or less. If the surface roughness is too high, the fouling may easily occur. In particular, since the olefin polymer of the present invention tends to have a high molecular weight, once fouling occurs, it is firmly fixed to the inner surface and tends to be difficult to eliminate. On the other hand, the preferred lower limit is naturally zero, but is more preferably 0.005 μm, more preferably 0.010 μm, still more preferably 0.015 μm. If the surface roughness is too small, the particle flowability may be lowered, depending on the particle shape of the olefin polymer.

The surface roughness Ra is a value measured according to the JIS B 0601 standard. A known method can be employed without limitation for the measurement method.

In the reaction apparatus of the present invention, the so-called reaction vessel portion can be a known reaction apparatus such as a vessel shape, a tubular shape, etc., without limitation. It is preferable to Also, a device such as a heat exchanger that removes and reuses reaction heat may be combined. A vessel-type reactor is most preferable as a reactor using baffles, stirring blades, etc. as described above.

In the case of a reactor equipped with the above-mentioned baffles, stirring blades, etc., not only the inner wall surface of the reaction vessel, but also the surfaces of the baffles and stirring blades, which may come into contact with the reaction medium described later, are the surfaces in the above range. It is preferably within the roughness range. In particular, the stirring blades, although depending on the stirring power, come into intense dynamic contact with the olefin polymer particles to be produced, and may be easily electrostatically charged. Therefore, a low surface roughness is preferred. The surface roughness Ra is preferably 0.10 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less.

Next, it is the baffle that preferably has the lowest surface roughness. If the heat exchanger is installed in the reaction liquid phase, the surface of the heat exchanger should also be within the above surface roughness range.

It is self-evident that the surfaces of the reaction apparatus of the present invention preferably all preferably have the surface roughness within the range of the surface roughness. (A prime example is a slurry containing a reaction medium and refined olefin particles, etc.) The portion considered to be unlikely to come into contact may not necessarily be within the range of surface roughness described above.

The reason why the reaction apparatus of the present invention needs to have the surface roughness within the above range is not clarified at present, but the present inventors believe as follows.
Olefin polymer particles have low polarity and tend to be easily charged. It is also known that fouling is likely to occur, but there are known methods of improving it by controlling the flow linear velocity in the reaction system. In the case of the present invention, since the particle size of the olefin polymerization catalyst particles used is small, olein polymer particles with a large specific surface area tend to be produced at least in the initial stage of polymerization, and are likely to tend to be more easily charged. Furthermore, aliphatic hydrocarbons and alicyclic hydrocarbons, which are fluid dispersion media, have a lower polarity than aromatic hydrocarbon liquids, so static electricity is less likely to be alleviated, and the reaction scale increases. It is likely that the number of particles relative to the surface area of the reactor increases, and the total charge amount of the particles in the reactor may exceed the static elimination capability of the reactor. When the particle diameter of the olefin polymer particles is small, the electrostatic adhesion force to the reactor surface increases against the peeling force from the reactor surface due to stirring and flow, and the particles tend to adhere to the reactor surface more easily. is expected. If the surface roughness of the reactor surface is high, the contact area between the olefin polymer particles in the initial stage of polymerization, which have a particularly small particle size, and the surface of the reactor increases, and it is thought that the electrostatic adhesion to the wall surface of the reactor tends to become stronger. be done. On the other hand, it can be considered that by reducing the surface roughness of the reaction device, it is possible to reduce the adverse effects such as the occurrence of fouling due to the charging or the like.

Iron-based metallic materials are generally suitable as materials for forming the reactor of the present invention. As is well known, iron has the property of being easily oxidized, so it can be used as an alloy such as so-called stainless steel containing other metal components and carbon. Alternatively, the surface thereof may be coated with a known material such as glass, titanium alloy, chlorofluorocarbon resin, or the like. As a coating method, known methods such as coating, plating, and vapor deposition can be used without limitation.

The surface roughness Ra of the reactor can be controlled by a known polishing method. More specifically, various methods such as mechanical polishing, chemical polishing, and electrolytic polishing can be employed. These polishing methods can be appropriately selected according to the shape of the apparatus, the material of the surface to be polished, and the thickness of the coating layer in the case of the surface layer being coated.

Aliphatic hydrocarbons, alicyclic hydrocarbons The liquid containing 95% by volume or more of hydrocarbons selected from aliphatic hydrocarbons and alicyclic hydrocarbons used in the present invention may be in a liquid state at the operating temperature and pressure. is not particularly limited. Aliphatic hydrocarbons and alicyclic hydrocarbons tend to have higher liquid viscosities as their molecular weights increase, so aliphatic hydrocarbons and alicyclic hydrocarbons having 3 to 20 carbon atoms are preferred. Preferably. The lower limit of the number of carbon atoms is more preferably 4, more preferably 5. On the other hand, the upper limit is more preferably 15, more preferably 13. Specific compounds include linear and branched aliphatic hydrocarbons such as propane, isobutane, pentane, isopentane, isohexane, heptane, octane, isooctane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane; Preferred examples include alicyclic hydrocarbons such as Among these, hexane, heptane, octane, decane, and cyclohexane can be mentioned as preferred examples in consideration of price, ease of management, recovery, and ease of purification. These compounds can also use 2 or more types together.

These aliphatic hydrocarbons and alicyclic hydrocarbons are safer, easier to recover and refine, and emit toxic gases when incinerated than the aromatic hydrocarbons and heteroatom-containing hydrocarbons described later. There are many advantages such as being difficult to generate.

The aliphatic hydrocarbon and alicyclic hydrocarbon are used as a so-called dispersion medium in the method for producing an olefin polymer of the present invention. Such a dispersion medium may contain other components as long as the content of aliphatic hydrocarbons and alicyclic hydrocarbons is not less than 95% by volume. Other components include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. These components can use 2 or more types together.

On the other hand, it is preferable to avoid components (for example, alcohols, carboxylic acids, amines, etc.) that cause deactivation or deterioration of the olefin polymerization catalyst, which will be described later.

The content of the aliphatic hydrocarbons and alicyclic hydrocarbons is preferably 96% by volume or more, more preferably 97% by volume or more, and still more preferably 98% by volume or more. A preferred upper limit is, of course, 100% by volume.

The reactor of the present invention has an internal volume of 30 L or more. A preferred lower limit is 70L, more preferably 90L, and even more preferably 100L. As described above, in the case of such a large-scale reactor, especially when producing polymer particles with a high molecular weight and a small diameter as described later, fouling due to electrostatic charging is likely to occur. The effect of controlling the surface roughness Ra of the present invention tends to be high.

<Catalyst component for olefin polymerization>
In the method for producing olefin polymer particles of the present invention, a particulate olefin polymerization catalyst component containing a transition metal element and having an average particle size of 1 nm or more and 300 nm or less is used. A preferable lower limit of the average particle diameter is 2 nm, more preferably 3 nm, still more preferably 4 nm, and particularly preferably 5 nm. On the other hand, the upper limit is preferably 250 nm, more preferably 200 nm, still more preferably 150 nm, particularly preferably 100 nm or less, particularly preferably 50 nm or less.

As such an olefin polymerization catalyst component, known catalyst components can be used without limitation, and the following aspects are preferred.

Preferred examples of the olefin polymerization catalyst component used in the method for producing ethylene-based polymer particles according to the present invention satisfy the following requirements (A) and (B).
(A) fine particles having an average particle size of 1 nm or more and 300 nm or less obtained through a specific process; (B) a transition metal compound represented by general formula (I) or general formula (II); A transition metal compound represented by the general formula (I) is preferred.

The above components (A) and (B) and other components that can be used as necessary are described in detail below.

[(A) fine particles having an average particle diameter of 1 nm or more and 300 nm or less]
Fine particles having an average particle size of 1 nm or more and 300 nm or less used in the present invention are obtained through at least the following two steps.

(Step 1) A step of contacting a metal halide and an alcohol in a hydrocarbon solvent (Step 2) Contacting the component obtained in (Step 1) with an organoaluminum compound and/or an organoaluminumoxy compound Steps Hereinafter, the content of each step and the compounds used in each step will be described.

○ Process 1
Step 1 is a step of contacting a metal halide and an alcohol in a hydrocarbon solvent to form an alcohol complex of the metal halide to be in a liquid state.

Process 1 is usually carried out under heating under normal pressure or under heating under pressure, although there are no particular limitations as long as the reaction conditions are such that the metal halide is in a liquid state. When heating under normal pressure, the temperature up to the boiling point of the hydrocarbon solvent used can be arbitrarily selected, and when heating under pressure, the boiling point of the hydrocarbon solvent or alcohol used under pressure can be selected arbitrarily.

When the metal halide and the alcohol are brought into contact with each other in the hydrocarbon solvent in step 1, ordinary stirring and mixing can be carried out. As a device used for stirring, a commonly used known stirrer and the like can be mentioned.

• Metal Halide Preferable examples of the metal halide used in the present invention include ion-bonding compounds having a CdCl ₂ -type or CdI ₂ -type layered crystal structure. Specific examples of compounds having a CdCl ₂ -type crystal structure include CdCl ₂ , MnCl ₂ , FeCl ₂ , CoCl _{2 , NiI 2} , NiCl ₂ , MgCl _{2 ,} ZnBr ₂ and CrCl ₃ . Specific examples of compounds having a _CdI2 type crystal structure include _CdBr2 , _FeBr2 , CoBr2, _NiBr2 , CdI2, _MgI2 , _{CaI2 , ZnI2} , _{PbI2 , MnI2} , _FeI2 , _CoI2 , Mg(OH) ₂ , Ca(OH) ₂ , Cd(OH) ₂ , Mn(OH) ₂ , Fe(OH) ₂ , Co(OH) ₂ , Ni(OH) ₂ , _ZrS4 , _SnS4 , TiS ₄ , PtS ₄ and the like.

Among these, _CdBr2 , _FeBr2 , CoBr2, _NiBr2 , _CdI2 , _MgI2 , CaI2, _ZnI2 , _{PbI2 , MnI2} , _{FeI2 , CoI2} , _CdCl2 , _MnCl2 and _FeCl2 are preferred. , CoCl ₂ , NiI ₂ , NiCl ₂ , MgCl ₂ and ZnBr ₂ , more preferably MnCl ₂ , FeCl ₂ , CoCl ₂ , NiCl ₂ and MgCl ₂ , most preferably MgCl ₂ .

The ion-binding compound as described above may be finally contained in the catalyst, and the ion-binding compound itself does not necessarily have to be used. Thus, during the preparation of the catalyst, compounds capable of forming an ion-binding compound may be used to form the ion-binding compound that is ultimately present in the catalyst. That is, using a compound that does not belong to either the CdCl ₂ type or the CdI ₂ type crystal structure, in the middle of the preparation of the catalyst, the compound and the halogen-containing compound or the hydroxyl group-containing compound are subjected to a contact reaction to finally obtain It may also be an ion-binding compound in the catalyst used.

For example, when MgCl ₂ or MgI ₂ is formed and finally present in the catalyst component, as compounds capable of forming these, a magnesium compound having reducing ability and a magnesium compound having no reducing ability are used as starting materials. can be used. Examples of magnesium compounds having reducing ability include organomagnesium compounds represented by the following formula.

_{XnMgR2 -n}
(Wherein, n is 0≦n<2, and R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 21 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. , two R may be the same or different when n is 0. X is halogen.)

Specific examples of organomagnesium compounds having such reducing ability include dialkyl magnesium such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, octylbutylmagnesium, and ethylbutylmagnesium. Magnesium compounds; alkylmagnesium halides such as ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride and amylmagnesium chloride; alkylmagnesium alkoxides such as butylethoxymagnesium, ethylbutoxymagnesium and octylbutoxymagnesium; Examples include alkylmagnesium hydride such as propylmagnesium hydride and butylmagnesium hydride.

Specific examples of organomagnesium compounds having no reducing ability include alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; phenoxymagnesium chloride, methylphenoxymagnesium chloride. alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; allyloxymagnesium such as diphenoxymagnesium and methylphenoxymagnesium; magnesium laurate , and magnesium carboxylates such as magnesium stearate.

In addition, magnesium metal, magnesium hydride, etc. can also be used. These magnesium compounds having no reducing ability may be compounds derived from the magnesium compounds having reducing ability described above, or compounds derived during preparation of the catalyst. In order to derive a magnesium compound having no reducibility from a magnesium compound having reducibility, for example, the magnesium compound having reducibility is combined with a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, It may be brought into contact with a halogen-containing compound, or a compound having an OH group or an active carbon-oxygen bond.

The above-mentioned magnesium compounds having reducing ability and magnesium compounds not having reducing ability form complex compounds and double compounds with other organometallic compounds such as aluminum, zinc, boron, beryllium, sodium, and potassium. may be the same or may be a mixture. Furthermore, the magnesium compound may be used singly or in combination of two or more of the above compounds, and may be used in a liquid state or in a solid state. When the magnesium compound having reducibility or the magnesium compound having no reducibility is solid, it is preferable to liquefy it using an alcohol, which will be described later.

-Alcohol Examples of alcohols used in the present invention include alcohols having 1 to 25 carbon atoms. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, 2-butyloctanol, 2-hexyldecanol, 2-hexyldodecanol, 2- Alcohols with 1 to 25 carbon atoms such as octyldecanol, 2-octyldodecanol, isohexadecanol, isoeicosanol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isobutyl alcohol and isopropylbenzyl alcohol halogen-containing alcohols having 1 to 25 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; and phenols having 6 to 25 carbon atoms which may be used.

These alcohols can be used singly or in combination of two or more. When used alone, among the above alcohols, alcohols having 1 to 25 carbon atoms are preferred, alcohols having 2 to 12 carbon atoms are more preferred, and ethanol, propanol and butanol are more preferred. , pentanol, hexanol, 2-ethylhexanol, heptanol and octanol.

When the two alcohols are used, the alcohol complexes of the metal halides containing the alcohols are classified by paying attention to the difference in reactivity between the below-described organoaluminum compound and/or organoaluminum oxy compound. It is preferable to use The use of two alcohols may be preferable from the viewpoint of production of fine particles with a narrow particle size distribution. One of the reasons is as follows.

An alcohol complex of a metal halide obtained from an alcohol highly reactive with an organoaluminum compound and/or an organoaluminumoxy compound reacts with the metal by a catalytic reaction with the organoaluminum compound and/or the organoaluminumoxy compound. The alcohol is abstracted from the alcohol complex of the halide, and the core portion of the fine particles of the metal halide can be rapidly produced.

On the other hand, an alcohol complex of a metal halide obtained from an alcohol having relatively low reactivity with an organoaluminum compound and/or an organoaluminumoxy compound is obtained by It is considered that the alcohol is withdrawn from the alcohol complex of the metal halide, and the metal halide is deposited outside the nuclei of the fine particles.

Therefore, by mixing and using the two types of alcohols, it is possible to reduce the contamination of by-products of extremely small fine particles, for example, particles of a size like the nucleus, and the fine particles of the component (A) of the present invention can be reduced. , it can be expected that the particle size distribution will be narrower even though the diameter is small.

Since the ethylene-based polymer particles described later are extremely susceptible to the particle size of the fine particles, if the fine particles, which are the component (A) of the present invention, are used as a component of an olefin polymerization catalyst, an amorphous ethylene-based polymer can be obtained. Particles are hard to form, and even nano-sized polymers are thought to be less likely to foul into reaction tanks and the like.

The difference in reactivity of the above-mentioned alcohol with the organoaluminum compound and/or the organoaluminum oxy compound is attributed to the difference in the molecular structure of the alcohol as shown in (i) to (iv) below. can be assumed.

(i) difference between linear and branched (ii) difference between aliphatic, alicyclic and aromatic (iii) difference in number of carbon atoms (iv) combination of (i) to (iii) above

Among these, for example, (iii) the difference in the number of carbon atoms, specifically, when the number of carbon atoms in R of the alcohol represented by R-OH is used as an index, alcohols with a relatively small number of carbon atoms , alcohols with a relatively large number of carbon atoms. At this time, alcohols with a relatively small number of carbon atoms generally have high reactivity with organoaluminum compounds and/or organoaluminumoxy compounds, while alcohols with a relatively large number of carbon atoms are organic It corresponds to those having low reactivity with aluminum compounds and/or organoaluminum oxy compounds.

In addition, according to the classification by the number of carbon atoms, alcohols corresponding to alcohols with a relatively small number of carbon atoms in one embodiment may also be alcohols with a relatively large number of carbon atoms depending on the type of the other alcohol. It is sometimes accredited. For example, using 2-ethylhexanol as the other alcohol, 2-octyldodecanol corresponds to a relatively low number of carbon atoms, and isobutyl alcohol as the other alcohol. , corresponds to alcohols with a relatively high number of carbon atoms. Since this method focuses on reactivity, there is no problem even if one type of alcohol falls into any category.

Here, when the two types of alcohols are used in combination, the difference in the number of carbon atoms between the two types of alcohols is preferably 4 or more in consideration of the manifestation of the effects from the viewpoint of reactivity.

Specific alcohol combinations include a combination of an alcohol having 2 to 12 carbon atoms and an alcohol having 13 to 25 carbon atoms, and a combination of two alcohols selected from alcohols having 2 to 12 carbon atoms. combinations, etc.

Here, the alcohol having 2 to 12 carbon atoms preferably has 2 to 10 carbon atoms, and is selected from ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, and octanol. is particularly preferred.

Further, the alcohol having 13 to 25 carbon atoms preferably has 15 to 25 carbon atoms, more preferably 16 to 25 carbon atoms, 2-hexyldecanol, 2-hexyldodecanol, 2-octyl Alcohols selected from decanol, 2-octyldodecanol, isohexadecanol, isoeicosanol, octadecyl alcohol and oleyl alcohol are particularly preferred.

When an alcohol having a relatively large number of carbon atoms, such as an alcohol having 13 to 25 carbon atoms, is present in the olefin polymerization catalyst, it can be expected that the ethylene polymerization reaction proceeds mildly. As a result, it can be expected that uneven distribution of heat generation during polymerization is suppressed. Suppression of uneven distribution of heat generated by polymerization leads to suppression of entanglement of the generated polymer chains, and as a result, it is thought that this leads to improvement in the performance of stretched molded articles such as solid phase stretched molded articles.

The amount of alcohol to be used for liquefying the metal halide is not particularly limited as long as it is an amount that dissolves the metal halide. It is 0.5 to 30 mol, more preferably 1 to 20 mol, still more preferably 2 to 15 mol. In addition, when two kinds of alcohols are mixed and used, the ratio of the alcohol having a relatively small number of carbon atoms and the alcohol having a relatively large number of carbon atoms should be an amount that dissolves the metal halide. Although there is no limitation, the lower limit of the proportion of alcohol having a relatively large number of carbon atoms is 10 mol%, preferably 20 mol%, more preferably 30 mol%, and the upper limit is 95 mol%, preferably 90 mol%, more preferably 85 mol %.

- Hydrocarbon solvent The hydrocarbon solvent used in the present invention is not particularly limited, but specific examples include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methyl Alicyclic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; and mixtures thereof.

Of these, decane, dodecane, toluene, xylene, and chlorobenzene are preferred from the viewpoint of solubility and reaction temperature, and have advantages such as high safety, easy recovery and purification, and less generation of toxic gas when incinerated. , decane and dodecane are particularly preferably used.

The amount of the hydrocarbon solvent to be used for liquefying the metal halide is not particularly limited as long as the amount dissolves the metal halide, and is 0.1 to 100 mol per 1 mol of the metal halide. more preferably 0.2 to 50 mol, still more preferably 0.3 to 40 mol, and particularly preferably 0.5 to 30 mol.

○ Process 2
In step 2, the liquid metal halide alcohol complex obtained in step 1 is brought into contact with an organoaluminum compound and/or an organoaluminum oxy compound to precipitate the dissolved metal halide to produce fine particles. It is a process.

Step 2 is usually carried out under reaction conditions in which the dissolved metal halide precipitates, preferably at a temperature of -50 to 200°C, more preferably -20 to 150°C, still more preferably 0 to 120°C. .

Further, in proceeding with step 2, the solution in the reactor is stirred and mixed when adding the organoaluminum compound and/or the organoaluminumoxy compound to the solution. Stirring and mixing may be carried out under normal stirring conditions, but high-speed stirring and mixing may be required.

Equipment used for high-speed stirring is not particularly limited as long as it is commercially available as an emulsifier or disperser. Examples include Ultra Turrax (made by IKA), Polytron (made by Kinematica), TK Auto Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), batch-type emulsifiers such as National Cooking Mixer (manufactured by Matsushita Electric Industrial Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Pipeline Homo Mixer, TK Homomic Line Flow (manufactured by Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (manufactured by Nippon Seiki Co., Ltd.), Thrasher, Trigonal Wet Mill (manufactured by Mitsui Miike Kakoki), Cavitron (manufactured by Eurotech), Fine Flow Mill (manufactured by Taiheiyo Kiko Co., Ltd.) Continuous emulsifiers such as Clearmix (manufactured by M-Technic Co., Ltd.), Batch or continuous emulsifiers such as Filmix (manufactured by Tokushu Kika Kogyo Co., Ltd.), Microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), Nano Maker, Nanomizer ( Nanomizer), high-pressure emulsifiers such as APV Gorin (manufactured by Gorin), membrane emulsifiers such as membrane emulsifiers (manufactured by Reika Kogyo), vibration emulsifiers such as Vibromixer (manufactured by Reika Kogyo), An ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson) can be used. Moreover, when stirring and mixing at high speed, the stirring speed is preferably 5000 rpm or more.

• Organoaluminum compound Examples of the organoaluminum compound that can be used in the present invention include compounds represented by the following formulas (Al-1), (Al-2) and (Al-3).

R ^a _n AlX _3-n (Al-1)
(In formula (Al-1), R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3.)

A hydrocarbon group having 1 to 12 carbon atoms is, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, Examples include a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a tolyl group.

Specific examples of such organoaluminum compounds include the following compounds. trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesqui bromide; , isopropylaluminum dichloride and ethylaluminum dibromide; and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

Moreover, an organoaluminum compound represented by the following formula can also be used.
R ^a _n AlY _3-n (Al-2)
(In formula (Al-2), R ^a is the same as in formula (Al-1) above, Y is —OR ^b group, —OSiR ^c ₃ group, —OAlR ^d ₂ group, —NR ^e ₂ group, — SiR ^f ₃ group or -N(R ^g )AlR ^h ₂ group, n is 1 to 2, R ^b , R ^c , R ^d and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc., R ^e is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R ^f and R ^g are methyl group, ethyl group, etc.)

As the organoaluminum compound represented by formula (Al-2), the following compounds are specifically used.

(i) compounds represented by R ^a _n Al(OR ^b ) _3-n , such as alkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide and diethylaluminum-2-ethylhexoxide; .

(ii) compounds represented by R ^a _n Al(OSiR ^c ₃ ) _3-n , such as Et ₂ Al(OSiMe ₃ ), (iso-Bu) ₂ Al(OSiMe ₃ ), (iso-Bu) ₂ Al( _OSiEt3 ) and the like.

(iii) compounds represented by R ^a _n Al(OAlR ^d ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ and (iso-Bu) ₂ AlOAl(iso-Bu) ₂ ;

(iv) compounds represented by ^RanAl ( ^NRe2 _{) 3-n} , such as _Me2AlNEt2 , _Et2AlNHMe , _{Me2AlNHEt , Et2AlN} ( _Me3Si ) ₂ , (iso-Bu) _{; 2AlN} ( _Me3Si ) ₂ and the like.

(v) Compounds represented by R ^a _n Al(SiR ^f ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe ₃ .

(vi) compounds represented by R ^a _n Al[N(R ^g )-AlR ^h ₂ ] _3-n , such as Et ₂ AlN(Me)-AlEt ₂ , (iso-Bu) ₂ AlN(Et)Al( iso-Bu) ₂ and the like.

As the organoaluminum compound, a compound represented by the following formula (Al-3), which is a complex alkylation product of a group I metal and aluminum, can be used.

M ¹ AlR ^j ₄ (Al-3)
(In formula (Al-3), M ¹ is Li, Na or K, and R ^j is a hydrocarbon group having 1 to 15 carbon atoms.)
Specifically, LiAl(C ₂ H ₅ ) ₄ , LiAl(C ₇ H ₁₅ ) ₄ and the like are mentioned.

Among the organoaluminum compounds mentioned above, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and diisobutylaluminum hydride are particularly preferred.

The amount of the organoaluminum compound used in precipitating the dissolved metal halide to produce the fine particles is preferably 0.1 to 50 mol, more preferably 0.2 to 50 mol, per 1 mol of the metal halide. It is 30 mol, more preferably 0.5 to 20 mol, particularly preferably 1.0 to 10 mol.

Organoaluminumoxy compound The organoaluminumoxy compound that can be used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687. may be Specific examples of organoaluminumoxy compounds include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound.
(2) A method in which water, ice or steam is directly acted on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic components. Alternatively, after removing the solvent or unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified above as the organoaluminum compound.

Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

The organoaluminum compounds as described above may be used singly or in combination of two or more.

Solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; , cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorine and hydrocarbon solvents such as sulfides and bromides. Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminumoxy compound used in the present invention, the Al component dissolved in benzene at 60° C. is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms. That is, it is preferably insoluble or sparingly soluble in benzene.

Examples of organoaluminumoxy compounds that can be used in the present invention include organoaluminumoxy compounds containing boron represented by the following general formula (III).

（一般式（ＩＩＩ）中、Ｒ²¹は炭素原子数が１～１０の炭化水素基を示し、４つのＲ²²は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数が１～１０の炭化水素基を示す。）

(In general formula (III), R ²¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ²² may be the same or different, and may contain a hydrogen atom, a halogen atom, or a 1 to 10 hydrocarbon groups are shown.)

The organoaluminumoxy compound containing boron represented by the general formula (III) is obtained by dissolving an alkylboronic acid represented by the following general formula (IV) and an organoaluminum compound in an inert gas atmosphere in an inert solvent. It can be produced by reacting at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

R ²² —B(OH) ₂ (IV)
(In general formula (IV), R ²² represents the same group as R ²² in general formula (III).)

Specific examples of alkylboronic acids represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid and n-hexylboronic acid. acids, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferred. These are used individually by 1 type or in combination of 2 or more types.

Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified above as the organoaluminum compound. As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used individually by 1 type or in combination of 2 or more types.

The above organoaluminum oxy compounds can be used singly or in combination of two or more.

The amount of the organoaluminumoxy compound used in precipitating the dissolved metal halide to produce fine particles is preferably 0.1 to 50 mol, more preferably 0.2 mol, per 1 mol of the metal halide. 30 mol, more preferably 0.5 to 20 mol, particularly preferably 1.0 to 10 mol.

The amount of the organoaluminumoxy compound used when depositing the metal halide is very small compared to the amount of the organoaluminumoxy compound used as a co-catalyst described in Patent Document 1.

○ Fine particles The fine particles obtained through at least the above steps 1 and 2 have an average particle size of 1 nm or more and 300 nm or less, preferably 1 nm or more and 250 nm or less, more preferably 1 nm or more and 200 nm, as measured by a dynamic light scattering method. It is more preferably 1 nm or more and 150 nm or less, still more preferably 1 nm or more and 100 nm or less, and particularly preferably 1 nm or more and 50 nm or less.

The reason why it is preferable to use fine particles having such a size is that it is easy to obtain an olefin polymer having a small particle size. It is considered that coalesced particles are easily obtained. By using the fine particles as a catalyst carrier, the specific surface area of the carrier is increased, so that the distance between active sites during ethylene polymerization generated when the (B) transition metal compound described later is supported becomes longer. When the distance between the active sites is increased in this way, heat generation around the active sites is reduced, the crystallization temperature of the ethylene polymer produced is lowered, and the lamella thickness is reduced. It is also possible to reduce the entanglement of the polymer molecular chains of the produced ethylene polymer. From these characteristics, when the fine particles of the present invention are used as a catalyst carrier, the obtained ethylene polymer particles have a high stretchability because the crystal part is easily crushed during stretching, resulting in a high degree of orientation. It is expected that the strength will increase and high strength will be developed.

In addition, by using fine particles having such a size as a catalyst carrier, the specific surface area of the carrier increases as described above. It becomes possible to increase the supported amount of the transition metal compound, and the olefin polymerization activity per catalyst weight can be increased. Furthermore, the diffusion of the monomer during polymerization is improved, and (C) a compound that reacts with a transition metal compound to form an ion pair and (D) an organoaluminum oxy compound, which will be described later, are used as components of an olefin polymerization catalyst. In some cases, the probability of contact between these compounds and the (B) transition metal compound supported on the carrier is increased, so that active sites are efficiently formed. Based on these characteristics, it is expected that the use of the fine particles of the present invention as a catalyst carrier will also improve the catalytic activity.

[(B) transition metal compound]
The transition metal compound used in the present invention is limited to known metallocene compounds and specific organic transition metal complex compounds such as so-called post-metallocene, as long as the intrinsic viscosity and crystallinity of the ethylene polymer particles described later can be achieved. can be used without

As the (B) transition metal compound contained in the olefin polymerization catalyst in the present invention, an organic transition metal complex having a so-called phenoxyimine ligand, which is described in Patent Document 2, is particularly preferable. Specifically, an organic transition metal complex having a structural formula such as the following general formula (I) is mentioned as a preferred embodiment.

In the above general formula (I), M represents a transition metal atom of Groups 4 and 5 of the periodic table, preferably a transition metal atom of Group 4. Specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc. are preferred, titanium, zirconium and hafnium are more preferred, and titanium or zirconium is particularly preferred.

The dotted line connecting N and M in general formula (I) generally indicates that N is coordinated to M, but in the present invention it may or may not be coordinated. .

In general formula (I) above, m represents an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 2.

In general formula (I) above, R ¹ to R ⁵ may be the same or different, and are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of which may be linked together to form a ring.

The halogen atoms include fluorine, chlorine, bromine and iodine.

The hydrocarbon group may be a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms. A hydrogen group is mentioned. Specifically, the number of carbon atoms in a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. 1 to 30, preferably 1 to 20, more preferably 1 to 10 linear or branched alkyl groups;
linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl groups, allyl groups, and isopropenyl groups;
linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms such as ethynyl group and propargyl group;
cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and adamantyl group;
Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group and fluorenyl group;
aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group;
alkyl-substituted aryl groups such as a tolyl group, an iso-propylphenyl group, a t-butylphenyl group, a dimethylphenyl group and a di-t-butylphenyl group;
etc.

Hydrogen atoms in the above hydrocarbon groups may be substituted with halogens, and such hydrocarbon groups with hydrogen atoms substituted with halogens include, for example, a trifluoromethyl group, a pentafluorophenyl group, a chlorophenyl group, and the like. Examples include halogenated hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms.

In addition, the above hydrocarbon group may be substituted with other hydrocarbon groups, and examples of hydrocarbon groups substituted with such hydrocarbon groups include aryl group-substituted alkyl groups such as benzyl group and cumyl group. etc.

Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic anhydride groups;
Ammonium salts of amino group, imino group, amide group, imido group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group and amino group Nitrogen-containing groups such as
Boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group;
Mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group, isocyanate group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group , a sulfonyl group, a sulfinyl group, a sulfur-containing group such as a sulfenyl group;
phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups;
It may have silicon-containing groups; germanium-containing groups; or tin-containing groups.

The heterocyclic compound residue includes residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocycles thereof. Examples include groups in which the residue of the formula compound is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, etc. More specifically, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, and a diethylsilyl group. group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl(pentafluorophenyl)silyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and the like are preferable, and particularly a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group. A dimethylphenylsilyl group is preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

Examples of the germanium-containing group or the tin-containing group include groups in which the silicon of the silicon-containing group is substituted with germanium or tin.

Among the groups exemplified as the groups that the hydrocarbon group may have,
Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and t-butoxy groups.
Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, a 2,4,6-trimethylphenoxy group, and the like.
Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and the like.
Specific examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group, etc.
Specific examples of the amino group include dimethylamino group, ethylmethylamino group, diphenylamino group and the like.
Specific examples of the imino group include methylimino group, ethylimino group, propylimino group, butylimino group, and phenylimino group.
Specific examples of the amide group include an acetamide group, N-methylacetamide group, N-methylbenzamide group, etc.
Specific examples of the imide group include an acetimido group and a benzimide group.
Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, a naphthylthio group, and the like.
Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.
Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

Examples of the hydrocarbon group include, in particular, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group and n-hexyl group. a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms;
aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group and anthracenyl group;
These aryl groups have substituents such as halogen atoms, alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl groups or aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. A substituted aryl group with 1 to 5 substitutions is preferred.

R ¹ to R ⁵ are heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups as described above. Examples of these include the same as those exemplified in the above description of the hydrocarbon group.

Among R ¹ to R ⁵ in the above general formula (I), R ¹ is a straight chain having 1 to 20 carbon atoms or a It is preferably a group selected from a branched hydrocarbon group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. R ² to R ⁵ may be the same or different, and are preferably hydrogen atoms, halogen atoms, or hydrocarbon groups.

In general formula (I) above, R ⁶ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting only of primary or secondary carbon atoms, an aliphatic hydrocarbon group having 4 or more carbon atoms, or an aryl group-substituted alkyl group. , monocyclic or bicyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms. Among these, aliphatic hydrocarbon groups having 4 or more carbon atoms, aryl group-substituted alkyl groups, single A group selected from a cyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group is preferable, more preferably a branched hydrocarbon group such as a t-butyl group; benzyl group, 1-methyl -Aryl-substituted alkyl groups such as 1-phenylethyl group (cumyl group), 1-methyl-1,1-diphenylethyl group, 1,1,1-triphenylmethyl group (trityl group); hydrocarbon group at 1-position cyclohexyl group, adamantyl group, norbornyl group, and tetracyclododecyl group having 6 to 15 carbon atoms or an alicyclic hydrocarbon group having a multiple ring structure.

In the above general formula (I), n is a number that satisfies the valence of M,
In the above general formula (I), X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic ring. represents a compound residue of the formula, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the plurality of groups represented by X may be the same or different, and are represented by X Multiple groups may combine with each other to form a ring.

In X, as the halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, tin-containing group are the same as those exemplified in the explanation of R ¹ to R ⁵ above. Preferred X is a hydrogen atom, a halogen atom, or a hydrocarbon group.

The transition metal compound represented by the general formula (I) in the present invention can be produced without limitation by the production method described in Patent Document 3 mentioned above.

Further, examples of the transition metal compound contained in the olefin polymerization catalyst of the present invention include metallocene compounds represented by the following general formula (II).

In general formula (II), M represents titanium, zirconium or hafnium.

In general formula (II), R ¹¹ to R ¹⁸ may be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of which are adjacent to each other may be linked to form a ring.

In R ¹¹ to R ¹⁸ , the halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, As the tin-containing group, the same groups as those exemplified for R ¹ to R ⁵ in the general formula (I) can be mentioned.

In general formula (II), X ¹ and X ² may be the same or different and represent a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

In the general formula (II), Y is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O- , -CO-, -S-, -SO-, _-SO2- , -Ge-, -Sn-, -NR-, -P(R)-, -P(O)(R)-, -BR- or -AlR- [where R may be the same or different and is a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group or an alkoxy group]. Examples of the hydrocarbon group, oxygen-containing group, sulfur-containing group, silicon-containing group, and halogen atom for Y include those exemplified in the explanation of R ¹ to R ⁵ in the general formula (I). .

Preferable examples of the above metallocene compounds include compounds having structures described in WO 01/27124 pamphlet, WO 2004/029062 pamphlet, and the like.

Among these, examples of metallocene compounds that can be particularly preferably used in the present invention include diphenylmethylene (cyclopentadienyl)(2,7-ditert-butylfluorenyl)zirconium dichloride, diphenylmethylene (cyclopenta dienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopenta dienyl)(2,7-ditert-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium dichloride, di( p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl) zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride and the like.

Furthermore, compounds in which "zirconium" in the above-described compounds is changed to "hafnium" or "titanium", and "cyclopentadienyl" to "3-tert-butyl-5-methyl-cyclopentadienyl", "3 ,5-dimethyl-cyclopentadienyl”, “3-tert-butyl-cyclopentadienyl”, “3-methyl-cyclopentadienyl” and the like are preferable examples.

[Other components that can be used in the olefin polymerization catalyst]
The olefin polymerization catalyst used in the method for producing olefin polymer particles according to the present invention must contain the components (A) and (B) described above.

For the purpose of carrying out the production method of the ethylene polymer particles with higher activity and adjusting the physical properties of the obtained ethylene polymer particles, the catalyst for olefin polymerization contains components other than the components (A) and (B). can be used additionally.

The other components can be used without any particular limitation as long as they do not impair the performance of the olefin polymerization catalyst containing components (A) and (B). Among them, (C): the compound that reacts with the component (B) to form an ion pair and (D) the organoaluminumoxy compound, which can be typically used, are described below.

[(C): Compound that forms an ion pair by reacting with component (B)]
In the present invention, the compound (C) that forms an ion pair by reacting with the component (B), which can be used as a component of the olefin polymerization catalyst, includes an organoaluminum compound, a boron halide compound, a phosphorus halide compound, Examples include halogenated sulfur compounds, halogenated titanium compounds, halogenated silane compounds, halogenated germanium compounds, and halogenated tin compounds.

Among these, as the organic aluminum compound, the above-mentioned (A) organic aluminum compound used for producing fine particles can be exemplified as a preferable compound.

Further, as the halogenated boron compound, the halogenated phosphorus compound, the halogenated sulfur compound, the halogenated titanium compound, the halogenated silane compound, the halogenated germanium compound, and the halogenated tin compound, the following compounds are specifically used. .

Boron halide compounds such as boron trifluoride, boron trichloride, boron tribromide;
Phosphorus trichloride, phosphorus tribromide, phosphorus triiodide, phosphorus pentachloride, phosphorus pentabromide, phosphorus oxychloride, phosphorus oxybromide, methyldichlorophosphine, ethyldichlorophosphine, propyldichlorophosphine, butyldichlorophosphine, cyclohexyldichloro Phosphine, phenyldichlorophosphine, methyldichlorophosphine oxide, ethyldichlorophosphine oxide, butyldichlorophosphine oxide, cyclohexyldichlorophosphine oxide, phenyldichlorophosphine oxide, methylphenylchlorophosphine oxide, dibromotriphenylphosphorane, tetraethylphosphonium chloride, dimethyldiphenylphosphonium halogenated phosphorus compounds such as iodide, ethyltriphenylphosphonium chloride, allyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, allyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide;
sulfur halide compounds such as sulfur dichloride, thionyl chloride, sulfuryl chloride, thionyl bromide;
titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytrichlorotitanium, ethoxytrichlorotitanium, butoxytrichlorotitanium, ethoxytribromotitanium, butoxytribromotitanium, dimethoxydichlorotitanium, diethoxydichlorotitanium, Halogenated titanium compounds such as dibutoxydichlorotitanium, diethoxydibromotitanium, trimethoxychlorotitanium, triethoxychlorotitanium, tributoxychlorotitanium, triethoxybromotitanium;
silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, methoxytrichlorosilane, ethoxytrichlorosilane, butoxytrichlorosilane, ethoxytribromosilane, butoxytribromosilane, dimethoxydichlorosilane, diethoxydichlorosilane, dibutoxydichlorosilane, diethoxydibromosilane, trimethoxychlorosilane, triethoxychlorosilane, tributoxychlorosilane, triethoxybromosilane, methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dibutyldichlorosilane, Halogenated silane compounds such as diphenyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, tributylchlorosilane, triphenylchlorosilane;
germanium tetrafluoride, germanium tetrachloride, germanium tetraiodide, methoxytrichlorogermanium, ethoxytrichlorogermanium, butoxytrichlorogermanium, ethoxytribromogermanium, butoxytribromogermanium, dimethoxydichlorogermanium, diethoxydichlorogermanium, dibutoxydichlorogermanium, germanium halide compounds such as diethoxydibromogermanium, trimethoxychlorogermanium, triethoxychlorogermanium, tributoxychlorogermanium, triethoxybromogermanium;
tin tetrafluoride, tin tetrachloride, tin tetrabromide, tin tetraiodide, methoxytrichlorotin, ethoxytrichlorotin, butoxytrichlorotin, ethoxytribromotin, butoxytribromotin, dimethoxydichlorotin, diethoxydichlorotin, dibutoxydichlorotin, diethoxydibromotin, trimethoxychlorotin, triethoxychlorotin, tributoxychlorotin, triethoxybromotin, methyltrichlorotin, ethyltrichlorotin, butyltrichlorotin, phenyltrichlorotin, dimethyldichlorotin, Halogenated tin compounds such as diethyldichlorotin, dibutyldichlorotin, diphenyldichlorotin, trimethylchlorotin, triethylchlorotin, tributylchlorotin, triphenylchlorotin.

These compounds may be used alone or in combination of two or more. Alternatively, it may be diluted with a hydrocarbon or a halogenated hydrocarbon.

Among specific examples of these compounds exemplified as component (C), preferred are trialkylaluminum, alkenylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, alkylaluminum alkoxide, (iso-Bu) ₂ Al(OSiMe ₃ ), (iso-Bu) ₂ Al(OSiEt ₃ ), Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl(iso-Bu) ₂ , LiAl(C ₂ H ₅ ) ₄ , halogenated silane compounds and halogenated titanium compounds, more preferably trialkylaluminum, alkenylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, alkylaluminum alkoxide, Trialkylaluminum and alkylaluminum halides are more preferred, and triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum are more preferred. is a dichloride.

[(D) Organic aluminum oxy compound]
In the present invention, (D) the organoaluminumoxy compound that can be used as a component of the olefin polymerization catalyst has been described as the organoaluminumoxy compound used in (Step 2) for producing the (A) fine particles described above. can be used.

<Method for producing ethylene-based polymer>
In the method for producing ethylene-based polymer particles according to the present invention, ethylene is homopolymerized in the presence of an olefin polymerization catalyst containing (A) fine particles and (B) a transition metal compound as described above, or ethylene and the number of carbon atoms are It is copolymerized with 3 to 20 linear or branched α-olefins.

In the method for producing ethylene-based polymer particles according to the present invention, polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method. Specific examples of inert hydrocarbon media used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. can also

When olefin polymerization is carried out using the above olefin polymerization catalyst, component (B) is generally 10 ⁻¹¹ to 10 millimoles, preferably 10 millimoles per liter of reaction volume, as metal atoms in component (B). It is used in an amount of 10 ^-9 to 1 mmol. Component (B) is generally used in an amount of 10 ^-4 to 100 millimoles, preferably 10 ^-3 to 50 millimoles, per gram of component (A).

Further, when using component (C), the molar ratio [(C)/M] of all transition metal atoms (M) in component (C) to component (B) is usually 0.01 to 100,000, preferably is used in an amount of 0.05 to 50,000.

Further, when component (D) is used, the molar ratio [(D)/M] of all transition metal atoms (M) in component (D) and component (B) is usually 0.01 to 100,000, preferably is used in an amount of 0.05 to 50,000.

The lower limit of the olefin polymerization temperature using such an olefin polymerization catalyst is -20°C, preferably 0°C, more preferably 20°C, and particularly preferably 30°C, and the upper limit of the olefin polymerization temperature is 150°C. , preferably 120°C, more preferably 100°C, and particularly preferably 80°C.

The polymerization pressure is usually normal pressure to 10 MPa, preferably normal pressure to 5 MPa.

The method for producing the ethylene-based polymer of the present invention may be a so-called multistage polymerization method in which the polymerization reaction conditions are changed and the reaction is performed in two or more stages.

The olefin polymerization catalyst component described above is preferably a so-called single-site catalyst.

In the present invention, the polymerization reaction of the ethylene-based polymer can be carried out in any of a batch system, a semi-continuous system and a continuous system. In the case of production by the multi-stage polymerization process as described above, it is preferable to employ a batch system. Ethylene-based polymers obtained by a batch process are considered to be advantageous due to their uniformly dispersed structure, with little variation in the ethylene-based polymers obtained in the first and second polymerization steps for each composition particle. This is because

The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature or polymerization pressure. Furthermore, it can also be adjusted by the amount of component (C) or component (D) present in the olefin polymerization catalyst.

Olefins to be polymerized in the present invention include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 2-butene and 1-pentene. , 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -octadecene, 1-eicosene; cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1, 4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride acids, α,β-unsaturated carboxylic acids such as bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, their sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts , α,β-unsaturated carboxylic acid metal salts such as calcium salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, α,β-unsaturated carboxylic acid esters such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate; vinyl acetate, propionic acid Vinyl esters such as vinyl, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate and monoglycidyl itaconate; be done. Vinylcyclohexane, dienes, polyenes, and the like can also be used. Cyclic or chain compounds having two or more double bonds having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, are used as dienes or polyenes. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 ,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4 -ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; also aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene , o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxy Functional group-containing styrene derivatives such as styrene, o-chlorostyrene, p-chlorostyrene and divinylbenzene; 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like. Among these, ethylene and propylene are particularly preferably used.

<Olefin polymer particles>
The (E) intrinsic viscosity [η] of the olefin polymer particles obtained by the method for producing olefin polymer particles according to the present invention is in the range of 5 to 50 dl/g.

The above intrinsic viscosity [η] is a value measured at 135°C in decalin solvent according to JIS K 7367-3 standard. The intrinsic viscosity [η] is preferably 10 to 45 dl/g, more preferably 15 to 40 dl/g.

The olefin polymer particles obtained by the method of the present invention preferably satisfy the following requirements (ii) and (iii).
(ii) The average particle size is in the range of 10 nm or more and less than 3000 nm.
(iii) Crystallinity is 70% or more.

The olefin polymer particles are formed of aggregates of microparticles, and the average particle size of the microparticles is determined by observation with a scanning electron microscope (SEM).

The fine particles of the olefin polymer particles have an average particle diameter of 10 nm or more and less than 3000 nm, preferably 10 nm or more and less than 2000 nm, more preferably 10 nm or more and less than 1000 nm. Olefin polymer particles having a structure within such an average particle size range have a large specific surface area, so that when the olefin polymer particles are brought into contact with each other, the contact area increases. Particles are likely to be pressed against each other during molding. As a result, a strong compression-molded product can be easily obtained, and interface breakage between particles is less likely to occur.

In addition, since the ethylene-based polymer particles are formed from aggregates of fine particles, there is a wide space between the fine particles, so that a uniform compression history is received during compression molding, resulting in a uniform structure with few defects. can be formed. As a result, breakage due to defects during stretching is less likely to occur, and molding at a high draw ratio can be expected to become easier.

The crystallinity of the olefin polymer particles is a value calculated from the heat of fusion using a differential scanning calorimeter (DSC). The lower limit of the crystallinity of the ethylene polymer particles is usually 70%, preferably 75%, more preferably 80%. Regarding the upper limit of the crystallinity, the higher the crystallinity, the higher the strength of the molded product can be obtained, and the tendency is that distortion and deformation such as volume shrinkage over time are less likely to occur. The upper limit of the crystallinity is naturally 100%, preferably 99%, more preferably 97%, and still more preferably 95%.

The olefin polymer particles according to the present invention can be obtained by polymerizing or copolymerizing the exemplified olefins in the presence of the olefin polymerization catalyst described above.

Among these, the olefin polymer particles according to the present invention are preferably ethylene-based polymers. More specifically, ethylene homopolymers, ethylene and a small amount of α-olefins such as propylene, -Methyl-1-pentene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc. are preferably crystalline copolymers mainly composed of ethylene obtained by copolymerization. As a raw material for solid phase stretching molding, an ethylene homopolymer is preferable from the viewpoint of increasing the degree of crystallinity and from the viewpoint of stretchability in solid phase stretching molding, which will be described later. On the other hand, when the molded article requires creep resistance, it is preferable that propylene or the like is copolymerized. Depending on the olefin polymerization catalyst used, even an ethylene homopolymer may yield an ethylene-based polymer having a branched structure. It is believed that such branching is extremely rare due to the use of a type olefin polymerization catalyst. A polymerization method capable of obtaining such a polymer increases the degree of freedom in controlling the molecular structure, and is advantageous in improving the performance of a solid-phase stretched molded article described later.

As described above, the olefin polymer particles obtained by the method of the present invention are suitably used for compression molding and solid-phase stretching molding, and can be used to obtain high-performance sintered filters and reinforcing fibers. In addition, it can be used for various purposes such as a sliding improver, typically an additive for water wiping members such as wipers.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[Experimental example 1]
(Method for measuring surface roughness Ra)
Using a small surface roughness measuring machine SURFTEST SJ-310 manufactured by Mitutoyo Corporation, two arbitrary points were measured according to the JIS B 0601 standard, and the average value was taken as the surface roughness Ra.

(1, Preparation step of MgCl ₂ /2-ethylhexanol/decane solution)
330.5 g (3.47 mol) of anhydrous magnesium chloride, 246 g of dehydrated decane and 1355 g (10.4 mol) of 2-ethylhexyl alcohol were stirred and mixed in a 5 L vessel equipped with a stirrer and sufficiently purged with nitrogen, and the temperature was raised to 145°C. By holding the mixture for 4 hours, a homogeneous and transparent component (i'1) of 1.0 mol/L in terms of Mg atoms was obtained. The component (i'1) was diluted with dehydrated decane to obtain a homogeneous and transparent component (i1) of 0.06 mol/L in terms of Mg atom.

(Catalyst preparation step and ethylene polymerization step)
After preparation of the solid catalyst, ethylene was polymerized in a pressure-resistant polymerization reactor equipped with a stirrer and baffles having the surface conditions shown below.

(Surface condition of the pressure-resistant polymerization reactor)
a. Reactor inner wall roughness (Ra)
Part 1: Ra = 0.076 μm area: 1/4 of the whole
Part 2: Ra = 0.11 μm area: 1/4 of the whole
Part 3: Ra = 0.19 μm area: 1/2 of the whole
b. Baffle surface roughness (Ra)
Part 4: Ra = 0.11 μm area: 1/3 of the whole
Part 5: Ra = 0.37 μm area: 2/3 of the whole
c. Roughness of stirring blade surface (Ra)
Part 6: Ra = 0.023 µm area: 1/2 of the whole
Site 7: Ra = 0.17 μm area: 1/2 of the whole

(2, catalyst preparation step)
120 liters of dehydrated decane and 6 liters of dehydrated hexane were introduced at room temperature into a 340 liter pressure-resistant polymerization reactor equipped with a stirrer and sufficiently purged with nitrogen. 68 liters was charged. The solution was heated and maintained at 60° C., and while stirring, 1.65 liters of the component (i1) was charged and maintained at 60° C. (granules are formed at this stage). After the completion of the above, 1.2 liters of dehydrated toluene solution (1.6 g/liter) of ADEKA Pluronic TR-701 (antistatic agent manufactured by ADEKA CORPORATION) was charged. Next, 0.1 liter of a dehydrated toluene solution (1.1 mmol-Zr/liter) of the transition metal complex (α) described below was charged to complete the preparation of the supported catalyst for olefin polymerization.

(3, Polymerization step of ethylene)
Ethylene was started to be supplied to the reactor at a rate of 3.6 kg/hour while the supported catalyst solution was kept at 40° C. with stirring. Subsequently, 0.01 mol of hydrogen was charged, and after the temperature in the system started to rise due to the heat of reaction, the temperature was maintained at 50°C by heating. After 130 minutes from the start of ethylene supply (the system internal pressure was about 0.3 MPaG), the supply of ethylene was stopped, and unreacted ethylene was purged (depressurization, nitrogen pressurization, and depressurization were repeated). : 7.7 kg). The volume ratio of decane:hexane:toluene in the ethylene polymerization reaction stage was about 94:5:1.

Next, the polymerization reaction solution was transferred to a washing vessel with a capacity of 1,300 liters with a stirrer via a metal pipe (bottom drain, nitrogen pressurization), and an appropriate amount of 2-ethylhexanol was added to deactivate the supported catalyst. turned into Subsequently, 250 liters of hexane was charged into the pressure-resistant polymerization reaction vessel, stirred, and then transferred to the washing vessel equipped with a stirrer via a metal pipe (bottom drain, nitrogen pressurization). Thereafter, sedimentation separation, deliquoring, and washing with dehydrated hexane were repeated five times. Subsequently, the polymerized reaction solution after washing is transferred to a filtration dryer with a capacity of 240 liters via a metal pipe (bottom drain, nitrogen pressurization), and a small amount of nitrogen is supplied to the solid portion separated by filtration under reduced pressure. After drying at 45° C. for 7 hours while heating, ethylene polymer particles (aggregates) were obtained.

Polymerization activity is 63.9 kg/mmol-Zr, in accordance with JIS K 7356-3 standard, intrinsic viscosity ([η]) measured at 135°C in decalin is 33.4 dl/g, polymer particle diameter (observed by operating electron microscope The average value obtained by measuring the primary particle diameters at arbitrary five locations) was 240 nm. The average particle size of the supported catalyst component for olefin polymerization used was calculated to be 40 nm from the primary particle size of this polymer, the amount of catalyst used, and the value of polymerization activity.

After the completion of the polymerization reaction, the conditions inside the polymerization reactor were visually confirmed to be as follows.
Site 1: Ra = 0.076 µm area: no fouling Site 2: Ra = 0.11 µm area: no fouling Site 4: Ra = 0.11 µm area: no fouling Site 6: Ra = 0.023 µm Area: No fouling Part 3: Area with Ra = 0.19 µm: With fouling Part 5: Area with Ra = 0.37 µm: With fouling Part 7: Area with Ra = 0.17 µm: With fouling

[Experimental example 2]
Preparation of a supported catalyst and polymerization of ethylene were carried out in the same manner as in Experimental Example 1, except that the pressure-resistant polymerization reactor equipped with a stirrer and baffles was set as follows.

(Surface condition of the above pressure-resistant polymerization vessel)
d. Reactor inner wall roughness (Ra)
Site 8: Ra = 0.045 μm area: 1/4 of the whole
Site 9: Ra = 0.12 µm area: 1/4 of the whole
Site 10: Ra = 0.17 μm area: 1/2 of the whole
e. Baffle surface roughness (Ra)
Site 11: area with Ra = 0.079 µm: overall f. Roughness of stirring blade surface (Ra)
Part 12: Ra = 0.040 μm area: whole

After the completion of the polymerization reaction, the conditions inside the polymerization reactor were visually confirmed to be as follows.
Site 8: Ra = 0.045 µm area: no fouling Site 9: Ra = 0.12 µm area: no fouling Site 11: Ra = 0.079 µm area: no fouling Site 12: Ra = 0.040 µm Area of: No fouling Part 10: Area of Ra = 0.17 μm: With fouling

[Experimental example 3]
(1, Preparation step of MgCl ₂ /2-ethylhexanol/decane solution)
The component (i′1) prepared in the same manner as in Experimental Example 1 was diluted with dehydrated decane to obtain a homogeneous and transparent component (i2) having a concentration of 0.25 mol/L in terms of Mg atom.

(Catalyst preparation step and ethylene polymerization step)
Polymerization of ethylene was carried out after preparation of the solid catalyst in a pressure-resistant polymerization reactor equipped with a stirrer and baffles having the following surface conditions.

(Surface condition of the above pressure-resistant polymerization vessel)
a. Reactor inner wall roughness (Ra)
Part 1: Ra = 0.026 μm area: 1/6 of the whole
Part 2: Ra = 0.079 μm area: 5/6 of the whole
b. Baffle surface roughness (Ra)
Site 3: Ra=0.11 μm area: whole c. Roughness of stirring blade surface (Ra)
Part 4: Ra = 0.041 μm area: whole

(2, catalyst preparation step)
990 liters of dehydrated decane and then 3.27 liters of a 0.82 mol-Al/liter solution of triisobutylaluminum were charged into a 1600 liter pressure-resistant polymerization reactor equipped with a stirrer and sufficiently purged with nitrogen at room temperature. . The solution was heated and maintained at 60° C., and while stirring, 2.68 liters of the component (i2) was charged and maintained at 60° C. (granules are formed at this stage). After the completion of the above, 1.25 liters of dehydrated toluene solution (12 g/liter) of ADEKA Pluronic TR-701 (antistatic agent manufactured by ADEKA CORPORATION) was charged. Next, 2.37 liters of a dehydrated toluene solution (0.35 mmol-Zr/liter) of the transition metal complex (α) was charged to complete the preparation of the supported catalyst for olefin polymerization.

(3, Polymerization step of ethylene)
Ethylene was started to be supplied to the reactor at a rate of 25 kg/hour while the supported catalyst solution was kept at 40° C. with stirring. Subsequently, 0.019 mol of hydrogen was charged, and after the temperature in the system started to rise due to the heat of reaction, the temperature was maintained at 50°C by heating. After 140 minutes from the start of ethylene supply (the system internal pressure was about 0.3 MPaG), the supply of ethylene was stopped and unreacted ethylene was purged (depressurization, nitrogen pressurization, and depressurization were repeated). : 58 kg). The decane:toluene volume ratio in the ethylene polymerization reaction stage was about 99:1.

Next, after inactivating the supported catalyst by adding an appropriate amount of 2-ethylhexanol to the polymerization reaction solution, the solution is transferred to a filtration dryer with a capacity of 2600 liters via a metal pipe (bottom drain, nitrogen pressurization). , deliquored. Subsequently, 1,200 liters of hexane was charged into the pressure-resistant polymerization reaction vessel, stirred, and then transferred to the filtration dryer via a metal pipe (bottom drain, pressurized with nitrogen) and deliquored. Next, the solid content in the filter dryer is washed three times with dehydrated hexane, and the solid portion separated by filtration is dried at 90° C. for 17 hours under reduced pressure while supplying a small amount of nitrogen to obtain an ethylene polymer. Particles (agglomerates) were obtained.

Polymerization activity is 60.1 kg/mmol-Zr, in accordance with JIS K 7356-3 standard, intrinsic viscosity ([η]) measured at 135°C in decalin is 34.9 dl/g, polymer particle diameter (manipulated electronic The average value obtained by measuring the primary particle size at any five locations by microscopic observation was 250 nm. The average particle size of the supported catalyst component for olefin polymerization used was calculated to be 40 nm from the primary particle size of this polymer, the amount of catalyst used, and the value of polymerization activity.

After the completion of the polymerization reaction, the conditions inside the polymerization reactor were visually confirmed to be as follows.
Site 1: Ra = 0.026 µm area: no fouling Site 2: Ra = 0.079 µm area: no fouling Site 3: Ra = 0.11 µm area: no fouling Site 4: Ra = 0.041 µm area: no fouling

[Experimental example 4]
The charge of dehydrated decane was 983 liters, the charge of 0.82 mol-Al/l solution of triisobutylaluminum was 4.29 liters, the charge of component (i2) was 3.53 liters, the transition The dehydrated toluene solution (0.35 mmol-Zr/liter) of the metal complex (α) was charged to 3.11 liters, and the dehydrated toluene solution of ADEKA Pluronic TR-701 (antistatic agent manufactured by ADEKA CORPORATION) was added to ADEKA. A supported catalyst was prepared in the same manner as in Experimental Example 3, except that Pluronic L-71 (an antistatic agent manufactured by Adeka Co., Ltd.) was changed to a dehydrated toluene solution (concentration: 3.66 g/liter, charging amount: 5.74 liters). was prepared and the polymerization of ethylene was carried out.

Polymerization activity is 49.1 kg/mmol-Zr, in accordance with JIS K 7356-3 standard, intrinsic viscosity ([η]) measured at 135°C in decalin is 32.9 dl/g, polymer particle diameter (manipulated electronic The average value obtained by measuring the primary particle diameters at arbitrary five locations by microscopic observation was 230 nm. The average particle size of the supported catalyst component for olefin polymerization used was calculated to be 40 nm from the primary particle size of this polymer, the amount of catalyst used, and the value of polymerization activity.

After the completion of the polymerization reaction, the conditions inside the polymerization reactor were visually confirmed to be as follows.
Site 1: Ra = 0.026 µm area: no fouling Site 2: Ra = 0.079 µm area: no fouling Site 3: Ra = 0.11 µm area: no fouling Site 4: Ra = 0.041 µm area: no fouling

[Experimental example 5]
(Catalyst preparation step and ethylene polymerization step)
Using the component (i2) prepared in the same manner as in Example 3 and the pressure-resistant polymerization reactor equipped with the same stirrer and baffle as in Experimental Example 3, a solid catalyst was prepared by the following method, and then ethylene was polymerized.

(1, catalyst preparation step)
975 liters of dehydrated decane and then 3.33 liters of a 0.82 mol-Al/liter solution of triisobutylaluminum were charged into a 1600 liter pressure-resistant polymerization reactor equipped with a stirrer and sufficiently purged with nitrogen at room temperature. . The solution was heated and maintained at 60° C., and while stirring, 3.48 liters of the component (i2) was charged and maintained at 60° C. (granules are formed at this stage). Subsequently, while the inside of the polymerization reaction vessel was maintained at 40° C., the pressure was increased to 0.1 MPa with ethylene, and then a dehydrated toluene solution (1.80 mmol-Ti/liter) of the following transition metal complex (β) was .41 liters were charged. After the completion of the above, 1.59 liters of dehydrated toluene solution (3.66 g/liter) of ADEKA Pluronic L-71 (antistatic agent manufactured by ADEKA CORPORATION) was added to complete the preparation of the supported catalyst for olefin polymerization.

(2, Ethylene polymerization step)
Ethylene was started to be supplied to the reactor at a rate of 68 kg/hour while maintaining the supported catalyst solution at 40° C. while stirring. Subsequently, 0.14 mol of hydrogen was added, and after the temperature inside the system started to rise due to the heat of reaction, the temperature was maintained at 50°C by heating. When the internal pressure in the system reached 0.6 MPaG, the amount of ethylene supplied was adjusted so that the pressure remained constant. was repeated.) was performed (supplied ethylene: 66 kg). The decane:toluene volume ratio in the ethylene polymerization reaction stage was about 99:1. Next, deactivation, washing and drying were carried out in the same manner as in Experimental Example 3 to obtain ethylene polymer particles (aggregates).

Polymerization activity is 11.6 kg/mmol-Ti, in accordance with JIS K 7356-3 standard, intrinsic viscosity ([η]) measured at 135°C in decalin is 37.7 dl/g, polymer particle diameter (manipulated electronic The average value obtained by measuring the primary particle diameters at arbitrary five locations by microscopic observation was 230 nm. The average particle size of the supported catalyst component for olefin polymerization used was calculated to be 40 nm from the primary particle size of this polymer, the amount of catalyst used, and the value of polymerization activity.

After the completion of the polymerization reaction, the conditions inside the polymerization reactor were visually confirmed to be as follows.
Site 1: Ra = 0.026 µm area: no fouling Site 2: Ra = 0.079 µm area: no fouling Site 3: Ra = 0.11 µm area: no fouling Site 4: Ra = 0.041 µm area: no fouling

[Experimental example 6]
973 liters of dehydrated decane was charged, and 4.05 liters of dehydrated toluene solution (concentration: 3.66 g/liter) of Adeka Pluronic L-71 (an antistatic agent manufactured by Adeka Co., Ltd.) was charged. Support was carried out in the same manner as in Experimental Example 5, except that the charge of the dehydrated toluene solution of -71 (Antistatic agent manufactured by Adeka) was changed after the component (i2) was charged and kept at 60 ° C. Catalyst preparation and ethylene polymerization were carried out.

Polymerization activity is 12.5 kg/mmol-Ti, in accordance with JIS K 7356-3 standard, intrinsic viscosity ([η]) measured at 135°C in decalin is 38.7 dl/g, polymer particle diameter (manipulated electronic The average value obtained by measuring the primary particle size at any five locations by microscopic observation was 240 nm. The average particle size of the supported catalyst component for olefin polymerization used was calculated to be 40 nm from the primary particle size of this polymer, the amount of catalyst used, and the value of polymerization activity.

After the completion of the polymerization reaction, the conditions inside the polymerization reactor were visually confirmed to be as follows.
Site 1: Ra = 0.026 µm area: no fouling Site 2: Ra = 0.079 µm area: no fouling Site 3: Ra = 0.11 µm area: no fouling Site 4: Ra = 0.041 µm area: no fouling

From the results of Experimental Examples 1 to 6 above, even if the size of the polymerization reaction vessel is changed, fouling can be effectively suppressed in the region where the surface roughness (Ra) of the reactor surface is 0.15 μm or less. I know it will be.

According to the method for producing ethylene polymer particles according to the present invention, even if a large-scale reactor is used, fouling of the ethylene polymer particles to the walls of the polymerization vessel, stirring blades, etc. can be minimized. , there is no need to stop the plant in industrial production, and it is advantageous in terms of cost.

1: Stirrer 2: Flange 3: Stirring blade 4: Baffle 5: Reaction vessel

Claims (9)

A method for producing olefin polymer particles that satisfies the following requirement (E),
In a reactor that satisfies the following requirements (α),
a liquid containing 95% by volume or more of a hydrocarbon selected from aliphatic hydrocarbons and alicyclic hydrocarbons;
A method for producing olefin polymer particles, comprising a step of polymerizing an olefin in the presence of a particulate olefin polymerization catalyst component containing a transition metal element and having an average particle size of 1 nm or more and 300 nm or less:
(E) the intrinsic viscosity [η] measured at 135°C in a decalin solvent is 5 to 50 dl/g;
(α) The internal volume is 30 liters or more, and the surface roughness Ra of the reactor surface determined by a method according to the JIS B 0601 standard is 0.15 μm or less. The reactor has a reaction vessel, a baffle, and a stirring blade,
the reactor surface comprises a reaction vessel inner wall surface, a baffle surface, and a stirring blade surface;
The method for producing olefin polymer particles according to claim 1. 3. The method for producing olefin polymer particles according to claim 2, wherein the surface of the stirring blade has an Ra of 0.05 [mu]m or less. The catalyst component for olefin polymerization is
(A) fine particles having an average particle size of 1 nm or more and 300 nm or less, which are obtained through at least steps 1 and 2 below;
2. The method for producing olefin polymer particles according to claim 1, further comprising (B) a transition metal compound having a structure represented by the following general formula (I).
(Step 1) A step of contacting a metal halide and an alcohol in a hydrocarbon solvent (Step 2) Contacting the component obtained in (Step 1) with an organoaluminum compound and/or an organoaluminumoxy compound process

(In formula (I), M represents a transition metal atom of groups 4 and 5 of the periodic table,
m represents an integer of 1 to 4,
R ¹ to R ⁵ , which may be the same or different, are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of which may be linked together to form a ring,
R ⁶ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting only of primary or secondary carbon atoms, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, monocyclic or bicyclic selected from alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and halogen atoms of
n is a number that satisfies the valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different, and the multiple groups represented by X may be bonded to each other. may form a ring. ) The olefin weight according to claim 4, wherein the alcohol is a combination of two alcohols selected from alcohols having 1 to 25 carbon atoms, and the difference in the number of carbon atoms between the two alcohols is 4 or more. A method for producing coalesced particles. 6. The method for producing olefin polymer particles according to claim 5, wherein the two alcohols are a combination of an alcohol having 2 to 12 carbon atoms and an alcohol having 13 to 25 carbon atoms. 6. The method for producing olefin polymer particles according to claim 5, wherein the two alcohols are a combination of two alcohols selected from alcohols having 2 to 12 carbon atoms. In the general formula (I), M is titanium, zirconium or hafnium,
m is 2;
R ¹ is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. indicating the group to be selected,
R ² to R ⁵ , which may be the same or different, each represent a hydrogen atom, a halogen atom, or a hydrocarbon group;
R ⁶ is selected from an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group;
6. The method for producing olefin polymer particles according to claim 5, wherein X represents a hydrogen atom, a halogen atom, or a hydrocarbon group. 2. The method for producing olefin polymer particles according to claim 1, wherein said olefin contains ethylene.

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