JPH0742328B2 - Method for producing ethylene-based polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an ethylene-based polymer by polymerizing ethylene or ethylene and another α-olefin, and more specifically, to a method for preparing the same. Using a simple catalyst,
It has a high bulk density, a narrow particle size distribution, good powder flowability, and is characterized by producing a polymer particularly suitable for powder molding.

(B) Conventional Technology Many methods have been proposed for controlling the powder characteristics of ethylene polymers, that is, the bulk density, particle size distribution or particle shape. As a typical example, (i) a method in which a magnesium compound such as magnesium hydroxide is spray-dried, granulated, and then classified (JP-A-54-41985), (ii) an inorganic oxide such as silica or alumina. Method of depositing catalyst component on the surface (JP-A-57-90004), (iii) Grinding low-molecular-weight polyethylene and catalyst component, embedding the catalyst component on the particle surface of polyethylene, and then heating in poor solvent of polyethylene Then, the particle shape is adjusted (JP-A-61-87711), (iv) a complex is formed from a magnesium halide active hydrogen compound, which is brought into a molten state, and then rapidly cooled and precipitated in an inert solvent. (JP-A-55-135102, JP-A-58-215408) and the like. Although these methods have achieved considerable results, all of them use powders, so that they are troublesome to handle and the catalyst preparation methods are complicated. On the other hand, Japanese Patent Publication Sho-25-25
The method disclosed in No. 361 is epoch-making in that the catalyst components are simply mixed and reacted, but the preparation reaction requires a high temperature in part, and the bulk density of the produced polymer is also maximum. It is around 0.35 and there is still room for improvement.

(C) Problems to be Solved by the Invention When an ethylene-based polymer is produced by polymerizing ethylene and copolymerizing ethylene with another α-olefin, it is necessary to satisfy the following conditions in particular.

a The catalyst is highly active.

This leads to omission of the catalyst removal step, assurance of polymer quality and reduction of plant construction costs.

b The powder property of the produced polymer is good. That is, the bulk density is high, the particle size distribution is narrow, the particle shape is good, and the fluidity of the powder is good.

As a result, troubles in the manufacturing process such as clogging of slurry or powder are eliminated during polymer manufacturing, and stable operation is possible. In addition, productivity will be improved by increasing the slurry concentration, and equipment costs will be reduced by downsizing the powder silo.

In addition, it can be used as a raw material resin for powder coating processing such as powder molding including rotation molding, fluidized dipping, sintering molding, and electrostatic powder coating.

c Catalyst preparation is simple and does not generate waste.

Catalyst preparation that involves complicated operations or has a large number of steps is
Not only does it take time and labor, but the reproducibility of the catalyst becomes poor. Therefore, it is desirable that the catalyst preparation be as simple as possible. Further, in general, a highly active catalyst that uses a carrier component and supports a titanium compound usually produces a large amount of waste containing the titanium compound because the solid component is separated and washed after the supporting reaction. This treatment requires considerable equipment and cost.

(D) Means for Solving Problems The present inventors have solved the above problems by selecting specific catalyst components and adopting preparation conditions based on JP-A-59-12906. . The method disclosed in JP-A-59-12906 has the advantage that it has high catalytic activity in so-called melt polymerization at a high temperature of 170 ° C. or higher and that it does not generate wastes containing transition metal compounds and the like. However, when it was used in the slurry polymerization method, the powder properties of the obtained polymer were poor and it was not practical.

That is, the present inventors have selected an intermediate reaction product [A] obtained by the reaction of the following components [I] to [III] [I] hydropolysiloxane and a Grignard reagent, and further selected from alcohol, aldehyde and ketone. The reaction product [B] obtained by reacting at least one kind of nucleophilic reagent, [II] transition metal compound, [III] organoaluminum compound In the method for polymerizing or copolymerizing with other α-olefins, as the component [II], (1) the general formula Ti (OR ⁷ ) _m X _4-m (wherein R ₇ is an alkyl group having 1 to 10 carbon atoms) Group, X is Cl atom or
Br atom, m is a number of 2 to 4) and / or (2) the general formula VO (OR ⁸ ) _n X _3-n or V (OR
⁹ ) _p X _4-p (where R ⁸ and R ⁹ are alkyl groups having 1 to 10 carbon atoms,
X is Cl atom or Br atom, n is a number of 2-3, and p is 2-4.
Of the general formula AlR ¹⁰ ₂ X (where R ¹⁰
Is a hydrocarbon group having 1 to 10 carbon atoms, X is Cl atom or Br atom)
Each of the organoaluminum compounds represented by
And a catalyst component [C] obtained by reacting the component [III] with each other, and a general formula AlR ¹¹ _q X _3-q (wherein R ¹¹ is an alkyl group having 1 to 10 carbon atoms, q is A method of polymerizing or copolymerizing in the form of a slurry at a polymerization temperature of 30 to 100 ° C in the presence of a catalyst composed of an alkylaluminum compound represented by Body properties, namely bulk density, particle size distribution, particle shape,
It has been found that the powder fluidity is good.

Further, in particular, the method of the present invention generally has an average particle size of 250μ or less, and further has excellent powder properties despite having a small particle size of 200μ or less, a polymer suitable for powder molding and powder coating processing. It has the characteristic that a powder is obtained.

The hydropolysiloxane used in the production of the intermediate product [A] of the present invention is represented by the general formula R ¹ _a H _b SiO _{(4-ab) / 2} (R ¹ is a C _{1 to} C ₁₂ hydrocarbon group or An alkoxy group or a phenoxy group, a is 0, 1, or 2, b is 1, 2, or 3, and is a chain-like or cyclic silicon-containing compound having a structural unit represented by a + b ≦ 3). The degree of polymerization of the hydropolysiloxane is not particularly limited, but the viscosity of the liquid low-polymerized product at 25 ° C is 100,
Grease-like or wax-like substances having various degrees of polymerization up to 000 centistokes can be used. It may be completely solid. The terminal structure of the hydropolysiloxane does not have a particularly great influence and may be blocked with an inert group such as a trialkylnolyl group.

Hydropolyloxane usually used in the present invention is tetramethyldisiloxane, tetraethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, etoxyhydrosiloxane. Examples thereof include polysiloxane, cyclooctylhydropolysiloxane and chlorophenylhydropolysiloxane.

The Grignard reagent used in the present invention is obtained by the reaction of a halogen-containing organic compound and metallic magnesium, and has the general formula (Mg ▲ R ² ₂ ▼) _p · (MgR ² X) _q (R ² is C _{1 to} C ₁₂ hydrocarbon group, X is a halogen atom, p and q are numbers from 0 to 1, and a compound represented by p + q = 1), an ether chain compound thereof, or a mixture thereof. For example, when p = 0 and q = 1,
It is a so-called Grignard reagent in a narrow sense and is MgR ² X. In the case of p = 1 and q = 0, it is dihydrocarbyl magnesium represented by MgR ² ₂ ▼. In addition, when p and q take various intermediate values, (Mg ▲ R ² ₂ ▼) _p・ (MgR ²
X) An organic magnesium halide represented by _q .
Further, all of them may be the ether complex compound or a mixture thereof.

The Grignard reagent is a known method, in an ether solvent such as diethyl ether, dibutyl ether or tetrahydrofuran, or in a hydrocarbon solvent such as heptane, octane, benzene or toluene, a suitable amount of ether, amine or the like is complexed. Easily synthesized in the presence of the agent.

Specific examples of the general formula MgR ² X include methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium chloride, n-butylmagnesium chloride, tert-butylmagnesium chloride, n-octylmagnesium chloride, phenylmagnesium chloride. , And the like.

As the general formula Mg ▲ R ² ₂ Examples of ▼, diethyl magnesium, di -n- propyl magnesium, di -n-
Butylmagnesium, di-tert-butylmagnesium,
Di-n-octyl magnesium, diphenyl magnesium, etc. are mentioned.

As a method for reacting the hydropolysiloxane with the Grignard reagent, the following method is used. Hydropolysiloxane is added little by little to the Grignard reagent synthesized in an appropriate solvent while stirring (conversely, the Grignard reagent may be added to the hydropolysiloxane).
After adding the whole amount, heat and react for a predetermined time. Alternatively, as in the case of synthesizing a Grignard reagent, metallic magnesium may be dispersed in a suitable solvent, and a mixture of an organic halogen compound and hydropolysiloxane may be added dropwise at a predetermined temperature with stirring and then reacted for a predetermined time. . This reaction proceeds at room temperature with intense heat generation, but in order to complete the reaction, it is preferable to heat at 20 to 100 ° C, particularly 30 to 80 ° C for 1 to 5 hours. Above 100 ° C, the Si-H bond is decomposed, which is not preferable. The hydropolysiloxane and the Grignard reagent were charged at a molar ratio of MgR ² : Si of 1: 1 to 20, particularly
1: 1-5 is preferable.

When methylhydropolysiloxane is used as the hydropolysiloxane, the reaction for obtaining the intermediate reaction product [A] is
It is known to proceed as follows (Japanese Patent Publication No. 52-13).
No.232).

(N is the degree of polymerization or the number of mols) The intermediate reaction product [A] is obtained in solution when the Grignard reagent synthesized in tetrahydrofuran is used,
When a chain ether compound such as diethyl ether is used, it is obtained in suspension.

The nucleophilic reagent used to obtain the reaction product [B] of the present invention is an alcohol represented by the general formula R ³ OH (R ³ is a C _{1 to} C ₁₈ hydrocarbon group).

Further, the general formula R ⁴ COR ⁵ (R ⁴ and R ⁵ are a hydrogen atom or C
_{1 to} C ₁₇ hydrocarbon group, which may be the same or different from each other), and a general formula An aldehyde or ketone represented by (R ⁶ is a C ₃ -C ₁₇ divalent hydrocarbon group) can be used.

Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, 2-ethylbutanol, n-.
Examples thereof include heptanol, n-octanol, 2-ethylhexanol, n-decanol, stearyl alcohol, cyclohexanol, benzyl alcohol, phenol and cresol.

Specific examples of the aldehyde include formaldehyde, acetaldehyde, n-propylaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, trimethylacetaldehyde, isohexaldehyde, n-octylaldehyde, 2-ethylhexaldehyde, n-deca. Aldehydes, tridecaaldehydes, stearaldehydes, benzaldehydes and the like can be mentioned.

Specific examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, di-n.
-Butyl ketone, di-n-octyl ketone, ethylhexyl ketone, benzophenone, cyclobutanone, cyclohexanone, cyclodecanone and the like can be mentioned.

These nucleophiles may be used alone or as a mixture of two or more kinds,
Used in the reaction with the intermediate reaction product [A].

The reaction for obtaining the reaction product [B] used in the present invention is carried out by dropwise adding the nucleophilic reagent to the intermediate reaction product [A] with stirring.

The reaction proceeds exothermically at room temperature. After completion of the dropping, the reaction is preferably completed at 30 to 100 ° C. for 1 to 5 hours in order to complete the reaction. This reaction can be carried out in a state where the desired inert hydrocarbon solvent is added to the intermediate reaction product [A] in advance and diluted.

The amount of the nucleophilic reagent used to obtain the reaction product [B] is 1 mol of Si-H group in the intermediate reaction product [A].
It is preferably 1.0 mol or less and 0.5 mol or more per 1 mol of magnesium in the intermediate reaction product [A]. The amount of the nucleophilic reagent used is 1 mol of magnesium in the intermediate reaction product [A].
On the other hand, when the amount is 0.5 mol or less, the ether compound, which is the solvent of the Grignard reagent, is insufficiently removed, and the reaction product becomes sticky.

In addition, the amount used is 1 mol of Si-H group in the intermediate reaction product [A].
If the amount is 1.0 mol or more, the catalyst activity may decrease and the solubility of the reaction product [B] in the hydrocarbon group may decrease, which is not preferable.

The ether compound which is the solvent of the Grignard reagent is removed from the reaction mixture of the intermediate reaction product [A] and the nucleophilic reagent,
Reaction product [B] soluble or suspended in an inert hydrocarbon
As a method of obtaining the above, a method of adding an inert hydrocarbon having a boiling point higher than that of the ether compound to the reaction mixture, distilling it under normal pressure or under reduced pressure, and distilling off the ether compound is preferable.

The residual amount of the ether compound in the reaction product [B] is closely related to the catalytic activity, and the smaller the residual amount, the better. Usually 0.4 mol or less per gram atom of magnesium in the reaction product [B],
Particularly, 0.2 mol or less is preferable.

The solubility of the reaction product [B] in an inert hydrocarbon varies depending on the type of the inert hydrocarbon, the type of the nucleophilic reagent, the hydrocarbon group of the Grignard reagent, the type of the ether compound and the remaining amount thereof in addition to the temperature. However, in order to achieve the object of the present invention, it is necessary to use the reaction product [B] in a state of being dissolved or suspended in an aliphatic hydrocarbon or an alicyclic hydrocarbon.

The chemical structure of the reaction product [B] thus obtained is
As a result of analysis, alcohol, aldehyde or ketone reacts with SiH bond in the intermediate reaction product [A],
It was found that a compound having a —O—C bond was formed.

A specific titanium compound can be used as the transition metal compound used in the present invention.

That is, the general formula Ti (OR ⁷ ) _m X _4-m (where R ⁷ is a carbon number 1 to
10 alkyl groups, X is Cl atom or Br atom, m is 2-4
A suitable alkoxy-containing titanium compound represented by number) are, for example, _{Ti (OC 2 H 5) 2} Cl 2, Ti (On-C 3 H 7) 2 Cl 2, Ti (Oiso-C 3 H 7) _{2 Cl 2, Ti (On-} C 4 H 9) 2 Cl 2, Ti (Oiso-C 4 H 9) 2 Cl 2, Ti (On-C 8 H 17) 2 Cl 2, Ti (OC 2 H 5) _{3 Cl, Ti (On-C} 3 H 7) 3 Cl, Ti (Oiso-C 3 H 7) 3 Cl, Ti (On-C 4 H 9) 3 Cl, Ti (Oiso-C 4 H 9) 3 Cl _{, Ti (On-C 8 H} 17) 3 Cl, Ti (OC 2 H 5) 4, Ti (On-C 3 H 7) 4, Ti (Oiso-C 3 H 7)
_{4, Ti (On-C 4} H 9) 4, Ti (Oiso-C 4 H 9) 4, Ti (On-C 8 H
₁₇ ) It is ₄ mag. Further, a low molecular weight condensate obtained by hydrolyzing these titanium compounds can also be used. Specific examples are nC ₄ H ₉ O _{[Ti (On-C 4 H 9} ) 2 O ] ₄ nC ₄ H ₉ and the like.

The transition metal compound may also be a vanadium compound, particularly a compound represented by the general formula VO (OR ⁸ ) _n X _3-n or V (OR ⁹ ) _p X _4-p (where:
R ⁸ and R ⁹ are alkyl groups having 1 to 10 carbon atoms, X is a Cl atom or B
An alkoxy group-containing vanadium compound represented by r atom, n is a number of 2-3, and p is a number of 2-4 can be used. Specific examples _{VO (OC 2 H 5) 2} Cl, VO (On-C 3 H 7) 2 Cl, VO (Oiso-C 3 H 7) 2 Cl, VO (On-C 4 H 9) 2 Cl, _{VO (On-C 3 H 7} ) 2 Cl, VO (OC 2 H 5) 3, VO (On-C
_{3 H 7) 3, VO (} Oiso-C 3 H 7) 3, VO (On-C 4 H 9) 3, VO (OC 2 H 5) 2
_{Cl 2, V (On-C} 3 H 7) 2 Cl 2, V (Oiso-C 3 H 7) 2 Cl 2, V (On-C 4 H 9) 2 Cl 2, V (OC 2 H 5) 3 Cl, V (On-C ₃ H ₇ )
_{3 Cl, V (Oiso-C} 3 H 7) 3 Cl, V (On-C 4 H 9) 3 Cl, V (OC
_{2 H 5) 4, V (} On-C 3 H 7) 4, V (Oiso-C 3 H 7) 4, V (On-C
_{4 H 9) 4, V (} Oiso-C 4 H 9) 4 , and the like.

When a titanium or vanadium compound that does not contain an alkoxy group or contains a small amount of an alkoxy group is used, a highly active catalyst is obtained, but a polymer having a low density and a wide particle size distribution is obtained, and the effect of the present application is sufficient. Can't be reached.

The organoaluminum compound used in the present invention has the general formula
AlR ₂ X (wherein R ¹⁰ is a hydrocarbon group having 1 to ¹⁰ carbon atoms, X is
It is a halogen-containing organoaluminum compound represented by Cl atom or Br atom). Specifically, for example, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, di-iso-butyl aluminum chloride, di-n.
-Hexyl aluminum chloride, di-n-octyl aluminum chloride, diethyl aluminum bromide and the like.

As the above-mentioned organoaluminum compound, when a halogen-free organoaluminum compound such as trialkylaluminum is used, the activity is remarkably low, while when an halogen-containing organoaluminum compound such as an alkylaluminum dihalide is used, However, only a polymer having a low bulk density and a wide particle size distribution can be obtained.

The catalyst component [C], which is one of the constituent components of the catalyst used in the polymerization of the present invention, comprises: component [I]: reaction product [B] component [II]: titanium and / or vanadium compound component [III]: It is obtained by contacting and reacting each component of the organoaluminum compound.

However, in order to sufficiently achieve the object of the present application, it was found that a specific reaction procedure needs to be taken. That is, it is necessary to first react the component [I] and the component [II], and then to react the component [III]. In other procedures, there are some problems such as a decrease in activity and deterioration of powder characteristics. It was found to appear.

The catalyst component [C] of the present invention does not require separation of fixed components or washing and removal of excess titanium or vanadium compound in the liquid phase, which is usually carried out in the preparation of a supported catalyst using a carrier. That is, the reaction product obtained by contacting and reacting the above three components can be used as it is, and the preparation is extremely easy and simple.

The preparation conditions for the catalyst component [C] of the present invention are as follows.
And the component [II] are contacted at 20 to 100 ° C for 0.5 to 3 hours, and then the component [III] is added, 0 to 100 ° C, preferably 30 to
Incubate at 80 ° C for 0.5-5 hours.

The ratio of each component is 0.005 to 0.5 mol, preferably 0.01 to 0.3 mol of the component [II], and 0.01 to 0.3 mol of the component [II] per 1 gram atom of magnesium in the reaction product [B] of [I].
It is 5 to 10 mol, preferably 1 to 5 mol.

The catalyst component [C] is generally prepared in a diluent of an aliphatic hydrocarbon or an alicyclic hydrocarbon. It is not preferable to use an aromatic compound or a mixture of a large amount of an aromatic compound as the diluent, since it causes a decrease in catalytic activity. Examples of preferred diluents are n-hexane, n-heptane, n-decane, cyclohexane, methylcyclohexane and the like.

The catalyst component [C] thus obtained is used for the polymerization or copolymerization of ethylene with the alkylaluminum compound which is the cocatalyst. The alkylaluminum compound used is a compound represented by the general formula AlR ¹¹ _q H _3-q (wherein R ¹¹ is an alkyl group having 1 to 10 carbon atoms, and q is a number of 2 to 3). Specific examples thereof include trimethyl aluminum, triethyl aluminum, tributyl aluminum, trioctyl aluminum, diethyl aluminum hydride and dibutyl aluminum hydride.

The catalyst used in the polymerization or copolymerization of ethylene of the present invention can be easily prepared by bringing the catalyst component [C] into contact with an alkylaluminum compound.

The preferable ratio of both as a polymerization and copolymerization catalyst of ethylene is 1 to 1000 of Al in the alkylaluminum compound per 1 gram atom of Ti and / or V in the catalyst component [C].
Gram atom, preferably 10 to 200 gram atom.

The method for polymerizing and copolymerizing ethylene of the present invention is the same as when using a general Ziegler type catalyst, and a method such as a slurry polymerization method or a gas phase polymerization method can be adopted. Also, the polymerization reaction can be carried out in two or more stages under different reaction conditions.

When the polymerization is carried out by the slurry polymerization method, the catalyst of the present invention is dispersed in a suitable inert hydrocarbon solvent such as hexane, heptane and kerosene, and ethylene or ethylene and α
-Easily done by feeding in olefins. The polymerization temperature is 30 to 100 ° C, preferably 60 to 90 ° C.

The polymerization pressure is preferably atmospheric pressure to 50 kg / cm ² . in this case,
Alkyl aluminum compound is 0.05-10 per 1 solvent
It is used in mmol, preferably 0.1-5 mmol.

The molecular weight of the polymer produced by the method of the present invention, the polymerization temperature,
It can be adjusted by the amount of the catalyst used and the addition of hydrogen to the polymerization system, but the addition of hydrogen is the most effective adjustment method.

The process of the present invention comprises the polymerization of ethylene and ethylene and up to about 20% by weight of ethylene of propylene, butene-
It is useful for producing an ethylene-based copolymer by copolymerization with α-olefins such as 1, 1, hexene-1 and octene-1.

(E) Examples Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

The measuring method in the following examples is as follows.

MI ₂ : ASTM-D-1238-65T Melt index at a temperature of 190 degrees and a load of 2.16 kg Bulk density: JIS K6721-1966 Particle size distribution: 50 g of polymer is used with 11 kinds of sieves from 32 to 270 mesh, It shook with a Ro-Tap type shaker for 15 minutes, classified, and determined. The 50% particle size is the average particle size.

Wide particle size distribution: Nikkan Kogyo Shimbun, "Dust collector", 15
~ 80, 1965 σ is the geometric standard deviation in the log probability distribution formula, and the smaller the value of Log σ, the narrower the particle size distribution.

Angle of repose: By injection method.

Example 1 (1) Production of Reaction Product [B] 800 ml of a di-isopropyl ether solution of n-butyl magnesium chloride (commercially available product: as n-butyl magnesium chloride) was placed in a glass reactor whose interior was thoroughly dried and nitrogen purged in advance. 1.34mol) was collected and the end was blocked with trimethylsilyl group while stirring. Methylhydropolysiloxane (viscosity at 25 ℃ was about 30 centistokes) 8
0.5 ml (1.34 mol as Si) was added dropwise over 1 hour while maintaining room temperature. After the dropping, stirring was continued for 1 hour to obtain a brown transparent intermediate reaction product [A].

When the infrared absorption spectrum of the intermediate reaction product [A] was measured, it was found that the SiH bond (2100 cm ^-1 ) and the Si-CH ₃ bond (1250 cm
⁻¹ ) absorption intensity ratio (SiH bond / Si—CH ₃ bond) was 1.10.

In the solution of the intermediate reaction product [A] thus obtained, n-
After adding and diluting 500 ml of heptane, 1.34 mol of 2-ethylhexanol was added dropwise at room temperature over 1 hour.

After completion of dropping, perform vacuum distillation at a pressure of 120-240 mmHg and
Was distilled. The reaction mixture was diluted with n-heptane to obtain a colorless transparent reaction product [B] in an n-heptane. The concentration of magnesium was 0.782 mol /, and as a result of analysis by gas chromatography, diisopropyl ether was not present. In addition, the infrared absorption spectrum of the reaction product [B] was measured. As a result, the absorption intensity ratio of Si—H bond / Si—CH ₃ bond was 0.10, and most of the Si—H bond reacted with 2-ethylhexanol. Was there.

(2) Preparation of Catalyst Component [C] 101 ml of n-heptane and 63 mmol of the reaction product [B] obtained in (1) were collected in advance in a glass reactor whose inside was dried and purged with nitrogen. While stirring, 6.3 mmol of tetraisopropoxy titanium was added at room temperature, and the mixture was heated at 50 ° C. for 1 hour. Then, the temperature is raised to 70 ° C. and n
-Diethyl aluminum chloride diluted with heptane
117 ml (189 mmol) were added over 1 hour. Then, it was further heated for 1 hour to obtain a catalyst component [C].

(3) Polymerization of ethylene The inside was dried, and 600 ml of n-hexane was charged into a 1.6-made autoclave made of ethylene and substituted with ethylene, and heated to 60 ° C. Next, the catalyst obtained in (2) was used as titanium.
20 mg and triethylaluminum 0.5 mmol were added successively.

Then, hydrogen was introduced at 2.5 kg / cm ² (absolute pressure), the temperature was raised to 75 ° C., and polymerization was carried out for 1 hour at 8 kg / cm ² (gauge pressure) while continuously introducing ethylene. The product was separated from the solvent and dried to obtain 60.8 g of white powdery polyethylene. The polyethylene had a MI ₂ of 0.74 and a density of 0.9580. Furthermore, the powder properties of this polyethylene are: bulk density 0.386 g / cm ³ , average particle size 126μ, Log σ 0.10, repose angle 33 °, particle size 63
The contents of fine particles of μ or less and large particles of 500 μm or more in particle size were 1% by weight or less, respectively, which were very small. That is, the bulk density is high, the particle size distribution is narrow, and the fluidity of the powder is extremely good.

The polymerization activity of the catalyst of this example was 304 kgPE / gTi · hr.

Example 2 Preparation of catalyst component [C] and polymerization of ethylene Catalyst component [C] was prepared in the same manner as in Example 1 except that the amount of diethylaluminum chloride used was 252 mmol and the stirring speed was slightly reduced. . Subsequently, ethylene was polymerized under the same conditions as in Example 1 to give polyethylene powder 55.2.
got g. The catalyst preparation conditions and polymerization results are shown in Table I,
Shown in Table II.

Example 3 Preparation of catalyst component [C] and polymerization of ethylene The amount of tetraisopropoxy titanium used was 12.6 mmol,
A catalyst component [C] was prepared in the same manner as in Example 1 except that the amount of diethylaluminum chloride used was 315 mmol. Using this catalyst component [C], ethylene was polymerized under the same conditions as in Example 1 to obtain 50.4 g of polyethylene. The polymerization results are shown in Table II.

Example 4 (1) Production of reaction product [B] A reaction product [B] was prepared in the same manner as in Example 1- (1) except that 2-ethylhexaldehyde was used instead of 2-ethylhexanol. Production of magnesium concentration
A 0.874 mol / colorless transparent n-heptane solution was obtained.

(2) Preparation of catalyst component [C] A catalyst component [C] was prepared under the same conditions as in Example 1 except that the above reaction product [B] was used.

(3) Polymerization of ethylene Ethylene was polymerized under the same conditions as in Example 1 to obtain 70 g of polyethylene. The polymerization results are shown in Table II.

Example 5 Preparation of catalyst component [C] and polymerization of ethylene A catalyst component [C] was prepared in the same manner as in Example 4 except that tetra-n-butoxytitanium was used as the titanium compound. Subsequently, ethylene was polymerized under the same conditions as in Example 1,
73 g of polyethylene was obtained. The polymerization results are shown in Table II.

Examples 6 to 8 Preparation of catalyst component [C] and polymerization of ethylene Catalyst component [C] was prepared in the same manner as in Example 1 except that triisopropoxyvanadyl was used together with tetraisopropoxytitanium in the ratio shown in Table I. Prepared. Polymerization of ethylene using each catalyst component [C] yielded 94.4 g of polyethylene in Example 6 and 110 g of polyethylene in Example 7. In Example 8, when the catalyst of Example 7 was used and the polymerization time was 3 hours, the yield of polyethylene was 270 g. In this case, the catalytic activity corresponds to 1.350 kg PE / gTi.
The results are summarized in Table II.

Example 9 Preparation of catalyst component [C] and polymerization of ethylene A catalyst component [C] was prepared in the same manner as in Example 1 except that diisobutylaluminum chloride was used instead of diethylaluminum chloride. When ethylene was polymerized, 68.4 g of polyethylene was obtained.

Comparative Example 1 Preparation of Catalyst Component [C] and Polymerization of Ethylene The reaction product [B] was reacted with diethylaluminum chloride first, and then tetraisopropoxytitanium was reacted with the same procedure as in Example 1. A catalyst component [C] was prepared. Example 1 using this catalyst component [C]
When ethylene was polymerized under the same conditions as above, 80 g of polyethylene which was extremely bulky and had irregular particle shapes was obtained.
The results are shown in Table II.

Comparative Example 2 Preparation of Catalyst Component [C] and Polymerization of Ethylene Catalyst was prepared in the same manner as in Example 1 except that tetraisopropoxy titanium and diethyl aluminum chloride were first reacted and then the reaction product [B] was reacted. Component [C] was prepared. When ethylene was polymerized, only a small amount of polymer was obtained.

Comparative Example 3 Preparation of catalyst component [C] and polymerization of ethylene A catalyst component [C] was prepared in the same manner as in Example 1 except that titanium tetrachloride was used as the titanium compound. Polymerization of ethylene gave 199 g of polyethylene.

Comparative Examples 4,5 Preparation of Catalyst Component [C] and Polymerization of Ethylene In Example 1- (2), ethylaluminum dichloride or triethylaluminum was used in place of diethylaluminum chloride, respectively. When ethylene was polymerized in the same manner using the obtained catalyst component [C], 85.4 g of polyethylene was obtained in Comparative Example 4, and no solid polymer was observed in Comparative Example 5.

(F) Effect of the invention a Catalytic activity In both homopolymerization and copolymerization of ethylene, the catalytic activity is 250 to 600 kgPE / gTi · hr, which is extremely high.
At the same time, this catalyst is characterized by long-term activity.

b Powder characteristics of produced polymer Ethylene homopolymer and copolymer have bulk density of 0.350
With the above, 0.37 to 0.41 is often reached.

The particle size distribution (Log σ) is very narrow at 0.09-0.11, and the content ratio of fine particles of 63μ or less and large particles of 500μ or more is 1% by weight or less, which is extremely small.

Furthermore, since the particle shape is close to a sphere, the repose angle of the powder is 30.
It is as small as -35 degrees and has good fluidity of powder. Further, particularly by the method of the present invention, it is possible to easily obtain a polymer powder having a small particle diameter of 250 μm or less.

Since the powder characteristics are excellent as described above, troubles in the manufacturing process can be eliminated, and stable long-term operation and productivity can be improved. Further, the obtained polymer powder has excellent suitability for powder molding such as rotational molding and powder coating processing such as fluidized dipping and sintering molding.

c Catalyst preparation Generally, a liquid commercial raw material can be used without using a solid or powder raw material which is difficult to handle as a catalyst raw material. The catalyst preparation is
It is very convenient because it only needs to mix and contact the raw materials and does not require isolation and washing of solid catalyst components. In addition, it does not require disposal of transition metal compounds and the like, which is required by many prior arts.

The method of the present invention is superior to the prior art in that it has the above three effects.

In Comparative Examples 1 and 2, the effect of the order of addition of the catalyst components was examined, but Comparative Example 1 has a low bulk density and Comparative Example 2 has a low activity. Further, Comparative Example 3 is a type of titanium compound, Comparative Example
Nos. 4 and 5 investigate the effect of the type of organoaluminum compound, but Comparative Examples 3 and 4 have poor bulk density, particle size distribution, etc., and Comparative Example 5 does not show catalytic activity.

d Differences from Prior Art FIG. 1 shows the present invention, and FIG. 2 shows the prior art (Japanese Patent Application No. 57-1217).
59) shows the flowchart. Therefore, the differences between these two technologies can be summarized as follows. In terms of constitution, in the present invention, compounds in which the transition metal component and the organometallic component (organoaluminum compound) are more limited than those in the prior art are used.

In the present invention, the reaction sequence of each catalyst component is limited, whereas the prior art is not limited.

In the present invention, the polymerization method is limited to the slurry polymerization method, whereas the prior art is not limited.

In terms of effects, the present invention has extremely good powder characteristics, that is, bulk density, particle size distribution, and powder fluidity, but the prior art was very poor.

You can point out such points.

[Brief description of drawings]

FIG. 1 shows a flowchart of the present invention. FIG. 2 shows a typical Japanese Patent Application No. 57-12 as a prior art of the present invention.
The method of 1759 is shown with a flowchart.

Claims (1)

[Claims] 1. An intermediate reaction product [A] obtained by the reaction of the following components [I] to [III] [I] hydropolysiloxane with a Grignard reagent, and at least one selected from alcohols, aldehydes and ketones. Using a catalyst obtained by contacting a reaction product [B] obtained by reacting one or more kinds of nucleophilic reagents, [II] transition metal compound [III] organoaluminum compound, ethylene or ethylene and other α - a method for polymerizing or copolymerizing olefins, as component [II], (1) the general formula ^{_{Ti (oR 7) m X 4}} -m ( wherein, R ₇ is an alkyl group having 1 to 10 carbon atoms, X is Cl atom or
Br atom, m is a number of 2 to 4) and / or (2) the general formula VO (OR ⁸ ) _n X _3-n or V (OR
⁹ ) _p X _4-p (where R ⁸ and R ⁹ are alkyl groups having 1 to 10 carbon atoms,
X is Cl atom or Br atom, n is a number of 2-3, and p is 2-4.
Of the general formula AlR ¹⁰ ₂ X (where R ¹⁰
Is a hydrocarbon group having 1 to 10 carbon atoms, X is Cl atom or Br atom)
Each of the organoaluminum compounds represented by
And a catalyst component [C] obtained by reacting the component [III] with each other, and a general formula AlR ¹¹ _q X _3-q (wherein R ¹¹ is an alkyl group having 1 to 10 carbon atoms, q is It is a number of 2 to 3) In the presence of a catalyst consisting of an alkylaluminum compound represented by the following formula, at the polymerization temperature of 30 to 100 ° C, polymerization or copolymerization in a slurry form is carried out, and an ethylene polymer is produced. Method.