JPS58453B2 - Ethylene polymerization or copolymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing or copolymerizing ethylene using a highly active catalyst.

More specifically, the present invention relates to a method for obtaining an ethylene polymer or copolymer having a suitably uniform polymer particle size.

The present invention further provides a method for controlling the particle size of the resulting polymer.

Conventionally, an olefin polymerization method using a highly active catalyst component in which a titanium or vanadium compound is supported on a magnesium halide compound has been known.

For example, Japanese Patent Publication No. 41467/1977 describes a catalyst component in which titanium tetrachloride is supported on magnesium halide activated by a ball mill;
No. 1-152 proposes a catalyst composition in which a titanium compound and/or vanadium compound is supported on a reaction product of anhydrous magnesium halide and an aluminum compound represented by the general formula AI(OR)3. .

Furthermore, in Japanese Patent Publication No. 50-32270, there is a description of the...ride of group Ⅰ metals of the periodic table coordinated with an electron donor and the
A transition metal catalyst component is described in which a reaction product of a group metal to a group II metal with an organometallic compound or hydride is reacted with a transition metal compound selected from the group consisting of a titanium compound and a vanadium compound.

When these conventionally known catalyst components are used in combination with an organometallic compound catalyst component for olefin polymerization, polymers with small particle sizes tend to be produced.

When fine powder polymer is produced during olefin polymerization, it becomes difficult to transport the polymer, it becomes difficult to recover the polymer from the polymer slurry, and the workability when pelletizing the polymer with an extruder becomes poor. Problems can easily occur.

As a result of our intensive search for a catalyst that has a large particle size to a certain extent and produces less fine powder polymers, we discovered that water in the contact between magnesium halogen compounds and electron bodies, which had not been recognized in this technical field, A new fact has been discovered that the presence of particles is one of the important controlling factors for the unfavorable atomization phenomenon in the particle size of the above polymers.

Further investigation into this fact revealed that the reaction product obtained by contacting the solid component obtained by reacting the electron donor-treated magnesium halogen compound with an aluminum or silicon compound and the titanium or vanadium halogen compound was titanium. It has been discovered that in a catalyst system as a catalyst component, the amount of water present needs to be selected within a specific range.

Therefore, an object of the present invention is to provide an industrially advantageous method for producing an ethylene polymer or copolymer having excellent particle size and distribution while avoiding the above-mentioned troubles.

The present invention also provides a catalyst that allows the particle size of the produced polymer to be arbitrarily controlled in order to obtain a polymer having a particle size that matches the polymerization apparatus.

That is, the present invention provides (A) (i) a magnesium halogen compound for an electron donor and the magnesium halogen compound,
After contacting with about 0.5 to about 10% by weight of water, (11) an organometallic compound or hydride of a metal of groups ■ to ■ of the periodic table, AI(OR)nX3-n (wherein R is carbide); At least one aluminum or silicon compound selected from the group consisting of an aluminum compound, a silicon halogen compound, and a hydropolysiloxane represented by a hydrogen group, X represents a halogen atom, and 0<n≦3. (iii) a catalyst component obtained by contacting the solid component obtained by the reaction with a halogen compound of titanium or vanadium; and (B) a catalyst consisting of an organometallic compound of a metal from Groups ■ to ■ of the periodic table; Alternatively, it is an ethylene polymerization or copolymerization method characterized by bringing ethylene into contact with a mixture of other olefins and/or diolefins.

It is known that a catalyst component obtained by reacting a hydrate of a magnesium halide compound with a titanium or vanadium compound is used for olefin polymerization.

For example, Japanese Patent Publication No. 48-19794 describes a catalyst component obtained by reacting magnesium halide represented by MgX2.nH2O (X is a halogen, n is a number larger than 0) with a titanium or vanadium compound, and also, JP-A No. 47-34783 discloses a catalyst component obtained by contacting a titanium compound with a reaction product of hydrated magnesium halide and an organometallic compound of a metal in groups ■, ■, or ■ of the periodic table. ing.

However, these known proposals do not mention anything about the particle size of the resulting polymer, and by polymerizing or copolymerizing ethylene using the catalyst component prepared by the specific method of the present invention, fine powder polymerization can be achieved. There is no mention or suggestion that it is possible to obtain a polymer with less coalescence and a large average particle size, and that the particle size of the polymer can be controlled arbitrarily.

(1) The magnesium halogen compound used in the present invention may contain other groups such as an alkyl group, an alkoxy group, or an acyloxy group, but magnesium cybalide and Brinillard reagents are preferably used. can.

The ones that give the best results are magnesium cybarides, such as magnesium chloride, magnesium bromide,
Examples include magnesium iodide, and magnesium chloride is particularly preferred.

The electron donor used in the present invention includes carboxylic acids, esters, ethers, ketones, aldehydes, alcohols, oxygen-containing compounds such as acid amides, nitriles, amines, phosphines, etc., and is preferably Mention may be made of oxygenates and nitriles.

More specifically, aliphatic or aromatic carboxylic acids, esters of aliphatic or aromatic carboxylic acids, aliphatic or cyclic ethers, aliphatic ketones, aliphatic aldehydes, aliphatic alcohols, aliphatic Preferred examples include oxygen-containing compounds such as acid amides, aliphatic or aromatic nitriles, aliphatic or aromatic amines, aliphatic or aromatic phosphines, etc. I can do it.

C1 to C12 aliphatic carboxylic acid, C7 to C12 aromatic carboxylic acid, C1 to C12 aliphatic carboxylic acid and C1 to C12 saturated aliphatic or unsaturated aliphatic alcohol Esters of aliphatic carboxylic acids, esters of aromatic carboxylic acids of aromatic carboxylic acids having 7 to 12 carbon atoms and aliphatic alcohols having 1 to 12 carbon atoms, aliphatic ethers having 2 to 12 carbon atoms, 3 to 12 carbon atoms 4 cyclic ethers, aliphatic ketones having 2 to 13 carbon atoms, aliphatic aldehydes having 1 to 12 carbon atoms, aliphatic alcohols having 1 to 12 carbon atoms, aliphatic acid amides having 1 to 12 carbon atoms, aliphatic acid amides having 2 to 12 carbon atoms, C12 aliphatic nitrile, C7 to C12 aromatic nitrile, C1 to C12 aliphatic amine, C6 to C10
A compound selected from the group consisting of aromatic amines having 3 to 18 carbon atoms, and aromatic phosphines having 6 to 21 carbon atoms is recommended as the electron donor used in the present invention.

Specific examples of such electron donors include aliphatic carboxylic acids such as acetic acid, propionic acid, valeric acid, acrylic acid, aromatic carboxylic acids such as benzoic acid, phthalic acid, methyl formate, dodecyl formate, and acetic acid. Aliphatic carboxylic acid esters such as ethyl, butyl acetate, vinyl acetate, methyl acrylate, octyl butyrate, ethyl laurate, octyl laurate; such as methyl monobenzoate, ethyl benzoate, octyl paraoxybenzoate, dioctyl phthalate aromatic carboxylic acid esters: aliphatic ethers such as ethyl ether, hexyl ether, acrylic butyl ether, methyl undecyl ether: tetrahydrofuran,
Cyclic ethers such as dioxane, trioxane; aliphatic amines such as methylamine, diethylamine, tributylamine, octylamine, dodecylamine; aromatic amines such as pyridine, aniline, naphthylamine; acetone, methylimbutylketone, ethylbutylene.

Aliphatic ketones such as acetophenone, dihexyl ketone: Aliphatic aldehydes such as propionaldehyde: Aliphatic ketones such as methanol, ethanol, impropatol, hexanol, 2-ethylhexanol, octatool, dodecanol Alcohol, aliphatic nitrile such as acetonitrile, valeronitrile, acrylonitrile; aromatic nitrile such as benzonitrile, phthalonitrile; aliphatic acid amide such as acetic acid amide; phosphine such as triethylphosphine, triphenylphosphine, etc. be able to.

Among these, aliphatic alcohols are preferred, and particularly preferred examples include methanol, ethanol, and isopropanol.

In the aluminum or silicon compound used in the present invention, (ii) the organometallic compound or hydride of a metal of Groups I to II of the Periodic Table has the general formula RM (where R is an alkyl group having 1 to 20 carbon atoms). or a galyl group, M represents Li, Na, K), an organometallic compound of a Group 1 metal represented by the general formula HM (M is the same as above), a hydride of a Group 1 metal represented by the general formula HM (M is the same as above); A complex alkylated product of Group 1 metal with A1 having the general formula MAlH4 (R and M are the same as above), the general formula MA
A complex hydride of a Group 1 metal and A1 which is represented by lH4 (M is the same as above), an organometallic compound of a Group 2 metal which is represented by the general formula RR'M' (where R is the same as above) , R' is an alkyl group or aryl group having 1 to 20 carbon atoms, M/ represents Mg, Zn, Cd), general formula RR'
R”Al, RR’AlX, RR’AI(OR”), RA
l(OR') (OR"), RAI(OR') and X represents a halogen atom), among which preferred are alkylaluminum compounds, particularly dialkylaluminum halides, and particularly preferred is diethylaluminum chloride.

In addition, in the aluminum compound represented by AI (OR) nX3-n (wherein R is a hydrocarbon group, X is a halogen atom, and 0<n≦3), R is a hydrocarbon residue having 1 to 20 carbon atoms. Groups are preferred.

The above aluminum compounds include aluminum trimethoxide, aluminum triethoxide, monomethoxyjethoxyaluminum, aluminum tri-n-propoxide, aluminum triisopropoxide, monomethoxydiisopropoxyaluminum, aluminum tri-n-butoxide, aluminum tri-5ec-butoxide, aluminum tri-t-butoxide, aluminum triphenoxide, aluminum dimethoxy monochloride, aluminum monomethoxy diclide, aluminum jetoxy monochloride, aluminum jetoxy monochloride, aluminum diisopropoxy monochloride,
Aluminum diphenoxy monochloride, aluminum 5ee-butoxy monochloride, aluminum di-5ee
-butoxy monopromide, aluminum diphenoxy monochloride, aluminum diphenoxy monochloride,
Examples include aluminum monoethoxy mono-5ee-butoxy monochloride.

The silicon halogen compounds used in the present invention include:
General formula RISimXp (where R represents an alkyl group, cycloalkyl group, or aryl group, X is a halogen atom, ■ is O or a positive integer, p and m are natural numbers, and 1+p=2 m +2) Examples include silicon compounds represented by:

Specific examples of such silicon halogen compounds include tetrahalogen compounds such as tetrachlorosilane, tetrabromosilane, tetraiodosilane, tetrafluorosilane, trichlorobromosilane, trichlorofluorosilane, dichlorodibromosilane, and chlorotribromosilane. Silane: Hexachlorodisilane, hexabromodisilane, octachlortrisilane, decachlortetrasilane, dodecachlorpentasilane, etc. Polysilane: Methyltrichlorosilane, ethyltrichlorosilane, chloromethyltrichlorosilane, dichloromethyltrichlorosilane, etc. Haloalkyltrichlorsilane Silane: Examples include arylhalosilanes such as diphenyldichlorosilane; cycloalkylhalosilanes such as cyclohexyltrichlorosilane;

The hydropolysiloxanes used in the present invention include tetramethylhydrodisiloxane, diphenylhydrodisiloxane, cyclic trimethylhydrotrisiloxane, cyclic tetramethylhydrotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, Examples include polysiloxane, cyclooctylhydropolysiloxane, chlorphenylhydropolysiloxane, and the like.

Among these, particularly preferred are organometallic compounds of metals from groups 1 to 2 of the periodic table or aluminum compounds represented by AI(OR)nX3-n.

Examples of the titanium or vanadium compound (iii) of the present invention include general formulas TiX4, Ti(0R)4-nXn,
Examples include compounds represented by VOX3VX4 (where X represents a halogen and R represents an alkyl group or an aryl group).

Specific examples include titanium compounds such as titanium tetrachloride, titanium tetrabromide, titanium ethoxytrichloride, titanium diethoxydichloride, titanium dibutoxydichloride, and titanium phenoxytrichloride, and vanadium tetrachloride compounds.

In the present invention, various methods can be used to bring the magnesium halogen compound into contact with water and electron donor.

The contact is preferably carried out at a temperature of about 100°C or lower.

For example, a magnesium halide can be contacted with a mixture of an electron donor and water.

Alternatively, the magnesium halogen compound can be brought into contact with water and then brought into contact with an electron donor.

Still another method is a method in which a halogen compound of magnesium is brought into contact with an electron donor and then water is brought into contact with the halogen compound.

The above contacting operation may be carried out in the presence of an inert solvent, such as an inert hydrocarbon such as hexane, heptane, or kerosene.

It is also possible to use electron bodies as a solvent.

Furthermore, the electron donor may be removed by evaporation or the solid product may be separated at any stage of the above-mentioned contacting operation.

For example, a method may be used in which a magnesium halogen compound is brought into contact with an electron body, and after removing as much of the electron donor as possible by evaporation, the compound is brought into contact with water.

The halogenated magnesium compound may be brought into contact with air, and the moisture in the air may be used to bring the halogenated magnesium compound into contact with water.

The amount of water used to contact the magnesium halide is about 0.5 to about 10% by weight, preferably about 0.5 to about 8%, more preferably about 1% by weight, based on the magnesium halide. .5 to about 5% by weight.

Further, the electron donor of the present invention is used in a proportion of at least about 0.01 mol, preferably at least about 0.1 mol, more preferably about 0.1 mol, per 1 mol of the magnesium halide compound. from about 10 moles.

By increasing the amount of water used, the particle size of the resulting polymer can be increased.

However, the use of water exceeding the above range is not preferable since it may reduce the polymerization activity of the catalyst.

In the present invention, the amount of water that is brought into contact with the magnesium halogen compound is an amount that includes water that the compound and the electron donor may contain.

In order to react the aluminum or silicon compound after contacting the magnesium halide compound with water and an electron donor, it is preferable to carry out the reaction in the presence of an inert solvent. It is also possible.

Therefore, the reaction can be carried out without removing the electron body used in the contact treatment with the electron donor.

After contacting the magnesium halogen compound with water and the electron donor, if a solid and a liquid phase coexist, the solid may be separated and reacted with the reaction component (ii).

In the above reaction, the reaction rate (ii
) is preferably used in a proportion of about 0.01 mol to about 20 mol, more preferably about 0.05 mol to about 10 mol, in terms of metal atoms.

The preferred temperature for the above reaction is about 0 to about 200°C, more preferably about 20 to about 150°C.

When the solid component obtained by the above reaction is brought into contact with a titanium or vanadium compound, the catalyst component of the present invention is obtained.

When the solid component is obtained as a suspension, the solid component may be separated from the suspension prior to contacting with the titanium or vanadium compound, or may be used as is without separation.

The catalyst component of the present invention can be obtained by bringing the solid component into contact with the titanium or vanadium compound in the presence or absence of an inert solvent.

The amount of the titanium or vanadium compound to be used is preferably 0.01 mol or more, more preferably about 0.01 mol or more in terms of titanium atoms, per 1 atom of magnesium in the reaction product.
The amount is preferably 1 mole or more.

Generally, it is preferred that the contact be carried out at a temperature of room temperature to about 130° C. for about 30 minutes or more.

At the end of the contacting operation with the titanium or vanadium compound, a hydrocarbon-insoluble product is formed.

Usually, this product is separated from the liquid phase by filtration, decantation or other suitable solid-liquid phase separation means, and more preferably washed with an inert solvent before being subjected to polymerization.

The contact operation and reaction operation in the present invention are preferably carried out under conditions involving ordinary stirring or mechanical pulverization using a ball mill or the like.

As the organometallic compound (B) of a metal in group ■ or ■ of the periodic table, those having a hydrocarbon group directly bonded to the metal can be used, such as alkyl aluminum compounds, alkyl aluminum alkoxides, alkyl aluminum halides, and alkyl aluminum alkoxy halides. .

Further, alkylaluminum hydride, dialkylzinc, dialkylmagnesium, alkylmagnesium halide, etc. may be used.

All of these are those used in normal Ziegler type polymerization.

Polymerization can be carried out in either liquid phase or gas phase.

When carried out in a liquid phase, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium.

In the case of liquid phase polymerization, the solid catalyst component (a
) is about 0.001 to about 0.5 in terms of titanium atoms.
It is preferable to keep the amount of the organometallic compound (b) of a metal of Groups 1 to 8 of the periodic table at about 0.1 to about 50 mmol in terms of metal atoms.

A molecular weight regulator such as hydrogen may be used during the polymerization.

The polymerization temperature of the olefin is preferably 20 to 200
℃, more preferably 50 to below the softening point of the resulting polymer, and the pressure is normal pressure to 50 kg/cm2. Preferably, it is carried out under pressurized conditions of about 2 to 20 kg/cm 2 .

Polymerization can be carried out in any of the batch, semi-continuous and continuous systems.

Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

The present invention will be explained in more detail below using Examples.

Example l Preparation of titanium catalyst component 0.105 mol of magnesium chloride (water content 0.3% by weight) was suspended in 750 ml of purified anhydrous hexane in a nitrogen stream and mixed with 0.0 ml of ethanol containing 0.3 g of water with stirring. .7
After adding 3 mol of the mixture and raising the temperature to 100°C, stirring was continued for 30 minutes.

Next, jetoxyaluminum chloride (1
005 mol was added, and the reaction was carried out at 200°C for 2 hours.

Thereafter, the distillate was distilled off under reduced pressure, and the residue was dried under reduced pressure.

Titanium tetrachloride (1455 mol) was added to the product to give 130
The mixture was stirred at ℃ for 1 hour, and the resulting solid was separated by filtration and washed 10 times with hexane to obtain a titanium catalyst component.

Kerosene 11 from which oxygen and moisture have been sufficiently removed is charged into an autoclave with an internal volume of 21 for ethylene polymerization, and 102 mmol of the titanium catalyst component prepared above and 1 mmol of triethylaluminum are added in terms of titanium atoms. .

The temperature was raised to 80°C, hydrogen was added at a pressure of 4 kg/cm2, and then ethylene was added at a total pressure of 8 kg/cm2.
The polymerization was carried out for 2 hours by continuously supplying the solution so that the following conditions were met.

After polymerization, methanol is added to stop the polymerization.

The polymerization results are shown in Table 1. Comparative Example 1 A titanium catalyst component was prepared in the same manner as in Example 1 except that dehydrated and purified ethanol was used, and ethylene was polymerized. The polymerization results are shown in Table 1.

From the results of Example 1 and Comparative Example 1, it is clear that the method of the present invention can suppress the formation of fine powder polymers and increase the average particle size.

Example 2 Preparation of titanium catalyst component 0.58 g of water was added to 0.167 mol of n-butylmagnesium fluoride (concentration 2 mol/l) dissolved in tetrahydrofuran, and after stirring for 30 minutes, methylhydropolysiloxane ( Viscosity 16cP25℃) 0.175ml
In addition, the temperature was raised to 70°C and the reaction was carried out for 1 hour.

Subsequently, the distillate was distilled off under reduced pressure at 50°C and dried under reduced pressure. After adding 0.81 mol of toluene and 1.47 mol of n-heptane, 0.78 mol of titanium tetrachloride was added and the mixture was heated to 100°C. The temperature was raised and stirred for 30 minutes.

The produced solid component was separated by filtration and purified with purified hexane.
A titanium catalyst component was obtained by washing 0 times.

, Ethylene Polymerization Using the titanium catalyst component obtained above, ethylene polymerization was carried out under the same conditions as in Example 1. Table 2 shows the results.

Comparative Example 2 A titanium catalyst component was prepared in the same manner as in Example 2 except that water was not added, and ethylene was polymerized under the same conditions as in Example 1 using the titanium catalyst component obtained.

The results are shown in Table 2. Example 3 Preparation of titanium catalyst component Magnesium chloride used in Example 1 0.1 in nitrogen stream
Ethanol 0.685 containing 0.3 f of water in 0.5 mole
After stirring thoroughly, tri-5ec-butoxyaluminum (1024 moles) was added, the temperature was raised to 200°C, and the mixture was reacted for 2 hours with stirring.

Subsequently, 0.364 mol of titanium tetrachloride was added to make 130
The mixture was stirred at ℃ for 1 hour.

The solid portion was separated by filtration and washed 10 times with purified hexane to obtain a titanium catalyst component.

Polymerization of ethylene Ethylene polymerization was carried out under the same conditions as in Example 1 using the titanium catalyst component obtained above.

The polymerization results are shown in Table 2.

Comparative Example 3 A titanium catalyst component was prepared in the same manner as in Example 4, except that dehydrated and purified ethanol was used, and ethylene was polymerized in the same manner as in Example 3 using the obtained titanium catalyst component.

The polymerization results are shown in Table 2.

Examples 4 to 6 Preparation of titanium catalyst component Refined kerosene 125 from which water and oxygen were sufficiently removed in a nitrogen stream
Magnesium chloride (water content 0.3% by weight) was suspended in m1 (1063 mol), then 0.38 mol of ethanol containing the amount of water listed in Table 3 was added, and after stirring for 30 minutes, 0.17 mol of diethylaluminium chloride was added and stirring was continued for an additional 30 minutes.

Thereafter, titanium tetrachloride (1375 mol) was added and the temperature was raised to 80°C, followed by stirring for 1.5 hours, and the produced solid was separated by filtration.

The separated solid product was washed 10 times with purified hexane to obtain a titanium catalyst component.

Into an autoclave with an ethylene polymerization internal volume of 21, add 11 kerosene from which oxygen and water have been sufficiently removed, 0.3 mmol of triethylaluminum, and 0.01 mmol of the titanium catalyst component prepared above in terms of titanium atoms, The system was heated to 80°C.

After injecting 4 kg/cm2 of hydrogen, the total pressure is 8 kg/c.
Ethylene was continuously supplied so that the amount was 2 m2, and polymerization was carried out for 1 hour.

The polymerization results are shown in Table 3.

Comparative Example 4 A titanium catalyst component was prepared in the same manner as in Example 4, except that dehydrated and purified ethanol was used.

Ethylene was polymerized using the obtained titanium catalyst component under the same conditions as in Example 4.

Claims (1)

[Scope of Claims] 1(A) (i) After contacting a magnesium halogen compound with an electron donor and water in an amount of about 9.5 to about 10% by weight relative to the magnesium halogen compound, (ii) ) An organometallic compound or hydride of a metal from Groups I to II of the Periodic Table, Al(OR)nX3-n (wherein R is a hydrocarbon group, X is a halogen atom, and 0<n≦3) (iii) a titanium or vanadium halogen compound is added to the solid component obtained by reacting at least one aluminum or silicon compound selected from the group consisting of an aluminum compound, a silicon halogen compound, and a hydropolysiloxane; ethylene or a mixture of ethylene and other olefins and/or diolefins is brought into contact with the catalyst component obtained by contacting the catalyst component and (B) the organometallic compound component of a metal of Groups I to II of the Periodic Table. Characteristic ethylene polymerization or copolymerization method. 2. The method of claim 1, wherein the dimagnesium halogen compound is a compound selected from magnesium cybaride and Grignard reagent.