JPH0135843B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a carrier for an olefin polymerization catalyst. In particular, the present invention relates to a method for preparing a carrier suitable for producing a polyolefin with good powder flowability.

Conventionally, in this type of technical field, many catalysts are known in which compounds of transition metals such as titanium or vanadium are supported on inorganic magnesium solids such as magnesium halides, magnesium oxides, and magnesium hydroxides. . However, in these known techniques, the obtained polymer particles generally have a small bulk specific gravity, a small average particle size, and a generally wide particle size distribution, so they have a large particulate powder portion, which reduces productivity and slurry. Improvements were strongly desired in terms of handling. Furthermore, when molding these polymers, problems such as generation of dust and reduction in efficiency during molding occur, so the above-mentioned increase in bulk specific gravity,
It was strongly desired to increase the average particle size and reduce the particulate powder portion.

The present invention improves the above-mentioned drawbacks and provides a highly effective catalyst carrier that makes it possible to obtain a polymer with high bulk specific gravity, narrow particle size distribution, and excellent powder flowability with significantly less fine particulate portions of the polymer. It provides:

That is, the present invention uses a liquid medium that dissolves a substance containing at least one component of magnesium dihalide (hereinafter abbreviated as magnesium halide) and that contains an oxide of a metal of group ~~ of the periodic table.
By gradually adding a saturated hydrocarbon (hereinafter referred to as an organic liquid compound) to at least one liquid medium selected from alcohols, organic acid esters, ketones, and ethers while maintaining the temperature at 10°C or less. The present invention relates to a method for producing a carrier for an olefin polymerization catalyst, which comprises depositing a carrier made of a substance having a precipitated particle size of 5 μm or more. A titanium compound and/or a titanium compound and/or
Or, when olefin polymerization or copolymerization is carried out using a catalyst that combines a solid catalyst component supported with a vanadium compound and an organometallic compound,
The polymer yield per solid and the polymer yield per transition metal are significantly increased, thereby eliminating the need for a step for removing catalyst residues in the resulting polymer, and the resulting polymer powder has a high bulk specific gravity. It has a narrow particle size distribution, less particulate powder, good powder fluidity, and is not only easy to handle during polymerization operations but also has few troubles during molding, making it possible to produce polyolefins extremely advantageously. .

The present inventors previously filed a patent application for the case in which oxides of metals from Groups ~ of the periodic table do not coexist, but in the case of the present invention in which oxides of metals from Groups ~ of the periodic table coexist. The formation of irregularly shaped fine powder in the produced polymer is further reduced, the particle size distribution is further narrowed, and the bulk specific gravity is further improved.
Therefore, the powder fluidity is also extremely good.

The present invention will be explained in detail below.

In preparing the olefin polymerization catalyst carrier of the present invention, first, a substance containing at least one component of magnesium halide is dissolved in an organic liquid medium in which the substance can be dissolved.

The organic liquid medium for dissolving the substance containing at least one component of magnesium halide used at this time includes alcohols, esters, ethers, and ketones. Preferred specific examples include methanol, ethanol, and isopropanol. , butanol, pentanol, hexanol,
Alcohols such as octanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, vinyl acetate, methyl acrylate, methyl methacrylate, octyl butyrate, ethyl laurate, lauric acid Esters such as octyl, methyl benzoate, ethyl benzoate, octyl paraoxybenzoate, dibutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl maleate, diethyl maleate, dimethyl ether,
Examples include ethers such as diethyl ether, diisopropyl ether, dibutyl ether, diamyl ether, tetrahydrofuran, dioxane, and anisole, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, acetophenone, diphenyl ketone, and cyclohexanone. be able to.

The substance containing magnesium halide as at least one component used in the present invention refers to magnesium halide or magnesium halide and another substance.
It is a reaction product with more than one kind of compound or a mixture thereof.

Magnesium halides include magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, with magnesium chloride being particularly preferred.

Various known magnesium halide-containing carriers are used as the reaction product of magnesium halide and one or more other compounds. Specific examples of these include magnesium halide and Si
(OR) Reaction product with _n X _4-n , Reaction product between magnesium halide and B(OR) _o X _3-o , Reaction product between magnesium halide and Al(OR) _o X _3-o , Halogen Reaction product of magnesium chloride and AlOX, reaction product of magnesium halide and compound having Al-O-C bond, reaction product of magnesium halide and aluminum chloride or aluminum chloride ether complex, magnesium halide and pentachloride Phosphorus, reaction product with phosphorus trichloride or phosphorus oxytrichloride, magnesium halide and dichloroethane,
Reaction products with organic halides such as trichlorobenzene, reaction products between magnesium halide and titanium oxyhalide, reaction products between magnesium halide and Si(OR) _n X _4-n and Al(OR) _o X _3-o reactant,
Magnesium halide, silicon tetrachloride and ROH
(In the formula,
R is a hydrocarbon residue having 1 to 20 carbon atoms, X is a halogen, and 0≦m≦4, 0<n≦3). of course,
Other known halogenated magnesium-containing carriers can also be used in the present invention.

There are no particular restrictions on the operation and conditions for dissolving the substance containing magnesium halide as at least one component, and the dissolution may be carried out, for example, at room temperature or by heating as appropriate. Although the concentration of the solution can be selected within a wide range, a range of 1 to 30% by weight is usually preferably used.

When using a reaction product of magnesium halide and another compound, these may be reacted in advance and then dissolved, or the reaction may be performed in an organic liquid medium in which the magnesium halide can be dissolved.

There is no particular restriction on the timing of incorporating the oxide of a metal of group ~~ of the periodic table into the organic liquid medium. Alternatively, it may be added after dissolution.

The oxides of groups 1 to 2 of the periodic table used in the present invention may be not only oxides of individual metals of groups 1 to 1 of the periodic table, but also double oxides of these metals, and of course may be mixtures thereof. Specific examples of these metal oxides include MgO, CaO,
_ZnO , _BaO2 , _Ba2O3 , _SiO2 , _SnO3 , _{Al2O3 ,}
MgO・Al ₂ O ₃ , SiO ₂・Al ₂ O ₃ , MgO・SiO ₂ ,
Examples include MgO・CaO・Al ₂ O ₃ , Al ₂ O ₃・CaO, etc., but especially SiO ₂ , Al ₂ O ₃ , SiO ₂・
Al ₂ O ₃ and MgO.Al ₂ O ₃ are preferred.

The proportion of these metal oxides is 10g of a substance containing at least one component of magnesium halide.
The amount ranges from 0.1 to 500 g, preferably from 1 to 100 g, and more preferably from 2 to 50 g. The thus obtained substance containing at least one component of magnesium halide is dissolved in a liquid medium containing an oxide of a metal from Groups 1 to 10 of the Peripheral Table at temperatures below 10°C, for example from -80 to 10°C, preferably from -80°C to The temperature is maintained at 0°C, more preferably between -80°C and -20°C. Next, an organic liquid compound in which magnesium halide does not dissolve is gradually added to the liquid medium maintained at 10°C or lower. The organic liquid compound used at this time is
Various saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, etc. are used. As for the rate of addition of the organic liquid compound, it is desirable to add it as slowly as possible, and by adding it as slowly as possible, a solid substance with a large particle size can be precipitated. Usually, a solution 1 containing a substance containing at least one component of magnesium halide
50 g or more, for example 50 to 5000 g, preferably 500 to 5000 g, of an organic liquid compound in which magnesium halide does not dissolve is added over 10 minutes or more, preferably 1 hour or more, for example 1 to 10 hours. As for the addition rate, it is desirable that the amount of organic liquid compound added per minute to solution 1 is 50 g or less, preferably 10 g or less, and most preferably 5 g or less. The addition method is not particularly limited and may be either a continuous addition method or a continuous addition method.

Among the solid substances thus precipitated, those with small particle sizes are not preferred, and those with a particle size of 5 μm or more are used as the carrier for the olefin polymerization catalyst targeted by the present invention. Particularly preferred is one of 10μ or more.

A titanium compound and/or a vanadium compound is supported on the carrier of the present invention thus prepared, and used in combination with an organometallic compound as a catalyst for polymerization or copolymerization of olefin.

A method for supporting the titanium compound and/or vanadium compound on the carrier of the present invention includes, for example, bringing the carrier of the present invention into contact with the titanium compound and/or vanadium compound under heating in the presence or absence of an inert solvent. This can be done by combining both, preferably in the absence of a solvent.
This is carried out by heating to 50-300°C, preferably 100-150°C. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and long-term contact may be allowed, although it is not necessary. For example, processing times can range from 5 minutes to 10 hours.

Titanium compound and/or used in the present invention
Alternatively, the amount of the vanadium compound may be used in excess, but it can usually be used in an amount of 0.001 to 50 times the weight of magnesium halide. Preferably, excess titanium compound and/or vanadium compound is removed by washing with a solvent after the mixing and heating treatment. After completion of the reaction, the means for removing the terminally reacted titanium compound and/or vanadium compound is not particularly limited, and may include washing the Ziegler catalyst several times with a solvent inert to the catalyst and evaporating the washing liquid under reduced pressure to obtain a solid powder. is usually done.

In addition, the amount of the titanium compound and/or vanadium compound to be supported is such that the titanium and/or vanadium content contained in the produced solid is 0.5 to 20.
It is most preferable to adjust the amount within a range of 1 to 10% by weight, and in order to obtain well-balanced activity per titanium and/or vanadium and activity per solid, a range of 1 to 10% by weight is particularly desirable.

Examples of the titanium compound and/or vanadium compound used in the present invention include halides, alkoxy halides, alkoxides, and halogenated oxides of titanium and/or vanadium. Preferred titanium compounds are tetravalent titanium compounds and trivalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula Ti(OR) _o X _4-o (where R is 1 carbon number) ~20 alkyl, aryl or aralkyl groups;
X represents a halogen atom. n is 0≦n≦4. ) is preferable, titanium tetrachloride,
Titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxy Trichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxytitanium Examples include cymonochlorotitanium and tetraphenoxytitanium. Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of group metals of the periodic table. It will be done. Also, the general formula Ti(OR) _n X _4-n (where R
represents an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom.
m is 0<m<4. ) A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by the following formula with an organometallic compound of a group metal of the periodic table is exemplified. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium; Examples include trivalent vanadium compounds such as trivalent vanadium compounds, vanadium trichloride, and vanadium triethoxide.

As the organometallic compound used in the present invention, organometallic compounds of groups 1 to 10 of the periodic table, which are known as components of Ziegler's catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formula R ₃ Al,
R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl(OR)X and
Organoaluminum compound _of R ₃ Al _{2 2} Zn (however, R is an alkyl group having 1 to 20 carbon atoms and may be the same or different), and is represented by an organic zinc compound of triethylaluminum,
triisopropylaluminium, triisobutylaluminum, trisec-butylaluminum,
Examples include tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. The amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound and/or vanadium compound.

Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization, and the polymerization reaction is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. Polymerization conditions for olefin include temperature of 20 to 120°C, preferably 50 to 100°C.
℃, and the pressure is normal pressure to 70 kg/cm ² , preferably 2 to 60 kg/cm ² . Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and α-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4-methyl Homopolymerization of α-olefins such as pentene-1 and octene-1, and ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1
- Suitable for use in copolymerization of butene, etc.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (a) Preparation of carrier 10 g of anhydrous magnesium chloride, 5 g of aluminum triethoxide and 10 g of silicon dioxide were added to 200 ml of tetrahydrofuran and heated at 100°C for 10 g.
After heating for an hour, keep at -60℃ and 200ml of hexane.
was gradually added over 30 minutes with stirring to precipitate a solid material. Next, after removing the supernatant liquid, drying was performed at 100° C. for 1 hour under reduced pressure to obtain a solid carrier having an average particle size of 60 μm.

(b) Production of catalyst components 2 g of the above solid support and 0.5 titanium tetrachloride
ml was added to 40 ml of hexane, and the reaction was carried out for 1 hour under reflux of hexane. Next, after removing the supernatant liquid, washing was repeated with hexane until no titanium tetrachloride was detected in the washing liquid, thereby obtaining a solid catalyst component. Each gram of solid catalyst component contained 22 mg of titanium.

(c) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower, a flow rate regulator, and a dry cyclone, and the temperature of the autoclave was adjusted by flowing hot water through the jacket.

The above solid catalyst component was fed to an autoclave adjusted to 80°C at a rate of 50 mg/hr and triethylaluminum at a rate of 5 mmol/hr, and the butene-1/ethylene ratio (molar ratio) in the gas phase of the autoclave was set to 0.28. Furthermore, hydrogen is added to 15% of the total pressure.
Polymerization was carried out by supplying each gas while adjusting the following, and by circulating the gas in the system using a blower to maintain the total pressure at 10 kg/cm ² ·G. The produced ethylene copolymer has a bulk specific gravity of 0.40, a melt index (MI) of 0.85, and a density
It was 0.9211.

Furthermore, the catalyst activity was extremely high at 341,000 g copolymer/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

The average particle size of the obtained polymer powder was as large as 1000μ, and the amount of fine powder with a particle size of 200μ or less was as low as 0.2%.

Example 2 10 g of anhydrous magnesium chloride, 3 g of aluminum triethoxide, 2 g of tetraethoxysilane and 10 g of silicon dioxide were added to 200 ml of ethyl acetate.
After heating at 100°C for 1 hour, the temperature was maintained at -30°C, and 200ml of hexane was gradually added over 30 minutes with stirring to precipitate a solid substance, thereby obtaining a solid support with an average particle size of 55μ.

The solid catalyst component (amount of titanium supported:
25 mg/g) and copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of 0.42, a melt index of 0.72, a density of 0.9206, and a catalytic activity of
The activity was extremely high at 322,500g copolymer/gTi.

The average particle size of the obtained polymer powder was as large as 950μ, and the amount of fine powder with a particle size of 200μ or less was as low as 0.3%.

Example 3 10 g of anhydrous magnesium chloride, 2 g of aluminum triethoxide, 2 g of diethoxydichlorosilane
g, 1 g of tetrabutoxysilane and 15 alumina
Add g to 200ml of ethyl acetate and heat at 100℃ for 1 hour, then keep at -30℃ and add 200ml of hexane with stirring.
Add gradually over 30 minutes to precipitate solid material,
A solid support with an average particle size of 50μ was obtained.

The solid catalyst component (amount of titanium supported:
Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of 0.41, a melt index of 0.95, a density of 0.9200, and a catalytic activity of
The activity was extremely high at 311,000g copolymer/gTi.

The average particle size of the obtained polymer powder was as large as 900μ, and the amount of fine powder with a particle size of 200μ or less was as low as 0.4%.

Example 4 In 200 ml of ethyl acetate containing 15 g of alumina,
After adding 10 g of anhydrous magnesium chloride and tetraacetoxysilane and heating at 100°C for 1 hour, -30
℃, 200 ml of hexane was gradually added over 30 minutes under stirring to precipitate the solid material, and the average particle size was determined.
A solid support of 53μ was obtained.

The solid catalyst component (amount of titanium supported:
Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of 0.39, a melt index of 1.1, a density of 0.9216, and a catalytic activity of
The activity was extremely high at 323,000g copolymer/gTi.

The average particle size of the obtained polymer powder was as large as 950μ, and the amount of fine powder with a particle size of 200μ or less was as low as 0.3%.

Example 5 10 g of anhydrous magnesium chloride, 4 g of tetraisopropoxy titanium, 2 g of silicon tetrachloride, and
Add 15 g of MgO.Al ₂ O ₃ to 200 ml of diethyl ether, heat at 100°C for 1 hour, then keep at -30°C,
200 ml of hexane was gradually added over 30 minutes with stirring to precipitate a solid substance, yielding a solid support with an average particle size of 45 μm.

A solid catalyst component (titanium supported amount: 15 mg/g) was produced in the same manner as in Example 1, except for using the above solid carrier and using tetraisopropoxy titanium instead of titanium tetrachloride. Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of 0.41, a melt index of 1.0, a density of 0.9219, and a catalytic activity of
The activity was extremely high at 207,000g copolymer/gTi.

The average particle size of the obtained polymer powder was as large as 870μ, and the amount of fine powder with a particle size of 200μ or less was as low as 0.5%.

Example 6 10 g of anhydrous magnesium chloride and 1 g of aluminum chloride diethyl etherate complex were added under nitrogen.
Ball milling took place for 16 hours. The resulting reaction product was dissolved in 200 ml of tetrahydrofuran.
After adding 10 g of silicon dioxide to this solution, -70℃
200 ml of hexane was gradually added over 30 minutes under stirring to precipitate the solid material, and the average particle size was
A 46μ solid support was obtained.

The solid catalyst component (amount of titanium supported:
21 mg/g) and copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of 0.43, a melt index of 0.80, a density of 0.9223, and a catalytic activity of
The activity was extremely high at 190,000g copolymer/gTi.

The average particle size of the obtained polymer powder was as large as 890μ, and the amount of fine powder with a particle size of 200μ or less was as low as 0.5%.

Example 7 10 g of anhydrous magnesium chloride, 5 g of aluminum triethoxide and 10 g of silicon dioxide were added to 300 ml of acetone, heated at 100° C. for 1 hour, and then
While maintaining the temperature at −60° C., 300 ml of hexane was gradually added over 30 minutes with stirring to precipitate a solid substance. Next, after removing the supernatant liquid, drying was performed at 100° C. for 1 hour under reduced pressure to obtain a solid carrier with an average particle size of 60 μm.

The solid catalyst component (amount of titanium supported:
24 mg/g) and copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of 0.39, a melt index of 0.90, a density of 0.9222, and a catalytic activity of
The activity was extremely high at 315,000g copolymer/gTi.

The average particle size of the obtained polymer powder was as large as 950μ, and the amount of fine powder with a particle size of 20μ or less was as low as 0.2%.

Example 8 Using the same solid catalyst component and equipment as in Example 1, the solid catalyst component was supplied at a rate of 50 mg/hr and triethylaluminum at a rate of 5 mmol/hr to an autoclave adjusted to 80°C, and propylene was supplied at a rate of 5 mmol/hr. The polymerization was carried out while maintaining the total pressure at 10 kg/cm ² ·G by circulating the gas in the system using a blower. The produced propylene polymer has excellent particle properties with a bulk specific gravity of 0.44, and has a high catalytic activity.
The activity was extremely high at 118,000g polymer/gTi.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing a method for producing an olefin polymerization catalyst carrier and a method for producing an olefin polymerization catalyst containing the same according to the present invention.

Claims (1)

[Scope of Claims] 1. A substance selected from alcohols, organic acid esters, ketones, and ethers that dissolves a substance containing at least one component of magnesium dihalide and contains an oxide of a metal of Groups 1 to 1 of the periodic table. An olefin polymerization catalyst characterized in that at least one liquid medium is maintained at a temperature of 10°C or less, and a saturated hydrocarbon is gradually added to the liquid medium to precipitate a carrier consisting of a substance with a particle size of 5μ or more. Method for manufacturing carrier. 2 The oxides of metals from groups ~ of the periodic table are MgO,
CaO, ZnO, BaO, _SiO2 , _SnO2 , _{Al2O3 ,}
MgO・Al ₂ O ₃ , SiO ₂・Al ₂ O ₃ , MgO・SiO ₂ ,
The manufacturing method according to claim 1, characterized in that the oxide is at least one type of oxide selected from the group consisting of MgO.CaO.Al ₂ O ₃ and Al _{2 O} 3.CaO.