JPS5865707A - Carrier for olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:The titled carrier suitable for the production of polyolefin having good powder flow, prepared by precipitation by mixing a low-temperature solution of a substance containing a magnesium halide as one component with an organic liquid compound in which the substance can not dissolve. CONSTITUTION:The titled carrier comprising a substance, particle diameter >=5mu, is prepared by holding a solution in, e.g., diethyl ether of a substance containing a magnesium halide as one component[e.g., magnesium halide (e.g., MgCl2) or its reaction product with another compound], at below 10 deg.C and slowly adding, to this solution, an organic liquid compound in which the magnesium halide can not dissolve (e.g., hexane) to effect precipitation. An olefin is (co)polymerized with the aid of a catalyst prepared by combining a component prepared by impregnating the carrier with a Ti compound (e.g., TiCl4) and/or a V compound (e.g., VCl4) with an organometallic compound (e.g., triethylaluminum). It is possible to produce a polyolefin having good powder flow.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 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 have been known in which a transition metal compound such as titanium or vanadium is supported on an inorganic magnesium solid such as magnesium halide, magnesium oxide, or magnesium hydroxide. There is. However, in these known techniques, the resulting polymer has a large particulate shape, generally has a small bulk specific gravity, a small average particle size, and a generally wide particle size distribution, resulting in poor productivity and slurry handling. Improvements were strongly desired. Furthermore, during the molding process of these polymers, K also causes the generation of dust, a decrease in efficiency during molding, rounding that occurs during molding, an increase in the bulk specific gravity, an increase in the average particle size, and a decrease in the fine particulate powder portion as mentioned above. A much-desired friend.

The present invention has improved the above-mentioned drawbacks, but has a high specific gravity, a narrow particle size distribution, and a polymer! As a result of intensive study to produce a polymer with good powder flowability that has significantly less θ fine particles, we found that
It has been found that the use of a specific carrier shows remarkable effects depending on a specific production method.

That is, the present invention provides a solution in which a substance containing at least one component of magnesium chloride is heated at a temperature of 10°C or less.
The carrier for an olefin polymerization catalyst consists of a substance with a particle size of 5 P or more obtained by precipitation by gradually adding an organic liquid compound in which magnesium no-logenide is not dissolved to the solution while maintaining the temperature at lf. When olefin polymerization or copolymerization is carried out using a catalyst that is a combination of a solid catalyst component in which a titanium compound and/or a vanadium compound are supported on the support of the present invention prepared in this way and an organometallic compound, The polymer yield per solid and the polymer yield per transition metal are significantly increased, thereby eliminating the need for removal of catalyst residues in the resulting polymer, and the resulting polymer powder has a high bulk specific gravity. It has a narrow particle size distribution, a small amount of fine particles, good powder fluidity, and is not only easy to handle during polymerization operations, but also has few troubles during molding, making it extremely advantageous to produce polyolefins. can.

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.
Any compound in which the substance can be dissolved, such as alcohols, esters, ethers, ketones, and amines, can be used as the organic liquid medium in which the substance containing magnesium halide as at least one component is dissolved. I can do it. Preferred specific examples of these include alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, octatool, 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, octyl laurate, methyl benzoate, ethyl benzoate, octyl paraoxybenzoate, dibutyl heptathalate, dioctyl phthalate, dimethyl malonate , esters such as dimethyl maleate and diethyl maleate, ethers such as dimethyl ether, diethyl ether, diisoglobyl ether, dibutyl ether, cyamyl ether, tetrahydrofuran, dioxane, anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl Keto/butyl ketone, diphenyl ketone, acetophenone, diphenyl ketone, cyclohexanone, etc.
Examples include amines such as diethylamine, triethylamine, dimethylamine, aniline, N,N-dimethylaniline, and pyridine.

The substance containing magnesium halide as at least one component used in the present invention is magnesium halide, a reaction product of magnesium halide and one or more other compounds, or a mixture thereof.

Examples of the magnesium halide include magnesium heptadide, magnesium chloride, magnesium bromide, and magnesium iodide. Magnesium chloride is preferable in t'LS% 〇 As an antinomian of magnesium halide and one or more other compounds, Various known magnesium ethanide-containing carriers can be used. Specific examples of these include magnesium genide and 5i (OR),! ,−,
, a reaction product with magnesium halide and B(OR),
! , - reactant with n, /- magnesium ethanide and AI
(OR),! , -, Reaction product between magnesium halide and MuIOX, Reaction product between magnesium ethanide and a compound having an Al-0-C bond, Magnesium halide and aluminum chloride, and Aluminum chloride Reaction products with mooether complexes, reactions between magnesium ethanide and phosphorus pentachloride, phosphorus trichloride or phosphorus oxytrichloride, reactions between magnesium halides and organic ethanates such as dichloroethane and trichlorobenzene. Magnesium halide and titanium oxy/SO
Reaction products with ge/chemicals, magnesium ethanide and 5i
(OR),.

Reaction product of X, -m and AI(OR)IIXs-n, no.
Examples include reaction products of magnesium ethanide, silicon tetrachloride, and ROM (in the formula, R has 1 to 1 carbon atoms).
20 hydrocarbon residues, 1 company halogen, 0≦m≦4.0
(n≦3)O Of course, other known supports containing magnesium ethanide can also be used in the present invention.

The operation and conditions for dissolving a substance containing at least one component of magnesium halide are not particularly limited; for example, it may be carried out at room temperature, it may be carried out by heating as appropriate, and the concentration of the O solution may vary within a wide range. You can choose, but usually 1~
When using a reaction product of 0 magnesium halide and other compounds, the range of 30 weight t- is preferably used, these may be reacted in advance and then dissolved. The reaction may also be carried out in a liquid medium.

A solution for dissolving the substance having at least one component of magnesium isogenide obtained in this way is heated to 10°C or lower, for example -80°C to 10°C, preferably -80°C to 0°C, more preferably -80°C to Keep at -20℃. Next, an organic liquid compound in which magnesium halide does not dissolve is gradually added to the solution maintained at 10° C. or lower. The organic liquid compound used at this time may be any organic compound that does not dissolve in the magnesium halide tube. For example, various saturated hydrocarbon compounds such as pentane, heptane, heptane, octane, and their halogenated derivatives are preferably 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, 7% per 1 ton of solution containing a substance tt containing magnesium halide as at least one component.
'<1 min or more, preferably 1 hour or more, e.g.
Add over 0 hours. As for the addition rate, it is desirable that the amount of organic liquid compound added per 1 ton of solution is 10 f per minute or less, preferably 5 f or less. Mori as an addition method,
There are no particular limitations, and either a continuous addition method or an intermittent addition method may be used.

Among the solid substances thus precipitated, those having a small particle size are not preferred, and those having a particle size of 5P or more are used as the carrier for the olefin polymerization catalyst targeted by the present invention.

In particular, books of 10 pages or more are preferred.

A titanium compound and/or a vanadium compound is supported on the carrier of the present invention prepared in this manner, and used in combination with an organometallic compound as a catalyst for polymerization or copolymerization of olefins. Alternatively, a method for supporting a panadium compound can be carried out, for example, by bringing the support of the present invention into contact with a titanium compound and/or a vanadium compound under heating in the presence or absence of an inert solvent, and is preferably carried out. In the absence of a solvent, both t-50 to 300°C, preferably 100 to 1
This is done by heating to 50°C. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and although it is not necessary, there is no problem with contacting for a long time. For example, the treatment time can be 5 minutes to 10 hours.

The amount of the titanium compound and/or vanadium compound used in the present invention is usually (1001 to 50
Can be used twice the weight. Preferably, the excess titanium compound and/or vanadium compound is removed by washing with a solvent after the mixing and heating treatment. After the O reaction is completed, the means for removing the unreacted titanium compound and/or vanadium compound is not particularly limited. It is customary to wash the catalyst several times with a solvent inert to the catalyst and evaporate the washings under reduced pressure to obtain a solid powder.

In addition, the amount of the titanium compound and/or vanadium compound to be supported is determined by the amount of titanium and/or vanadium compound contained in the produced solid.
It is most preferable to adjust the vanadium content to a range of α5 to 20% by weight, and in order to obtain well-balanced activity per titanium and/or vanadium and activity per solid, the content should be adjusted to a range of 1 to 10% by weight. Range 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. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are suitable. Specifically, as a tetravalent titanium compound, the general formula Ti(OR)nX4-, (R is 1 carbon number)
~20 alkyl, aryl or aralkyl groups; LAX represents a halogenated acid; n is 0≦n≦4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, dimethoxydichlorotitanium, trichlorotitanium Ethoxymonochlorotitanium, tetraethoxytitanium, monoisoprofoxytrichlorotitanium, diiso10boxydichlorotitanium, triisopropoxymonochlorotitanium, tetrainoboxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monoindoxytrichlorotitanium, monophenoxy Examples include ditrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxybutane. 5
Examples of trivalent titanium compounds include trivalent titanium compounds obtained by reducing tetrahalogenated titanium such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of metals from groups 1 to 1 of the periodic rule. Examples include titanium halides. In addition, the general formula 'rl (OR),, if O
Examples of vanadium compounds include pentavalent titanium compounds obtained by reducing a tetravalent alkoxy titanium halide represented by (m (4)) with an organometallic compound of a metal from Group 1 to 1 of the Periodic Table. , tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium; pentavalent vanadium compounds such as vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl, and triptoxyvanadyl. , trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide.

As the organometallic compound used in the present invention, organometallic compounds of Groups 1 to 1 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. A specific example is the general formula RsAIX RaiAIX, RAI! snow,
R11101% RAI(OR)X and R, A1
．． Organoaluminum compound of X3 (however, Ra carbon number is 1
~20 alkyl, aryl or aralkyl groups,
X represents a halogen atom (L/X R may be the same or different) or the general formula R, Zn (where R is
~20 alkyl groups, which may be the same or different), such as triethylaluminum, triisopropyla^.minilam,
Trioctylaluminium, Trihata C-butylaluminum, trit@rt-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, sulfurviraluminum chloride, ethyl aluminum sesquichloride, diethylzinc and mixtures thereof etc. can be mentioned. The amount of the organometallic compound to be used is not particularly limited, but it is usually in the range of (11 to 10
It can be used 0100 times.

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 the olefin include: The temperature is 20 to 120°C, preferably 50 to 100°C, and the pressure is normal pressure to 7014/d, preferably 2 to 6011/ai. Although the molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization fullf and the molar ratio of the catalyst, it is more effective than adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, two-stage or more multi-stage polymerization reactions with different polymerization conditions such as hydrogen concentration and degree of polymerization can be carried out without any hindrance.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst.
α-olefins such as ethylene, propylene, 1-butene, hexene-1,4-methylpentene-1, octene-1, etc. are preferred, and homopolymerization of α-olefins such as 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.

The following Examples are provided for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (a) Preparation of carrier 10 f of anhydrous magnesium chloride and 4 ft of aluminum triethoxide were added to 100 g of tetrahydrofuran and heated at 100° C. for 1 hour.

The solution was maintained at -70° C., and 100° C. of hexane was gradually added over 30 minutes 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 50 μm.

伽) Manufacture of catalyst components: Added to the solid support 2t described above and tetra-titanium CLSdt Hexa/40-, and reacted for 1 hour under reflux of hexane. Next, after removing the supernatant liquid, titanium tetrachloride was added to the washing liquid. Washing with hexane was repeated until no more was detected to obtain a solid catalyst component.

(,) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower-1 flow rate regulator and a formal cyclone, and ILF was adjusted by flowing hot water through the autoclave's jacket.

The above solid catalyst component t was placed in an autoclave adjusted to 80°C.
S6wg/hr, and triethyl aluminum 1ft
In addition, the butene-17 ethylene ratio (molar ratio) in the gas phase of the autoclave is supplied at a rate of S mm·l/hr.
(Hydrogen was further supplied to L28 while adjusting the total pressure to 15 mm, and the gas in the system was circulated using a blower to maintain the total pressure at 1 aKg/-.G. The bulk specific gravity α' of the ethylene copolymer produced by polymerization was 15, and the melt index (MI) was 90.
, the density was a9210.

The Maku catalyst activity was extremely high at 514,000f copolymer/fat.

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 900μ,
In addition, the amount of fine powder with a particle size of 200μ or less was as low as 1.0.Example 2 10f of anhydrous magnesium chloride, 4t of aluminum triethoxide, and 1ft of tetraethoxysilane were added to #111 ethyl IQ [)- and heated at 100°C for 1 hour. did. The solution was kept at -20°C, and hexane was gradually added over several minutes to precipitate a solid substance, with an average particle size of 48.
A solid support of p was obtained.

A solid catalyst component was produced in the same manner as in Example 1, except for using the above solid carrier, and ethylene and butene-10 copolymerization was carried out in the same manner as in Example 1.

The produced copolymer has a bulk specific gravity αs8, a melt index cL7, a density α9208, and a catalytic activity of 252.
, 5onf copolymer/fTi, which showed extremely high activity.

The average particle size of the obtained polymer powder was as large as 870μ,
In addition, the amount of fine powder with a particle size of 200μ or less was as low as 1.2%.

Example 5 10t of anhydrous magnesium chloride, 4f of aluminum triethoxide, 1f of jetoxydichlorosilane and 11f of tetrabutoxysilane were added to 10Osd of ethyl acetate and heated at 100°C for 1 hour. This solution was maintained at -20° C., and hexane (10 ml) was gradually added over 30 minutes to precipitate a solid substance to obtain a solid support having an average particle size of 47 μm.

A solid catalyst component was prepared in the same manner as in Example 1, except for using the above-mentioned solid carrier. Ethylene and butene-1 were copolymerized in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of α36, a melt index of 1.0, a density of α9199, and a catalytic activity of 300.
The average particle size of the obtained polymer powder was as large as 830μ, and the fine powder with a particle size of 200μ or less was as small as (L, 6-) and had extremely high activity with copolymer/f Ti. Example 4 10F of anhydrous magnesium chloride and 5FF of tetraacetoxysilane were added to 100% of ethyl acetate and heated at 100°C for 1 hour.The solution was kept at 20°C and 100% of hexane was gradually added over 50 minutes. A solid substance was precipitated in this manner to obtain a solid support having an average particle size of 45 μm.

A solid catalyst component was produced in the same manner as in Example 1, except for using the above solid carrier, and ethylene and butene-10 copolymerization was carried out in the same manner as in Example 1.

The produced copolymer has a bulk specific gravity α35, a melt index t2, a density α9215, and a catalytic activity of 33aO.
OO2 copolymer/fTi has extremely high activity.

The average particle size of the obtained polymer powder was as large as 670μ,
In addition, the amount of fine powder with a particle size of 200P or less was as low as 1.7-0.
Example 5 10f of anhydrous magnesium chloride 3t of tetraisopropoxy titanium and 1f of silicon tetrachloride were mixed with 1f of diethyl ether
00d and heated at 100°C for 1 hour. This solution was kept at t-20°C, and 100 dff of hexane was gradually added over 50 minutes to precipitate a solid substance, with an average particle size of 40 μm.
90 A solid catalyst component was produced in the same manner as in Example 1, except that the above solid support was used and tetraisopropoxytitanium was used instead of titanium tetrachloride. Copolymerization of ethylene and butene-1 was carried out in the same manner.Produced copolymer structure, bulk specific gravity Q, 37, melt index 1
．． 1, density α9220, and catalyst active line 197.
000f copolymer/f Ti, which showed extremely high activity.

The average particle size of the obtained polymer powder was as large as 500μ,
In addition, the amount of fine powder with a particle size of 200P or less was as low as 1.1-0.
Example 6 Anhydrous magnesium chloride 10IF and alunium chloride Φ diethyl etherate complex 1f'iil under 16
Time ball milling was performed. The obtained reaction product was dissolved in tetrahydrofuran. This solution was maintained at t-70 DEG C. and hequinane was gradually added at 100 m/'i over 50 minutes to precipitate a solid substance to obtain a solid support with an average particle size of 40 .mu.m.

A solid catalyst component was produced in the same manner as in Example 1, except for using the above solid carrier, and ethylene and butene-1 were copolymerized in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of α3B, a melt index of α8, and a density of α9221, and has a catalytic activity of 17mm.
00f copolymer/fTi, which showed extremely high activity.

The average particle size of the obtained polymer powder was as large as 600μ,
Further, the amount of fine powder with a particle size of 200μ or less was as low as 1.5s.

Procedural amendment (method) % formula % 1. Indication of the case 1920 Patent Application No. 164106 2. Name of the invention Carrier for olefin polymerization catalyst 3. Relationship with the case to be amended Patent applicant name (444) E1 Column 6 of Detailed Description of the Invention in the Specification of Honjo Oil Co., Ltd., Contents of the Amendment (1) Page 10 of the specification, line 4: “102 f/min or less, preferably 5 f/min or less” t “50 f/min or less, preferably 10 f/min or less” "below, most preferably 5f or less".

Claims (1)

[Claims] t By maintaining a solution containing a substance containing magnesium halide as at least one component at Ii[K below 10°C, and gradually adding to the solution an organic liquid compound in which magnesium halide is not dissolved. Particle size obtained by precipitation 5
An olefin polymerization catalyst carrier made of a substance of P or more. 2. Particles obtained by precipitating a solution containing a substance containing at least one component of magnesium halide by maintaining IiI[K at 10°C or lower and gradually adding an organic liquid compound in which magnesium halide does not dissolve to the solution. Polymerization or copolymerization of olefins using a catalyst consisting of a combination of a titanium compound and/or vanadium compound supported on a solid carrier made of a substance having a diameter of 5P or more and an organometallic compound. Production method.