JPS58122904A - Carrier for olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To obtain a carrier for olefin polymerization catalysts suitable for the production of polyolefins having a spherical particle form and good powder fluidity, by adding a poor solvent to a solution containing a magnesium halide and a Group II-IV metal oxide, and heat-treating the mixture. CONSTITUTION:A substance containing a magnesium halide as one component (e.g., magnesium chloride, a reaction product between magnesium chloride and aluminum chloride) is dissolved in an organic liquid medium (e.g., isopropanol, ethyl acetate) and then an oxide of a Group II-IV metal (e.g., SiO2, Al2O3) is added. Next, at least about 50g, per 1 of the resulting solution, of an organic liquid compound which does not dissolve the magnesium halide (e.g., pentane) is added to precipitate a solid substance. This mixture is heat-treated at about 40-200 deg.C for about 5min-24hr and then the solvent is removed to obtain a solid carrier for olefin polymerization catalysts.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a carrier for an olefin polymerization catalyst. In particular, polyolefins with a spherical shape and good powder flowability? This invention relates to a method for preparing a carrier suitable for production.

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 leads to problems in productivity and slurry handling. Improvements were strongly desired. Furthermore, when molding these polymers into gold, there are problems such as generation of dust and reduction in efficiency during molding. Therefore, it has been strongly desired to increase the bulk specific gravity, increase the average particle size, and decrease the fine particulate powder portion as described above.

The object of the present invention is to improve the disadvantages of the upper rudder and obtain a polymer having a high bulk specific gravity, a narrow particle size distribution, a spherical shape, and excellent powder flowability with significantly less fine particulate portions of the polymer. It provides a complete catalyst support with remarkable effects.

That is, the present invention provides for the addition of an organic liquid compound in which magnesium halide does not dissolve into a liquid medium in which at least one of the constituent substances of magnesium halide is dissolved and which contains all of the oxides of metals of Groups 1 to 2 of the periodic table. Thereafter, the carrier for an olefin polymerization catalyst is made of a material obtained by heat treatment at a temperature of 40 to 200°C. When olefin polymerization and copolymerization were carried out using a catalyst consisting of a combination of a solid catalyst component containing a titanium compound and/or batudium compound rf and two organometallic compounds on the support of the present invention prepared in this way, the solid The overall polymer yield and transition metal yield are increased, thereby eliminating the need for a step to remove catalyst residue from the resulting polymer, and the resulting polymer powder is less bulky. It has a high specific gravity, a narrow particle size distribution, a small particulate powder portion, and an almost spherical shape, so it has good powder flowability and is easy to handle during polymerization operations. Polyolefins can be completely produced very advantageously, with fewer troubles during molding and processing.

The present invention will be described in full detail below.

In preparing the olefin 1 [gold catalyst carrier of the present invention], first, a substance containing magnesium halide as at least one component is bath-dissolved in an organic liquid medium in which the substance can be dissolved.

The organic liquid medium that dissolves all of the substances containing at least one component of magnesium halide used at this time is any compound that can be bath-dissolved by the substance, such as alcohols, esters, ethers, ketones, and amines. Sound can be used. Preferred specific examples of these include methanol, ethanol, inglobanol, butanol,
Alcohols such as pentanol, hegisanol, 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 phthalate, diocnal phthalate, malon Esters such as dimethyl acid, dimethyl maleate, diethyl maleate, ethers such as dimethyl ether, diethyl ether, diimpropyl ether, dibutyl ether, cyamyl ether, tetrahydrofuran, dioxane, anisole, etc.
Acetone, methyl ethyl ketone, methyl imbutyl ketone, ethyl butyl ketone, diphenyl ketone, acetophenone, diphenyl ketone, ketones such as cyclohexanone, diethylamine, triethylamine, tetramethylenediamine, aniline, N,N-dimethylaniline,
Examples include amines such as pyridine.

The substance which constitutes at least one component of all the magnesium halides used in the present invention is magnesium halide, a reaction product of magnesium halide and one or more other compounds, 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 a reaction product of magnesium halide and s i (oR) J4-1, a reaction product of magnesium halide and B(OR)nX31, a reaction product of magnesium halide and Al (OR)nX
Reaction product with J3-tz, magnesium halide and A
Reactant with l0X, magnesium halide and At −
Reactant with compound containing 0-C bond, magnesium halide and aluminum chloride or aluminum chloride.
Contrary to ether complex! 6 compounds, reaction products of magnesium halide and phosphorus pentachloride, phosphorus trichloride or phosphorus oxytrichloride, reaction products of magnesium halide 6-- and organic halides such as dichloroethane and trichlorobenzene, halogenation Reaction product of magnesium and titanium oxyhalide, magnesium halide Sic.

R~, ¥4. ．． ．． Reaction product with self-Al (OR),
All examples of reactants with 1-1 can be shown (in the formula,
R is a hydrocarbon bed residue having 1 to 20 carbon atoms, X is halogen, 0
≦m≦4.0<n≦3). Of course, other known magnesium halide-containing J'fj bodies can also be used in the present invention.

A substance containing at least one component of magnesium halide? There are no particular restrictions on the dissolution operation or conditions;
For example, it may be carried out at room temperature or may be carried out with appropriate heating.

When a reaction mixture of magnesium halide and other compounds is used, these may be reacted in advance and then dissolved, or the reaction may be carried out in an organic liquid medium in which the fine magnesium halide can be dissolved.

There are no particular restrictions on IJJ when all oxides of metals from Groups ■ to ■ of the periodic table are contained in the organic liquid medium, and magnesium halides? It may be present before at least one component is dissolved, or it may be added during or after dissolution.

The oxides of Groups ■ to ■ of the periodic table used in the present invention may be not only oxides of individual metals of Groups It's okay.

Specific examples of these metal oxides include Mg(L
Cab.

ZnO, BaO, 5in2. SnO2, Al2O3,
MgO'Al2O3゜SiO2・Al 203. A
faO-8iO,,,MgO-Ca0-Al 203.
Al 203, CaO etc? For example, Sz Q 21A1203. SiO2・A12
032Mg0-A1203 is preferred.

The proportion of these metal oxides is 0.1 to the substance 102 which is at least one component of the magnesium halide.
-5007y, preferably 1-100y, more preferably 2-50y. Thus, (a) an organic liquid compound in which the magnesium halide gold listed in Table 4 completely dissolves the substance of which it is a component, and in which the magnesium halide does not dissolve in a liquid medium containing an oxide of a metal of group ■ to ■ of the periodic table; Add all. Regarding the concentration of the substance containing at least one component of magnesium halide in the liquid medium when all organic liquid compounds are added, Fi is not particularly limited and can be used within a wide range, but is usually 1 to 30.
The preferred range is 5% to 30% by weight.

The organic liquid compound used at this time may be any organic liquid compound that does not completely dissolve the magnesium halide. For example, pentane, hexane, heptane,
At-saturated hydrocarbon compounds such as octane and their halogenated derivatives are preferably used.

Addition amount of organic liquid compound, magnesium halide 2
9. Add at least an amount necessary for precipitation of the substance as an ingredient. Usually magnesium halide? 50 organic liquid compounds in which magnesium halide does not dissolve per 1 ton of solution containing at least one component
2 or more, for example 50~5000F, preferably 500~
Add 5000 f.

There are no particular restrictions on the addition rate or addition method.

Solid substances are precipitated by the addition of the organic liquid compound, but in the present invention, the total temperature of the mixed liquid containing all of these solid precipitates is lowered to 40 to 200°C, preferably 50 to 10°C.
All heat treatments are performed at 0°C. The heat treatment time is not particularly limited, but is usually 5 minutes to 24 hours, preferably 10 minutes.
It is desirable to set it as 10 minutes to 10 hours. After the heat treatment, the solvent is completely removed to obtain the solid support of the present invention.

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

A method for supporting a titanium compound and/or a vanadium compound on the carrier of the present invention includes, for example, contacting the carrier of the present invention with a titanium compound and/or a vanadium compound under heating in the presence or absence of an inert solvent. Preferably in the absence of a solvent at a temperature of 50 to 300°C, preferably 100 to 1
This is done by heating to 50°C. The reaction time is not particularly limited, but is usually 5 minutes or more, and although it is not necessary, there is no problem in making the contact for a long time.

For example, the processing time can be from 5 minutes to 10 hours.

The sweetness of the titanium compound and/or vanadium compound used in the present invention is usually o, o o i to magnesium halide, although it may be used in excess.
Can be used at 50 times the weight. Preferably, excess titanium compound and/or vanadium compound is removed by washing with a solvent after the mixing and heating treatment. After the reaction is completed, the method for removing unreacted titanium compounds and/or vanadium compounds is not particularly limited. The Ziegler catalyst is washed several times with a solvent inert to it, and the washing liquid is evaporated under completely reduced pressure conditions. It is common practice 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 0.5 to 20% by weight, and to obtain a well-balanced titanium and/or vanadium activity and solid activity, A range of 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. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are suitable, and the tetravalent titanium compound is specifically represented by the general formula T Z (OR)nx4. ,.

(R represents an alkyl group having 1 to 20 carbon atoms, an aral group or an aralkyl group, and L/SX represents a total of 10 atoms). n is O≦n≦4), titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, jetoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, Monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoimpropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium Titanium,
Mono/pentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, tetraphenoxytitanium, etc. can be used. As trivalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide, total hydrogen,
Examples include titanium trihalide obtained by reduction with an organometallic compound of aluminum, titanium, or metals of groups 1 to 1 of the periodic law. Also, the general formula T z (OR) Jt-1
(Here, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralgyl group, and LAX represents a halogen atom.

A trivalent titanium compound obtained by reduction with an organometallic compound of a metal of Groups 1 to 2 of the Periodic Table of Tetravalent alkoxytitanium halides represented by m (0<971<4) can be mentioned. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium, vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl, and trib-14-toxyvanadyl. Examples include trivalent vanadium compounds such as pentavalent vanadium compounds, 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 R3Al.

I2□AIX, RAIX2. R2A101? ,,
Organoaluminum compounds of RAl(01bi) or general formula R2
Zn (however, R is an alkyl group having 1 to 20 carbon atoms and may be the same or different by 1), and is represented by an organic zinc compound such as triethylaluminum, triinpropylaluminum, triinpropylaluminum, or Examples include butylaluminum, tri-agc-butylaluminum, 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 01 to 1000 mo 1 times the amount of the titanium compound and/or vanadium compound.

Polymerization of olefins 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 olefin polymerization reactions using ordinary Tegler type catalysts. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. The polymerization conditions for olefin are a temperature of 20 to 120C, preferably 50 to 100C, and a pressure of normal pressure to 70Kg/! , preferably 2 to 5QKy/i. 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 completely adding hydrogen to the polymerization system. Of course, using the catalytic converter 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 problems.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Tegler'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, ethylene and propylene, ethylene and 1-butene,
It is suitably used for copolymerization of ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, and propylene and 1-butene.

17-1. Copolymerization with a diene 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 are given below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 Preparation of 1° (α) Solid Support A inch diameter? Stainless steel split ball with 2
Contents of 5 pieces: Put 10f of commercially available anhydrous magnesium chloride and 51 aluminum triethoxide into a $400 stainless steel pot and ball mill for 16 hours at room temperature under a nitrogen atmosphere. A reaction product was obtained. stirrer,
and reflux condenser? A total nitrogen tank was exchanged in a 18-digit 3-meter flask, and the above ge reaction product 152 and 50% was calcined at 600 °C.
iO2 (Fuji Devin, Su952) 101 was added to the solution, then added to 350 m of tetrahydrofuran, heated at 80°C for 2 hours, and then removed by total distillation of 200 m of tetrahydrofuran. Next, at 60°C hexane 5
00 mJi was added to completely precipitate the solid material. Subsequently,
The mixed solution containing the precipitate basin was heat-treated at 80° C. for 1 hour while completely stirring. After the heat treatment, the supernatant was removed several times and then dried at 100° C. for 2 hours under reduced pressure to obtain a solid carrier.

(b) Preparation of solid catalyst component The solid support 2y and 0.5d titanium tetrachloride were added to 40% of total hexane, and the mixture was reacted for 1 hour under refluxing hexane. Next, after removing several layers of the supernatant, the washing solution is washed repeatedly with reeds so that titanium tetrachloride is no longer detected, and the solid catalyst component is removed. Obtained.

Each 12 solid catalyst components contained 40 d of titanium.

(c) Polymerization Is a stainless steel autoclave suitable for gas phase polymerization equipment? A blower, a flow regulator, and a dry cyclone were used to close the loop, and the temperature of the autoclave was fully regulated by running hot water through the jacket.

Place the above solid catalyst components in an autoclave adjusted to 80°C and add triethylaluminum.
z 5 mmol/hr, and
The butene-1/ethylene ratio (molar ratio) in the gas phase of the autoclave was adjusted to 0.28 in total, and the gas was adjusted to 15% of the total water pressure, and the blower was used to By circulating the gas in the system, the total pressure is k 10 Ky/l:
Seven polymerizations were carried out while maintaining nl -G. The produced ethylene copolymer has a specific gravity of 0.38 and a melt index (CMI) of 0.88. , the density was 0.9210.

Further, the catalyst activity was extremely high at 300,000 r copolymer/gTi.

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 obtained polymer particles were spherical, had a large average particle size of 880 μm, and contained only 0.1% of fine powder with a particle size of 200 μm or less.

Comparative Example 1゜A solid support and a solid catalyst component (titanium-supported solid 40%
■/r)k was manufactured.

The entire copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 using the solid catalyst component.

The produced copolymer had a bulk specific gravity of 0.22, a melt index of □21-0.85, a density of 0.9205T, T/C, and an extremely high catalyst activity of 290,000f copolymer/fTi. .

However, the obtained polymer particles were amorphous, had a small bulk specific gravity of 0.22, and had a small average particle diameter of 350μ.
The amount of fine powder with a particle size of 200 μm or less was extremely high at 10.5%.

Example 2 A reaction product of 101 parts of anhydrous magnesium chloride, 32 parts of aluminum triethoxide and 22 parts of tetraethoxysilane and 1 part of silicon dioxide (1 part added to 350 parts of total ethyl acetate)
After heating at 00C for 1 hour, 500 m/f of hexane was added at 60C to precipitate all the solid material. Subsequently, the mixture was heat-treated for 1 hour at 1,000 ℃ while stirring the mixture. The supernatant was then removed, and then the
A solid carrier was obtained by drying at ℃ for 2 hours.

EXAMPLE 22 A solid catalyst component (titanium content: 40η/2) was produced in the same manner as in Example 1, except for using the solid carrier sound, and ethylene and butene were produced in the same manner as in Example 1. All copolymerizations of 1 were carried out.

The resulting copolymer had a bulk specific gravity of 037, a melt index of 0.90, and a density of 0.9220, and had an extremely high catalytic activity of 24-0.0002 copolymer/yI'i.

Obtained polymer particles d: spherical, average particle size 78
The particle size was as large as 0μ, and the particle size was as small as 0.2μ.

Example 3 A solid carrier was prepared in the same manner as in Example 1, except that 500 ml of pentane was used instead of hexane 5(t)- in preparing the solid carrier in Example IVC.
A solid catalyst component (titanium supported i: 401 ng/V) was produced using the solid carrier in the same manner as in Example 1. When ethylene and butene-1 were copolymerized in the same manner as in Example 1 using the solid catalyst component, the resulting copolymer had a bulk density of 037, a melt index of 0.87, and a density of 0.
．． 9207, and the catalyst activity is 270,000 f
Copolymer/? It had extremely high activity with Ti.

The obtained polymer particles were almost spherical, with an average particle size of 790
The particle size was as large as μ, and the amount of fine powder with a particle size of 200μ or less was as low as 0.1%.

Example 4゜Tetra-cracked 1 furan 350 containing alumina ior'l
102 parts of anhydrous magnesium chloride and 52 parts of magnesium jet oxide were added to mt, heated at 100°C for 1 hour, and then distilled off with 200 ml of tetrahydro 7 run. Afterwards, 500% hexane was added at 60°C.
dk was added and precipitated on solid material. Subsequently, the mixture was heat-treated at 100° C. for 1 hour while being thoroughly stirred. Next, after removing the supernatant metal, drying was performed at 100° C. for 2 hours under reduced pressure to obtain the entire solid carrier.

Should I use the above solid carrier? A solid catalyst component (amount of titanium supported: 40η/1) was produced in the same manner as in Example 1, except for this, and ethylene and butene-1 were copolymerized in the same manner as in Example 1.

The resulting copolymer had a bulk specific gravity of 039, a melt index of 0.85, and a density+i of 0.9215, and had an extremely high catalytic activity of 230.0002 copolymer/fTi.

The obtained polymer particles were approximately spherical, with an average particle size of 7.
The fine powder is as thick as 80μ, and the particle size is 200μ or less.
It was low at less than 2%.

Example 5゜In Example 2, 500 m of hexane! 500ml of heptane instead? The entire carrier was prepared in the same manner as in Example 2, except that the solid catalyst component (
Titanium 43'' content: 40~/7) Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1, using the solid catalyst component as a whole, and the resulting copolymer was Ka25- Specific gravity 0.40, Melt index 0.88, Density 0
．． 9212, and the catalyst activity is 280.00+l
Copolymer/17"i and extremely high activity Vt were used.

The obtained polymer particles were approximately spherical and had a large average particle size of 900 μm, and the amount of fine powder with a particle size of 200 μm or less was as low as 0.1%.

Special [Applicant: Nippon Oil Co., Ltd.] ／′−ゝ～ Agent: Patent Attorney Ryoji Yosera 1,・'1. \−26=

Claims (1)

[Claims] To a liquid medium containing at least one component of all magnesium halides and all oxides of metals from Groups 1 to 2 of the Periodic Table, add /% (1% organic liquid compound in which magnesium halides do not dissolve). , then the temperature is 40~2
An olefin polymerization catalyst carrier made of a material obtained by heat treatment at 00°C.