JPH01261407A - Titanium catalytic component and preparation thereof - Google Patents

Abstract

PURPOSE:To make it possible to obtain a highly active polymn. catalyst for olefin, which provide an olefin polymer having narrow compositional and particle size distributions and a high bulk specific gravity, by supporting Mg, Al, halogen and Ti on a porous carrier by a specified method. CONSTITUTION:A titanium catalyst component is a substance obtd. by a catalytic reaction of a carrier (A), especially pref. an Mg-contg. carrier obtd. by bringing an org. Al compd. into contact with a porous inorg. oxide having an average particle diameter of 10-100mum, a specific surface area of 100-700m<2>/g and a cell vol. of 0.5-2.5cm<3>/g and reacting it with a liq. Mg compd. having no reducing activity (e.g., a soln. prepared from MgCl2, 2- ethylhexanol and n-decane), a reductive organometallic compd. (B) (e.g., Et2AlCl) with a liq. Ti compd. (C), e.g., 2-ethylhexoxytrichlorotitanium.

Description

[Detailed Description of the Invention] 1. Hada Yukyatama-nuri 1 The present invention is capable of polymerizing olefins with high activity,
Moreover, the present invention relates to a titanium catalyst component and a method for producing the same, which can produce a copolymer having a narrow composition distribution, a narrow particle size distribution, and a crystalline granular +/r-shaped olefin polymer having a polymer bulk specific gravity. 9L! J1gtu

It is well known that when ethylene and a small proportion of α-olefin are copolymerized using a one-point Ziegler catalyst, an ethylene copolymer having a density comparable to that of high-pressure polyethylene can be obtained. It is being Generally, since the polymerization operation is easy, it is advantageous to employ high-temperature dissolution polymerization in which the polymerization is carried out at a temperature higher than the melting point of the copolymer to be produced using a carbonized ice water solvent. However, in order to obtain a polymer with a sufficiently large molecular weight, the viscosity of the polymerization solution increases, so the concentration of the polymer in the solution must be reduced, and therefore the amount of copolymer per polymerization vessel must be reduced. The problem is that the gender must be low. On the other hand, when trying to obtain the above-mentioned low-density ethylene copolymer using the slurry polymerization method that is often used in the production of high-density polyethylene, the resulting copolymer tends to dissolve or swell in the polymerization solvent, and the polymerization solution There were problems such as an increase in the viscosity of the slurry, adhesion of the polymer to the walls of the polymerization vessel, and a decrease in the bulk density of the polymer, which not only made it impossible to increase the slurry concentration but also made long-term continuous operation impossible. . In addition, the obtained copolymer was sticky, so there was a problem of quality F. These problems can be solved using specific catalysts.
Several methods have been proposed that attempt to improve by employing prevalent polymerization. As a result of investigating catalysts suitable for producing low-density ethylene copolymers, the inventors have discovered a catalyst system that has excellent slurry handling properties and is capable of operating at high slurry concentrations. On the other hand, many attempts have been made to improve catalyst activity in producing low-crystalline copolymers of ethylene and α-olefins. Examples include a method of supporting a copolymerizable vanadine compound on a carrier, a method of adding an oxidizing agent to improve the activity, and a method of improving the copolymerizability of supported titanium compounds with high activity. . However, these methods still have low polymerization activity and copolymerizability, and improvements have been desired. The present invention relates to the homopolymerization of ethylene or the polymerization of ethylene and α-
By copolymerizing with olefins, it has excellent slurry polymerization properties even when producing low-density ethylene copolymers, and it is also easy to use in gas phase polymerization, making it possible to produce copolymers with a narrow composition distribution. When the obtained low-density ethylene copolymer is molded into a film, etc., it is possible to produce a crushed molded product with transparency, blocking resistance, heat sealability, etc. Even in a process where all of the copolymers produced are products, such excellent molded products can be obtained, and in addition, when preparing the catalyst, the utilization efficiency of catalyst raw materials is high, and waste liquid treatment is therefore easy. The purpose of this invention is to provide such ingredients and methods for producing them. The support-supported titanium catalyst component according to the present invention, which has magnesium, aluminum, halogen, and titanium as essential components, comprises at least [I] support (i), organoaluminum compound (ii)
), and then a magnesium compound (iii) in a liquid state having no reducing ability is brought into contact with the magnesium compound (iii), whereby a magnesium-containing support [n] is reduced by a contact reaction with a liquid magnesium compound (iii) having no reducing ability [n] a reducing organometallic compound and [Iff] f
It is characterized by being obtained by a catalytic reaction of titanium compounds in the f state. Further, the method for producing a support-supported titanium catalyst component containing magnesium, aluminum, halogen, and titanium as essential components according to the present invention includes: [T] The support (i) is brought into contact with the organoaluminum compound (it), and then , a magnesium-containing support [I] is prepared by contacting with a liquid magnesium compound 0J(i) having no reducing ability, and then the obtained magnesium-containing support is mixed with [II
] A reducing organometallic compound and a titanium compound in a liquid state are brought into contact with each other. The present invention will now be described in detail. In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymers but also copolymers. There is. The support-supported titanium catalyst component according to the present invention is obtained by a catalytic reaction of [I] a magnesium-containing support, [II] a reducing organometallic compound, and [I] a titanium compound in a liquid state, and , aluminum, halogen, and titanium as essential components, typically the support (i) and the organoaluminum compound (ii)
After contacting in advance, the contact material is brought into contact reaction with a liquid magnesium compound (i) having no reducing ability, and then a reducing organometallic compound [II] and a liquid titanium compound [I1[] are reacted. Obtained by contact reaction. Examples of the support (i) that can be used in the present invention include inorganic or organic porous supports, which preferably contain hydroxyl groups. ,! ! Organic oxides are preferably used, specifically S10, A, l1203, MgO1Z
rO2, T10, B2O3, CaO1ZnO1[3a
O1Th02 etc. or mixtures thereof, e.g. Si
O-MgO, 5iO2-Al203, SiO-TiO,
SiO-V2O3, SiO-CrO, SiO-Ti02-Mg0, etc. are used. Among these, a carrier containing at least one component selected from the group consisting of 5I02 and A12o3 as a main component is preferable.The above-mentioned inorganic oxides may contain small amounts of Na2CO3, K2CO3, CaCO3, etc.
3, MgCO3, Na2SO4, Al2 (S04)3
, Ba5O, KNO3, Mg(NO3)2, Al<NO
), carbonate, sulfate, nitrate, and oxide components such as Na2O, K2O, and Li2O may be contained. Although the properties of such a support that is 11 oxide vary depending on its type and manufacturing method, the support preferably used in the present invention has an average particle size of 5 to 200 μm, preferably 10 to 100 μm, Specific surface area is 50-1000
rrf/r, preferably 100 to 700 rf/g, and a pore volume of 0.3 to 3.0 aIl/g, preferably 0
．． It is 5 to 2.5 i/g. The support which is such an inorganic oxide is usually heated at 150 to 1000°C, preferably 2
It can be used after being fired at 00 to 800°C. As the organic support, organic polymers such as polyethylene, polypropylene, and polystyrene are used. Among these supports, porous inorganic compounds are preferred, and porous inorganic oxides are particularly preferred. By using the support (1) as described above, it is possible to relatively easily produce large and spherical polymer particles. Therefore, handling of the resulting polymer particles is facilitated, and furthermore, since the destruction of the polymer particles is prevented, adhesion of the finely powdered polymer to the polymerization wall surface or piping surface is prevented. In the present invention, first, the support as shown in ``-'' is prepared in advance.
M! The organoaluminum compound (ii) used in this case, which is brought into contact with the A aluminum compound (it), is an organoaluminum compound that can be used when polymerizing an olefin in combination with titanium II + a medium component, as described below. The components can be exemplified. Specifically, trialkyl aluminum such as trimethylaluminum, triethylaluminum, and tributylaluminum, algenylaluminum such as isoprenylaluminum, dialkylaluminum alkoxide such as dimethylaluminum, methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide, and methyl Alkylaluminium sesquialkoxides such as aluminum sesquimethoxide, ethylaluminum sesquiethoxide, partially alkoxylated alkylaluminums having an average composition expressed as RAl12.5 (OR), etc.
Dimethylaluminum chloride, diethylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquihalide such as methylaluminum sesquihalide, methylaluminum dichloride, ethylaluminum dig1furide, etc. Partially halogenated alkylaluminum such as alkylaluminum cybaride, alumoxanes such as methylalumoxane, ethylalumokichisan, imbutylalumoxane, and partially halogenated methylalumoxane are used. As the organoaluminum compound, trialkyl aluminum and dialkyl aluminum chloride are preferred, and trimedel aluminum, triethyl aluminum, and triisobutyl aluminum 5-diethyl aluminum chloride are particularly preferred. Two or more of these organoaluminum compounds are used. It can also be used. Support (i) and organoaluminum compound 'f4fJ (i
i), the organoaluminum compound (11) contains 0.1 to 100 milligram atoms, preferably 0.5 to 50 milligram atoms, as aluminum atoms in the organoaluminum compound, per g of support]; More preferably a range of 1 to 30 milligram atoms is used, particularly preferably 1.5 to 20 milligram atoms. The contact between the support (i) and the organoaluminum compound (11) is carried out, for example, by adding one or more of the above organoaluminum compounds to an inert solvent in which the support is dispersed, and usually - 50°C or higher, preferably 10~
By contacting both at a temperature of 200°C, preferably 20 to 130"C, for 1 minute or more, preferably 20 minutes to 5 hours, more preferably 30 minutes to 3 hours under normal pressure, vacuum pressure or pressurization. When bringing the support (i) into contact with the organoaluminum compound (ii), the support (i) is usually mixed in an inert solvent at 10 to 800 g per 11 reaction volumes, preferably 50 to 400 ir. It is preferable to conduct the reaction while dispersing the support (i) in the organic aluminum compound (H). When contacting the support (i) with the organoaluminum compound (H), as an inert solvent, pentane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane, kerosene; Alicyclic hydrocarbons such as dichloropentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, cyclohexene; benzene; Examples include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, and cymene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, carbon tetrachloride, and chlorobenzene. The above support (i) and organoaluminum compound (ii)
It is preferable to remove free organoaluminum compounds or their reactants that are not immobilized on the support by contact with the support by a decandation method, a filtration method, or the like. Next, after bringing the support (i) into contact with the organoaluminum compound (ii) in this way, the magnesium-containing support is brought into contact with a liquid magnesium compound that does not have reducing ability. can get. Examples of the magnesium compound (i) in the 'tf★ state without reducing ability include a magnesium compound dissolved in a hydrocarbon, an electron donor (a), or a mixture thereof, or a solution of a magnesium compound in a hydrocarbon. used. Magnesium compounds used in this case include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, impropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride, etc. alco-A-simamagnesium halides; allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxy-magnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, octoxymagnesium, and 2-ethylhexoxymagnesium; phenoxymagnesium,
Allyloxymagnesium such as dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate are used. Further, the magnesium compound may be a complex compound or composite compound with another metal, or a mixture with another metal compound J, or may be a mixture of two or more of these compounds. Among these, preferable magnesium compounds include (X is a halogen and R5 is a hydrocarbon group)
Magnesium halides, alkoxymagnesium halide, allyloxymagnesium halide, alkoxymagnesium, and allyloxymagnesium are used, and halogen-containing magnesium compounds, especially magnesium chloride, alkoxymagnesium chloride, allyloxymagnesium chloride, and particularly magnesium chloride are preferably used. . These magnesium compounds Th(ii) in liquid state
As mentioned above, a magnesium compound solution prepared by dissolving the magnesium compound in a hydrocarbon solvent or an electron donor (a), or a combination of a hydrocarbon solvent and an electron donor (a) such as A magnesium compound solution obtained by dissolving the magnesium compound in a mixture is suitable. Hydrocarbon solvents used in this case include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, and kerosene; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, Alicyclic hydrocarbons such as cyclohexene; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, carbon tetrachloride, and chlorobenzene An example of this is the series. In order to dissolve the above-mentioned magnesium compound in a hydrocarbon solvent, the method differs depending on the type of magnesium compound and solvent, but there is a method of simply mixing the hydrocarbon solvent and the magnesium compound (for example, Mg having 6 to 2 carbon atoms as R). (OR5)), a method of heating after mixing a hydrocarbon solvent and a magnesium compound, an electron donor (a) capable of dissolving the magnesium compound, such as alcohol, aldehyde, amine, carboxylic acid, etc. A mixture, or even a mixture of these and other electron donors, etc., is made to coexist in a hydrocarbon solvent, and the mixture of this hydrocarbon solvent and electron donor (a) is mixed with a magnesium compound, and if necessary, , heating method, etc. can be adopted. For example, when we discuss the case where a halogen-containing magnesium compound is dissolved in a carbonization-accepting solvent using alcohol as the electron donor (a), it will vary depending on the type of hydrocarbon solvent, the certificate of use, the type of magnesium compound, etc. The alcohol is used in an amount of about 0.5 mole or more, preferably about 1 to about 20 moles, more preferably about 1.5 to about 12 moles, per mole of the halogen-containing magnesium compound.
Moles, particularly preferably in the range of about 1.8 to 4 moles. The amount of al:1-l varies somewhat depending on the type of hydrocarbon solvent used, and when an aliphatic hydrocarbon and/or alicyclic hydrocarbon is used as the hydrocarbon,
The alcohol having 6 or more carbon atoms is added in an amount of about 1 mol or more, preferably about 1.0 mol or more, preferably about 1.
If 5 mol or more is used, it is possible to solubilize a halogen-containing magnesium compound with a small total amount of alcohol used,
This is preferable because it provides a contact component with a good shape.On the other hand, if only an alcohol having 5 or more carbon atoms is used, a large amount of alcohol is required per mole of the halogen-containing magnesium compound. On the other hand, if an aromatic hydrocarbon is used as the hydrocarbon, the amount of alcohol required to solubilize the halogen-containing magnesium compound can be reduced regardless of the type of alcohol. The contact between the halogen-containing magnesium compound and the alcohol is preferably carried out in a hydrocarbon solvent, and usually -5
0° C. or higher, depending on their type, about room temperature or higher, preferably about 80-300° C., preferably about 100-20° C.
At a temperature of 0°C, usually 1 minute or more, preferably 15 minutes to 5 minutes.
This is carried out by contacting for about an hour, more preferably for about 30 minutes to 2 hours. Specifically, alcohols having 6 or more carbon atoms are preferably used, such as 2-methylpentanol, 2-ethylbutanol, n-heptatool, n-
Octatool, 2-ethylhexanol, decanol,
Aliphatic alcohols such as dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol, stearyl alcohol, alicyclic alcohols such as cyclohexanol, methylcyclohexanol, benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α-methylbenzyl alcohol, α ,α
Aromatic alcohols such as -dimethylbenzyl alcohol, aliphatic alcohols containing alkoxy groups such as rope tyl cellosolve, 1-butoxy-2-propatol, and 1-butoxy-6-hexanol are used. Alcohols other than the above include methanol, ethanol,
Alcohols having carbon atoms of 5 or less, such as propatool, butanol, ethylene glycol, and methylcarpitol, are used. The hydrocarbon solvent has a concentration of magnesium chloride compound (j) in the solution [I] of 0.1 to 10 mol/1, more preferably 0.5 to 3 mol/l! Used in large quantities. When contacting the contact material of support (i) and organoaluminum compound < ii) with a liquid magnesium compound that does not have reducing ability, the liquid magnesium compound that does not have reducing ability is, for example, attached to the support. per gram atom of aluminum in the magnesium compound (ii), typically 0.1 or more gram atoms, preferably from about 0.1 to about 6 gram atoms,
Particularly preferably, amounts from about 0.5 to about 3 gram atoms are used. In addition, in such a catalytic reaction, the support is, for example, 10 to 800 f/j, preferably 50 to 4
It can be carried out under conditions where the concentration is such that 00 g/It is present. A hydrocarbon solvent, which will be described later, may be added as appropriate to achieve such a concentration. The above-mentioned contact reaction is usually carried out at -50°C or higher, preferably at room temperature to 200°C, preferably at 30 to 100°C.
This is carried out by contacting at a temperature of usually 1 minute or more, more preferably 30 minutes to 3 hours. The support-supported titanium contact component according to the present invention is produced by a contact reaction between the magnesium-containing support [■] obtained as described above, the reducing organometallic compound [II], and the liquid titanium compound [I1 []. It can be obtained by As a method for bringing these respective components into contact, for example, the magnesium-containing support [I] and the organometallic compound [
A method of contacting a titanium compound [I[I] after contacting a magnesium-containing support [I], or a method of contacting an organometallic compound [III] after contacting a magnesium-containing support [I] and a titanium compound [If[]. , or magnesium-containing support [I], organometallic compound '$JJ [II]
For example, a method of simultaneously contacting the titanium compound [If[] and the titanium compound [If[] can be exemplified. When carrying out such contact, a hydrocarbon solvent as described below can be used. When contacting each component as described above, for example, 0.1 to 10 g atoms of the organometallic compound [II], preferably 0.3 to 5 g atoms, per 1 g atom of magnesium in the magnesium-containing support [I]. gram atoms, particularly preferably in the range from 0.5 to 2 gram atoms, and the titanium compound [I[[] is usually less than 2, preferably 0.0
It is used in amounts ranging from 1 to 1.5, particularly preferably from 0.08 to 1.2. Further, when contacting each component as described above, the concentration of the magnesium-containing support [I] is, for example, 10 to 800 t/J, preferably 50 to 400 g.
/ , G using a magnesium-containing support. A hydrocarbon solvent, which will be described later, may be used as appropriate to achieve such a concentration. Further, the contact reaction is carried out, for example, at a temperature of usually -50°C or higher, preferably room temperature to 200°C, preferably 30 to 100°C, for usually 1 minute or more, more preferably 30 minutes to 30 minutes. It will be done for about an hour. Organometallic compounds that can be used in the above-mentioned catalytic reactions!
As m[II], in addition to the organoaluminum compound used in the polymerization of olefin as described below or the above-mentioned organoaluminum compound (ii),
Organic dimite or organolithium such as diethylzinc, as well as Grignard reagents, dialkylmagnesiums or complex compounds of these organomagnesium compounds with other organometallic compounds, such as MaMcJβRpR, XrY, [wherein M is aluminum, tin, boron or is a beryllium atom, R1,
R2 is a hydrocarbon group, and X and Y are OR3,08iR4
R5R6, NR7R8, SR groups, R3, R4
, R5, R6, R7, R8 are hydrogen atoms or hydrocarbon groups, R9 is a hydrocarbon group, α, β>O, p, q
, r, s≧0, m is valence, β/α≧0.5, pmoq+
r+s=mα+2β, 0≦(r+s)/(αmoβ)<1
．． Magnesium compounds having a reducing ability such as 0 can be exemplified. Among these organometallic compounds, organoaluminum compounds or organomagnesium compounds are preferred, and organoaluminum compounds are more preferred. Among organoaluminum compounds, trialkylaluminum and dialkylaluminum halides are particularly preferred, and these can also be used in combination. In addition, the liquid titanium compound [I[[] is usually Ti(OR)X (R is a hydrocarbon group).
4-Q, X is a halogen, and a tetravalent titanium compound represented by 0≦Q≦4) is suitable. More specifically, Ti
Tetrahalogenated titanium such as CJl, TiI3r, T+I4; TifOCl-I)Cj, Ti(OC2H5)C
l3, Ti(On-C4H9)C13, Ti(Oiso-C4H9)C13, Ti(OC2H5)B'3, Ti(Oiso-CH)Br, Ti(02-edylhexyl)Cj3, and other trihalogenated alkoxytitaniums ; Ti(OCH3)2Cj2, Ti(OC2H5)2C12, Ti(On-C4H9) 2CJI 2, Ti(OC2
■(5) 2B “Dihalogenated alkoxytitanium such as 2; Ti(OCH3)3 Cj, Ti(OC2H5)3 C
j. Ti(On-C4I(9)3CJl, monohalal]trialkoxytitanium with Ti(OC2H5)3Br; Ti(OCH), Ti(OC2H5) 4, Ti(
On-CH), Ti(OiSO-C4H9) 4,
Tetraalkoxytitanium such as Ti(02-ethylhexyl)4 or a mixture of these and other metal compounds such as an aluminum compound or a silicon compound can be used. Furthermore, R2TiX, (R is a hydrocarbon group and j4-
” R and X are halogens, and tetravalent organic titanium compounds represented by O<J≦4) can also be exemplified. More specifically, halogenated titanium such as biscyclopentadienyltitanium dichloride, and halogen-free titanium compounds such as biscyclopentagenyltitanium dimethyl can be used. Furthermore, Ti(OR)
3-h is an elementary group, X is a halogen, and a trivalent titanium compound represented by 0≦h≦3) can also be used. Among these trivalent titanium compounds, when these compounds themselves are not in a liquid state, the titanium compound can be dissolved in a hydrocarbon, alcohol, ether, etc. and used in a liquid state. Examples of these trivalent titanium compounds include TiCl, Ti[0C2H5)3, Ti
(On-CH), TifOiSO-C4H9) 3
, Ti(02-ethylhexyl), Ti(02-ethylhexyl)CJ12, and the like are used. Among the above-mentioned Ti compounds, the liquid titanium compound [I[II] that can be used in the present invention is preferably a tetravalent titanium compound, particularly a halogen-containing tetravalent titanium compound. The liquid titanium compound [III] may be used as it is when the titanium compound is liquid, or may be used as a mixture thereof, or may be used by dissolving the titanium compound in a solvent such as a hydrocarbon. You can. In the support-supported titanium catalyst component thus obtained, 'r''i/M(] (atomic ratio) is usually greater than 0.01 and less than or equal to 1, preferably greater than 0.05 and 0,
6 or less, A, ll/'MO (atomic ratio) is greater than 0.5 and 4 or less, preferably greater than 1 and 3 or less, and halogen/MQ (atomic ratio) is greater than 2 and 10 or less. , preferably greater than 3 and less than or equal to 6, and R
O; u/Mg (R is a hydrocarbon group) has a weight ratio of greater than 1 and less than or equal to 15, preferably greater than 1.5 and less than or equal to 10, particularly preferably greater than 2 and less than or equal to 6; Surface area is 50-1000rd/g, preferably 100rd/g
~500rrr/g. The average valence of Ti is usually less than 4, preferably 3.5 to 2.5. Further, the particle size of the titanium catalyst component is usually 5 to 20
The particle size is 0 μm, preferably 10 to 100 μm, particularly preferably 20 to 60 μm, and the particle size distribution is usually in the range of 1.0 to 2.0 in terms of geometric standard plane difference. Hydrocarbon solvents that can be used in preparing the titanium catalyst component of the present invention are aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, and kerosene; cyclopentane; ,
Alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclohexene; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene; dichloroethane, dichloropropane, trichloroethylene, Examples include halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene. In the present invention, ethylene polymerization or ethylene and α
- Organoaluminum compounds that can be used together with the titanium catalyst component described above when copolymerizing with olefins include at least one A,
Compounds having a g-carbon bond, for example, (where R1 and R2 are usually hydrocarbon groups containing 1 to 15, preferably 1 to 4 carbon atoms, and may be the same or different from each other, X is halogen, m is O
<m≦3, n is O≦n×3, and P is 0≦p<
3, q is 0≦q×3, and m + n
+-p-1-q = 3), (ii) -MAJR (where Ml is Li, Na, and R1 is the same as above) Examples include complex alkylated products of Group 1 metals and aluminum. Examples of the organoaluminum compounds belonging to (i) above include the following. General formula RAJI(OR) (where R1 and R
2 is the same as above 0m is preferably 1.5≦m<3
), one mathematical formula RAlX (where R1 is the same sign as above)
3-11 are the same, X is halogen, m is preferably 0<m
<3), one mathematical formula R, l) (<where R1 is the same ra as above
0m which is the same as 3-n+ is preferably 2≦m<3), and R2 is the same as above. X is halogen, O<m
≦3.0≦n<3.0≦q 3, m-1-n+q
= 3). More specifically, the aluminum compounds belonging to (i) include trialkylaluminum such as triethylaluminum and tributylaluminium, trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, dibutylaluminum butoxide, etc. , ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, etc.
R) 0.5 partially alkoxylated alkyl aluminum having an average composition such as
dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminium bromide, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide, ethylaluminum dichloride, propylaluminum dichloride, Partially halogenated alkylaluminiums such as alkylaluminum cybarides such as butylaluminum dibromide, dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dicdride, probylaluminum dihydride, etc. Partially hydrogenated alkyl aluminums such as alkyl aluminum dihydride, partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide are used. Further, as a compound similar to (i), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom is used. Examples of such compounds include (CH) AlOAJ (C2H5)2, (C4H
s )2 AN OAl (C4Hg )2, Ce
Hs I can give an example. Compounds belonging to (ii) above include LiAl(C
Examples include H), Li, 1(C7H15)4, and the like. Among these compounds, the average composition is RA, l! X3-1 (wherein, R is an alkyl group, X is a halogen,
Preferred examples include the above-mentioned organoaluminum compounds or arbitrary mixtures of the above-mentioned organoaluminum and aluminum trihalide so as to satisfy 2≦n≦3). Further, in the formula, R is an alkyl group having 1 to 4 carbon atoms, X is chlorine, and 2.1≦n≦2.9
Organoaluminum compounds that satisfy the following are particularly preferably used. The polymerization catalyst comprising a titanium catalyst component and an organoaluminum compound according to the present invention can be used for ethylene homopolymerization or ethylene and olefin copolymerization, and can also be used for ethylene and polyene copolymerization or ethylene and α-olefin and polyene polymerization. It can also be used for copolymerization with 0
Examples of olefins that can be used for polymerization in the present invention include, in addition to ethylene, propylene, 1-butane,
Examples include 1-pentene, 1-hexene, 4-, methyl-1-pentene, 3-methyl-1-pentene, 3-methyl-1-butane, 1-octene, 1-decene, and the like. Examples of the above-mentioned polyenes include butadiene, isoprene, hexadiene, dicyclopentadiene, 5-ethylidecy-2-norbornene, etc. In the case of ethylene copolymerization, especially about 70% by weight of ethylene
It is preferable to carry out the copolymerization so that ethylene and a small amount of α-olefin are contained, and in the present invention, the density is 0.880 to 0.970 g/c.
d, especially when producing a low density ethylene copolymer of 0.890 to 0.940 g/ad by slurry polymerization or especially gas phase polymerization. The polymerization of olefins can be carried out in the liquid or gas phase, in the presence or absence of an inert solvent. Examples of inert solvents that can be used for the polymerization include propane,
Aliphatic hydrocarbons such as butane, pentane, hexane, octane, decane, kerosene; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene ; etc. can be exemplified. When producing an ethylene copolymer having a particularly low density, it is preferable to employ a gas phase polymerization method. The amount of each catalyst component used in carrying out the olefin polymerization reaction can be changed as appropriate or selected from three options, but for example, the amount of titanium catalyst component is preferably about 0.0001 to 1 in terms of titanium atoms per 11 reaction volumes. The organoaluminum compound is used in an amount such that the aluminum/titanium (atomic ratio) is about 1 to about 2000, preferably about 5. The degree of polymerization, which is preferably used in an amount of 100 to about 100, is preferably 20 to 150°C, particularly preferably 40 to 100"C. Well? - The polymerization pressure is from atmospheric pressure to about 100 kg/aJ -G
, preferably about 2 to about 501 f/cJ-c. In olefin polymerization, in order to adjust the molecular weight,
It is preferable to allow hydrogen to coexist in the reaction system. Polymerization can be carried out batchwise or continuously. Furthermore, the process can be carried out in two or more stages with different conditions. Prior to carrying out the polymerization or copolymerization of ethylene using the titanium catalyst component of the present invention, in the presence of at least a titanium catalyst component and an organoaluminum compound component, usually 5 g is added per milligram atom of titanium in the titanium catalyst component.
Above, preferably 10 to 3000g, particularly preferably 2
Preferably, ethylene or ethylene and α-olefin are prepolymerized in a polymerization amount in the range of 0 to 1000 g. Prepolymerization can be carried out in the presence or absence of a fugitive hydrocarbon melt. That is, the preliminary polymerization can be carried out by slurry polymerization, gas phase polymerization, or the like. As the inert hydrocarbon solvent, the above-mentioned hydrocarbon solvents are used, and among these, aliphatic hydrocarbons having R3 to R10 or alicyclic hydrocarbons having R5 to R10 are particularly preferably used. The α-olefin used in prepolymerization includes ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-bentene, 1-heptene, 1-octene, α-olefins having 10 or less carbon atoms such as 1-decene are preferable, and α-olefins having 2 to 6 carbon atoms are more preferable, and ethylene alone or a combination of ethylene and a J2 α-olefin is particularly preferable. . These α-olefins may be used alone, or two or more types may be used in combination as long as a crystalline polymer is produced. The polymerization temperature in preliminary polymerization is generally -40~. 100°C5, preferably -20 to 60°C, more preferably -10 to 40°C. Hydrogen can also be present in the prepolymerization. When carrying out the prepolymerization, the organoaluminum component is usually at least 0.1 gram atom, preferably 0.5 to 200 gram atom, more preferably 0.5 to 200 gram atom, per gram atom of titanium in the titanium catalyst component. The amount used is about 1 gram atom to 30 gram atoms. Furthermore, when performing the pre-OI polymerization, various electron donor components such as those described above may be present. When olefins are polymerized using the titanium catalyst component according to the present invention, olefins can be polymerized with high activity,
Moreover, the resulting copolymer has a narrow composition distribution, and a finely divided olefin polymer having a narrow particle size distribution and high polymer bulk specific gravity can be obtained. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. [Preparation of titanium catalyst component] 10 g of Fuji Davison silica (F952) calcined at 200°C for 2 hours and then at 700°C for 5 hours was purified n-
5 ml of an n-decane solution containing 50 mmol of triethylaluminum in 40 ml of decane and then containing 50 mmol of triethylaluminum in this suspension.
After adding 0 ml, the resulting suspension was stirred at 90° C. for 2 hours to carry out a contact reaction between the silica and triethylaluminum. After the reaction was completed, the solid portion was separated from the reaction solution by filtration. The resulting solid portion contained aluminum equivalent to 1.1 mmol atom per gram of silica. This solid part9.
Re-install Og with n-deca 7100011! After clouding, 48 g of magnesium chloride, 197 g of 2-ethylhexanol and 175 g of n-decane were added to the resulting suspension at 140 g.
6.4 ml of magnesium chloride decane i8 M (corresponding to about 6.4 mmol of Mg) obtained by heating and stirring at °C for 2 hours was added, the temperature was raised to 80 °C, and after about 1 hour 7. 7 mmol was added and the reaction was further carried out at 80°C for 1 hour.Next, a solid portion was separated from this reaction solution by filtration, and this solid portion was resuspended in 100 ml of n-decane. Thing 2-
Add ethylhexoxytrichlorotitanium to 80
A catalytic reaction was carried out by stirring at °C for 1 hour. The solid portion was then separated by filtration and washed twice with 100 ml of hexane to prepare titanium catalyst component [A]. The amount of titanium supported in the obtained titanium catalyst component was 0.5% by weight. [Prepolymerization] In a 400 a+I cylindrical flask with a stirrer, 200 ml of purified hexane, 0.6 mmol of triethylaluminum, and the above titanium catalyst component [A] were added to O-2 mmol in terms of titanium atoms, and the mixture was heated to 30°C. and add ethylene to 8
Prepolymerization of ethylene was carried out by feeding at a rate of N1/hour over a period of 3 hours. The amount of polyethylene produced was 142 g/mmol Ti. [Ethylene polymerization] Add 150 g of sodium chloride as a dispersant to a two-layer autoclave that has been sufficiently purged with nitrogen, and while heating to 90°C, raise the internal pressure of the autoclave to 50 rur H.
The pressure in the autoclave was reduced to below IJ for 2 hours using a vacuum pump.Then, the temperature of the autoclave was lowered to room temperature.
After replacing the inside of the autoclave with ethylene, 0.5 mmol of triethylaluminum, 0.5 mmol of diethylaluminum chloride, and 19 ml of hexene were added, the system was sealed, the temperature was raised, and hydrogen was added at 60°C.
kg/-, and while further pressurizing with ethylene, the catalyst component subjected to the above prepolymerization was 0.005 in terms of titanium atoms.
During the polymerization, the temperature was maintained at 80° C. and the pressure was maintained at 8 kg/aJG by supplementing with ethylene gas. After adding the titanium catalyst component, 136ml of hexene was added to
The zero polymerization, which was supplied using a pump over a period of time, was terminated one hour after the addition of the titanium catalyst. After the polymerization was completed, the contents of the autoclave were poured into about 11 g of water. After about 5 minutes of stirring, almost all of the sodium chloride was dissolved in the standing water, leaving only the polymer floating on the water surface. After harvesting this floating polymer and thoroughly washing it with methanol,
Drying was carried out overnight at 80°C under reduced pressure. Table 1 shows the composition and polymerization results of the titanium catalyst component obtained. ! A titanium catalyst was prepared in the same manner as in Example 1, except that 50 mmol of triethylaluminum and 7.7 mmol of diethylaluminium chloride used in the preparation of the titanium catalyst in Example 1 were replaced with the compounds shown in Table 1. Shi, pre(i)
Copolymerization of ethylene and hexene-1 was carried out on a tiff stand. The composition and polymerization results of the obtained catalyst are shown in Table 1. Note that methylalumoxane used in Example 5 was synthesized by the following method. 2074 g of AN (So) 14H was placed in an aluminium-sized glass flask with a stirrer, which was sufficiently purged with nitrogen.
and 250ml of toluene and cooled to 0°C,
Toluene 25 containing 100 ml of trimethylaluminum
0ml was added dropwise over 1.5 hours. Next, the temperature was raised to 10°C over 2 hours, and at that temperature
After 8 hours of continuous reaction, solid-liquid separation was performed by filtration to remove low boiling point substances from the separated M solution using an evaporator, toluene was added to the residue, and a toluene solution was collected. The molecular weight of aluminoxane determined from the freezing point depression of benzene was 891. A titanium catalyst was prepared in the same manner as in Example 1, except that the mono-2-ethylhexoxy-1-helichlorotitanium used in the preparation of the titanium catalyst in Example 1 was replaced with the compound shown in Table 2. Silica Log and 50 mmol of triethylaluminum were reacted in the same manner as in Example 1, and aluminum was A treated carrier was prepared in which 1.3 mmol atoms were immobilized per gram of silica. Treat the carrier with n-decane 1000
) Magnesium decane: 8 liquid 6 obtained by resuspending 104.8 g of ethoxymagnesium chloride, 390 g of 2-ethylhexanol, and 355 g of n-decane at 140°C for 2 hours after resuspending it in I.
/Ill11 was added, the temperature was raised to 80°C, and after about 1 hour, the temperature was lowered to 55°C, and 30ml of silicon tetrachloride was added.
The reaction was carried out at the same temperature for 2 hours, then the solid part was separated by V filtration, resuspended in 100 ml of n-decane, 7.7 mmol of diethylaluminum chloride was added, and the mixture was heated at 80°C.
The reaction was carried out for 1 hour. Thereafter, a titanium compound loading reaction was carried out in the same manner as in Example 1 to prepare a titanium catalyst component, and prepolymerization and copolymerization of ethylene and hexene-1 were also carried out in the same manner as in Example 1. The catalyst composition and polymerization results are shown in Table 2. In Example 13, 10.1.8 g of fried ethoxy magnesia lamb, 390 g of 2-ethylhexanol, and 355 g of 0-decane were heated and reacted at 140°C for 2 hours. A catalyst was prepared in the same manner as in Example 13, except that the catalyst was replaced with a heptane solution containing 4 mmol of magnesium bis-2-ethylhexoxide, and prepolymerization and copolymerization of ethylene and hexene-1 were carried out. . The catalyst composition and polymerization results are shown in Table 2.

[Brief explanation of the drawing]

The figure shows Il! used in the present invention! l! FIG. 2 is a flowchart showing medium components and preparation steps. Agent Patent attorney Shunichi Meiki JE book (Method) % formula % 1. Indication of the case 1989 Patent Application No. 89,600 2. Name of the invention Titanium catalyst component and its manufacturing method 3. Amendment Relationship with the famous case Patent applicant Name Mitsui Petrochemical Industries Co., Ltd. 4, Agent (Postal code 141) N.M. Building 4, Higashigotanda-chome-25-4, Tokyo Parts Ward
Floor: June 8, 1988 (Shipping port: June 28, 1988)
7. Details of amendments 1) The drawings will be amended as shown in the attached sheet. (No change in content) 2) In the second line of page 48 of the specification, the text ``J'' in ``The figure shows the present invention'' is amended to read ``Figure 1 shows the present invention.'' July 28, 1988 Director General of the Japan Patent Office Yoshi 1) Takeshi Moon 1. Indication of the facts 1989 Patent Application No. 89,600 2. Name of invention titanium catalyst component and its manufacturing method 3. Amended. Relationship with the patent applicant name Mitsui Petrochemical Industries Co., Ltd. 4, agent (zip code 141) N.M. Building 4, Higashigotanda-chome-25-4, Tokyo Parts Ward
Floor [Telephone Tokyo (444) 3151] Voluntary amendment 6, Column 7 of "Detailed explanation of the invention J" of the specification subject to amendment, Contents of amendment (1) Line 6 and line 7 of page 8 of the specification Insert the following sentence between the eyes.

Claims (10)

[Claims] (1) At least [I] The organoaluminum compound (i) is added to the support (i).
A magnesium-containing support obtained by contacting i) with a liquid magnesium compound (i) having no reducing ability, [II] a reducing organometallic compound, and [III] a liquid magnesium compound (i). A support-supported titanium catalyst component containing magnesium, aluminum, halogen, and titanium as essential components obtained by catalytic reaction of titanium compounds. (2) The liquid magnesium compound without reducing ability is a magnesium compound selected from the group consisting of MgX_2, Mg(OR)X, Mg(OR)_2 and magnesium carboxylates (where X is a halogen and ,
R is a hydrocarbon group), an electron donor (a), and a hydrocarbon solvent, or a magnesium compound selected from the group consisting of Mg(OR)_2 and carboxylic acid salts of magnesium and a hydrocarbon solvent. A catalyst component according to claim 1, which is a solution formed from. (3) The catalyst component according to claim 2, wherein the electron donor (a) is an alcohol. (4) The catalyst component according to claim 1, wherein the liquid titanium compound [III] is a tetravalent titanium compound. (5) The average valence of titanium atoms in the titanium catalyst component is
4. The catalyst component of claim 1, wherein the catalyst component is less than 4. (6) The average particle diameter of the titanium catalyst component is 10 to 100 μm
The catalyst component according to claim 1. (7) The catalyst component according to claim 1, wherein the support is an inorganic oxide containing a hydroxyl group. (8) The catalyst component according to claim 1, wherein the reducing organometallic compound [II] is an organoaluminum compound. (9) Ti/Mg (atomic ratio) in the titanium catalyst component is 0.
01 to 1 or less, Al/Mg (atomic ratio) to 1 to 3 or less, halogen/Mg (atomic ratio) to 3 to 6 or less, RO group/Mg (R is a hydrocarbon group) by weight The catalyst component according to claim 1, wherein the ratio is greater than 1 and less than or equal to 15. (10) [I] A magnesium-containing support [I] is prepared by contacting the support (i) with the organoaluminum compound (i) in advance and then contacting the magnesium compound (ii) in a liquid state with no reducing ability. ] and then contacting the obtained magnesium-containing support with [II] a reducing organometallic compound and [III] a titanium compound in a liquid state. A method for producing a support-supported titanium catalyst component as an essential component.