JPH01287107A - Titanium catalyst component and production thereof - Google Patents

Abstract

PURPOSE:To provide a Ti catalyst component containing Mg, Al, halogen and Ti as essential components, capable of polymerizing an olefin in high activity and giving an olefin polymer having narrow compositional distribution and particle size distribution and high bulk density of the polymer. CONSTITUTION:The objective Ti catalyst component containing Mg, Al, halogen and Ti as essential components and supported on a carrier can be produced by contacting and reacting (A) a Mg-containing carrier produced by preliminarily contacting a carrier with a liquid organometallic compound (e.g. diethylmagnesium or butylethylmagnesium) which is an organometallic compound of a metal of group II-IIIA of the periodic table except for Al and having >=2 hydrocarbon groups directly bonded to the metal atom and then contacting and reacting the organometallic compound with a liquid Mg compound (e.g. MgCl2) free from reducing power, (B) an organic Al compound (e.g. trimethylaluminum) and (C) a liquid Ti compound (e.g. TiCl4).

Description

[Detailed Description of the Invention] Nine Blood Cutting Stones 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 granular olefin polymer having a narrow composition distribution of the produced copolymer, a narrow particle size distribution, and a high polymer bulk specific gravity.

Technical background of the invention and its problems It is known that when ethylene and a small proportion of α-olefin are copolymerized using a Ziegler type catalyst, an ethylene copolymer having a density comparable to that of high-pressure polyethylene can be obtained. Are known. 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 above the melting point of the copolymer to be produced using a hydrocarbon 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 with this is that it has no choice but to be of low quality.

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, which caused problems in terms of quality. These problems can be solved using specific catalysts.
Several methods have been proposed that attempt to improve by employing prepolymerization.

The present inventors have already studied catalysts suitable for producing low-density ethylene copolymers, and as a result, they have discovered a catalyst system that has even better 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 vanadine compound with excellent copolymerizability 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. It will be done. 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 molded product with excellent transparency, blocking resistance, heat sealability, etc. Even in the process where all of the copolymers produced are made into 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 therefore waste liquid treatment is easy. The object of the present invention is to provide a titanium catalyst component and a method for producing the same.

9.11 The support-supported titanium catalyst component according to the present invention, which has magnesium, aluminum, halogen, and titanium as essential components, has at least [III] support (i) containing a member of the periodic table group II or IIIA other than aluminum. After contacting a liquid organometallic compound (it) in which at least two hydrocarbon groups are directly bonded to metal atoms in advance,
Magnesium compound (i) in liquid state without reducing ability
A magnesium-containing support obtained by contacting [II] a reducing organometallic compound and [II] a titanium compound in a liquid state.

Further, in the method for producing a support-supported titanium catalyst component containing magnesium, aluminum, halogen, and titanium as essential components according to the present invention, [III] the support (1) is brought into contact with a liquid organometallic compound (it) in advance. After that, a liquid magnesium compound (iii
) by contacting the magnesium-containing support [
[III], and then the obtained magnesium-containing support is coated with [n] a reducing organometallic compound and [II[
] It is characterized by contacting with a titanium compound in a liquid state.

9 匪Δ 1 body shun 1 泪 The present invention will be explained in detail below.

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. .

The support-supported titanium catalyst component according to the present invention is obtained by a catalytic reaction of [III] a magnesium-containing support, [n] a reducing organometallic compound, and [III] a titanium compound in a liquid state. , aluminum, halogen and titanium are the essential ingredients,
Typically, support (i) and an organometallic compound of group I to I of the periodic table other than aluminum, which is an organic metal compound in a liquid state in which at least two hydrocarbon groups are directly bonded to a metal atom. After contacting the metal compound (ii) in advance,
The contact material is reacted with a liquid magnesium compound (if >) having no reducing ability, and then a reducing organometallic compound [II] and a liquid titanium compound [1] are reacted.
It is obtained by contact reaction with 1[].

The support (i) that can be used in the present invention includes inorganic or organic porous supports, and it is preferable that this support contains hydroxyl groups. As the inorganic support, inorganic oxides are preferably used, and specifically, 5i02, A, l1203, MgO, Z
rO2, T i O, B 203, Ca 01 Zn O
, BaO1ThO2, etc. or a mixture thereof, for example, Si02-MgO5Si02-A layer 203, S
iO-TiO2,5iO2-■205,S10-C"2
03.5iO2-T102-MQO, etc. are used. Among these, a carrier containing as a main component at least one component selected from the group consisting of 5102, A, and O203 is preferred. In addition, the above-mentioned inorganic oxides include
Small amounts of Na2CO3, K2CO3, CaCO3, MQ
CO3, Na2SO4, Aj2 (804)3
, Ba SO4, KNO3, M(](NO3)2, Aj
(NO), Na O, 20, Li 20
Carbonates such as vi'fm salts, nitrates, and oxide components may be contained.

Although the properties of such an inorganic oxide support 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 1
0~100μm, specific surface area 50~1000rr
1'/g, preferably 100 to 700 pi/g, and the pore volume is 0.3 to 3.0all/g, preferably 0.5
~2.5 dl/g. The support which is such an inorganic oxide is usually heated at 150 to 1000°C, preferably 2°C.
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 (i) as described above, it is possible to relatively easily produce large and spherical polymer particles. Therefore, handling of the obtained polymer particles becomes easy, and furthermore, the destruction of the polymer particles is prevented, and adhesion of the finely powdered polymer to the polymer wall surface and the inner surface of the pipe is also prevented.

In the present invention, first, the above-mentioned support is an organometallic compound of group I or InA of the periodic table other than aluminum, which is a liquid organic compound directly bonded to at least two hydrocarbon groups or metal atoms. Contacted with a metal compound (11). The liquid organometallic compound (i
Examples of i) include organic magnesium compounds, organic boron compounds, organic beryllium compounds, and organic zinc compounds. Among these compounds, organic magnesium compounds are preferred. In particular, the organomagnesium compound RM represented by the following formula! 1IR2 (wherein R1 and R2 may be the same or different and are an alkyl group or an aryl group having 1 to 12 carbon atoms) is preferred. More specifically, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, butylethylmagnesium, dihexylmagnesium, diphenylmagnesium, etc. are used. These organometallic compounds (ii) can be used in the form of complexes with ethers such as diethyl ether, aluminum alkoxides such as aluminum isopropoxide, organoaluminiums, particularly organometallic compounds such as triethylaluminum. Further, these organometallic compounds (it) or complex compounds of these organometallic compounds and the above-mentioned compounds can be used as a solution in a hydrocarbon solvent. Examples of the hydrocarbon solvent that can be used in this case include the hydrocarbon compounds described below.

Support (i) and Periodic Table ■ to I other than aluminum
When contacting the liquid organometallic compound (11), which is a Group IIA organometallic compound and has at least two hydrocarbon groups directly bonded to a metal atom, the liquid organometallic compound (ii ) is 0.1 to 100 metal atoms in the organometallic compound per 1 g of support.
It is used in amounts ranging from milligram atoms, preferably from 0.5 to 50 milligram atoms, more preferably from 1 to 30 milligram atoms, particularly preferably from 15 to 20 milligram atoms.

The contact between the support (i) and the above-mentioned liquid organometallic compound <ii) can be carried out by, for example, adding one or two of the above-mentioned organometallic compounds into an inert solvent in which the support is dispersed. Usually -50°C or higher, preferably 10 to 200°C, more preferably 20 to 130°C
This can be carried out by contacting the two under normal pressure, reduced pressure or increased pressure at a temperature of 1 minute or more, preferably 20 minutes to 5 hours, more preferably 30 minutes to 3 hours.

When bringing the support (i) into contact with the above liquid organometallic compound (11), the support N)
10 to 800 g per 1j of reaction volume, preferably 50 to 4
It is preferable to carry out dispersion in an inert solvent in an amount of 0.00 g.

When the support (i) is brought into contact with the liquid organometallic compound (ii) as described above, a hydrocarbon solvent as described below is used as the inert solvent.

In addition, free organoaluminum compounds or their reactants that are not fixed on the support by contacting the support (i) with the liquid organometallic compound (11) as described above can be removed by decantation method. It is preferable to remove it by a filtration method or the like.

Next, the support N) and a liquid organometallic compound of Group H or IA of the periodic table other than aluminum, in which at least two hydrocarbon groups are directly bonded to metal atoms ( After contacting ii) in advance, a magnesium-containing support is obtained by bringing this into contact with a liquid magnesium compound having no reducing ability.

Magnesium compound (i) in liquid state without reducing ability
For example, 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 can be 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, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride, etc. Alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride, etc. Allyloxymagnesium halides such as ethoxymagnesium isopropoxymagnesium, butoxymagnesium, octoxymagnesium, 2-ethylhexoxymagnesium; phenoxymagnesium, dimethylphenoxymagnesium Allyloxymagnesium such as magnesium laurate, magnesium carboxylate such as magnesium stearate, etc. are used.

Moreover, the magnesium compound may be a complex compound with other metals, a composite compound, or a mixture with other metal compounds. Furthermore, a mixture of two or more of these compounds may be used.

Among these, preferable magnesium compounds include (X is a halogen and R5 is a hydrocarbon group)
Magnesium halides represented by: alkoxymagnesium halide, allyloxymagnesium halide, alkoxymagnesium, allyloxymagnesium are used, and halogen-containing magnesium compounds, especially magnesium chloride, alkoxymagnesium chloride, allyloxymagnesium chloride, especially magnesium chloride are preferably used. .

These magnesium compounds in liquid state 'IIJ (ii
i), as mentioned above, is a magnesium compound solution prepared by dissolving the magnesium compound in a hydrocarbon solvent or an electron donor (a), or a solution of the above-mentioned hydrocarbon solvent and electron donor (a). A magnesium compound solution obtained by dissolving the magnesium compound in a mixture is suitable.

Hydrocarbon solvents used at this time include pentane, hexane, heptane, octane, decane, dodecane, and
~Aliphatic hydrocarbons such as radecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, methylcyclopenkune, cyclohexane, methylcyclohexane, cyclooctane, and cyclohexene: benzene, toluene, xylene,
Examples include aromatic hydrocarbons such as ethylbenzene, cumene, and cymene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, carbon tetrachloride, and chlorobenzene.

In order to dissolve the above-mentioned magnesium compound in a hydrocarbon solvent, it depends 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 20 carbon atoms as R). (OR)2), a method of heating after mixing a hydrocarbon solvent and a magnesium compound, an electron donor (a) that can dissolve the magnesium compound, such as an alcohol, an aldehyde, an amine, a 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, A method such as heating can be adopted. For example, let's talk about dissolving a halogen-containing magnesium compound in a hydrocarbon solvent using alcohol as the electron donor (a). , the alcohol is about 0.5 mol or more, preferably about 1 to about 20 mol, more preferably about 1.5 to about 12 mol, per mol of the halogen-containing magnesium compound,
Particularly preferably, it is used in a range of about 1.8 to 4 mol. The amount of alcohol varies somewhat depending on the type of hydrocarbon solvent used, and when using an aliphatic hydrocarbon and/or alicyclic hydrocarbon as the hydrocarbon, the amount of alcohol may vary depending on the type of hydrocarbon solvent used.
By using about 1 mol or more, preferably about 1.5 mol or more of the above alcohol per 1 mol of the halogen-containing magnesium compound, it is possible to solubilize the halogen-containing magnesium compound with a small total amount of alcohol. It is also preferable because it provides a catalyst component with a good shape. On the other hand, if only an alcohol having carbon atoms of 5 or less is used, a large amount of alcohol will be 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 medium, usually -5
0°C or higher, depending on their type, about room temperature or higher, preferably about 80-300°C 1-layer preferably about 100-2
At a temperature of 00°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 dotecanol, 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 n-butyl 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 is a magnesium chloride compound (iii)
It is used in an amount such that the concentration in the solution [II is 01 to 10 mol/p, more preferably 0.5 to 3 mol/p.

Support (i) and periodic table other than aluminum ■ or ■
An organometallic compound of A#, which is in contact with a liquid organometallic compound (ii) in which at least two hydrocarbon groups are directly bonded to a metal atom, and a liquid magnesium compound that does not have reducing ability. When contacting the liquid magnesium compound with no reducing ability, for example, the amount of magnesium in the liquid magnesium compound @ (ii) is usually 0.0% per gram atom of the organic metal in the support. 1 gram atom or more, preferably from about 0.1 to
The amount used is about 6 gram atoms, particularly about 0.5 to about 3 gram atoms. In addition, in such a catalytic reaction, the support is, for example, 10 to 800 g/Jl,
It can be carried out under conditions where the concentration is preferably 50 to 400 g/'. 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 a temperature of -50°C or higher, preferably room temperature to 200°C, preferably 30 to 100°C, usually for 1 minute or more, more preferably for 30 minutes to This is done by contacting for 3 hours.

The support-supported titanium catalyst component according to the present invention can be obtained by contact-reacting the magnesium-containing support [■] obtained as described above, the organoaluminum compound Th [n], and the liquid titanium compound [II []. can get.

As a method of bringing these components into contact, for example, after bringing the magnesium-containing support [II and the organoaluminum compound [II] into contact with each other, the titanium compound [II[
], or a method of contacting a magnesium-containing support [II and a titanium compound [III] and then contacting an organoaluminum compound [n], or a method of contacting a magnesium-containing support [■], an organoaluminum compound [■] For example, a method of simultaneously contacting the titanium compound [111[] and the titanium compound [111] 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 gram of the organoaluminum compound [n] is added per 1 gram atom of magnesium in the magnesium-containing support [III].
~10 gram atoms, preferably 0.3-5 gram atoms,
Particularly preferably, amounts in the range from 0.5 to 2 gram atoms are used, and the titanium compound [1[III] is usually less than 2, preferably from 0.01 to 1.5, particularly preferably from 0.08 to
Used in amounts in the range of 1.2. In addition, when contacting each component as described above, a magnesium-containing support [III
] can be carried out using a magnesium-containing support in an amount such that the concentration of magnesium is, for example, 10 to 800 g/fJ, preferably 50 to 400 g/fJ. A hydrocarbon solvent, which will be described later, may be used as appropriate to achieve such a concentration. Further, the catalytic reaction is, for example, usually -
50°C or higher, preferably room temperature to 200°C, - layer preferably 3
It is carried out at a temperature of 0 to 100° C. for usually 1 minute or more, more preferably for about 30 minutes to 3 hours.

As the organoaluminum compound [II] that can be used in the above-mentioned catalytic reaction, the same organoaluminum compound as the organoaluminum compound component used in olefin polymerization is used. Specifically, trialkyl aluminum such as trimethylaluminum, triethylaluminum, and tributylaluminum, alkenylaluminum such as imprenylaluminum, dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide, and methylaluminum sesquimethoxy. Alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, R,5,
0 with an average composition expressed as AJl(OR) etc.
．． 5 partially alkoxylated alkyl aluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, alkylaluminum cybarides such as methylaluminum dichloride, ethylaluminum dichloride Alumoxanes such as partially halogenated alkyl aluminum, methylalumoxane, ethylalumoxane, isobutylalumoxane, and partially halogenated methylalumoxane are used. ' The organoaluminum compound mentioned above is preferably 1-realkylaluminiumriethylaluminium, triisobutylaluminum diethylaluminum chloride.

Two or more kinds of these organoaluminum compounds can also be used.

In addition, the liquid titanium compound [1[] is usually Ti(OR)X (R is a hydrocarbon group and 4-
g and X are halogens, and a tetravalent titanium compound represented by 0≦q≦4) is suitable. More specifically, Ti
Tetrahalogenated titanium such as Cj, TiBr, TiI4: TI(OCH)CfJ, T1(OC2H5)C'3
, T1(On-C H )CfJ3, T I(0!So-C4 I9) CfJ3, T1(
OC2H5) Br3, T i (O iso-C l-I ) Br
, T i (02-c tylhexyl)C. Trihalogenated alkoxy titanium such as Q3: Ti(OCI-1) Cj12, T1(QC
I-I) Cj2, TI(On-C4H9)2C
．． Q2, dihalogenated alkoxyditane such as Ti(OCH)Br2; Ti(OCH3)3CL, Ti(QC2J-I5)
3Cj.

Ti(On-C4H9) 3C,ll, T1(OC2H
5) Monohalogenated 1-realkoxytitanium such as 38'; Ti(OCR), Ti(0(,R5), 4, Ti(
On-CH), Ti(Oiso-C4H9)4, T
Tetraalkoxytitanium such as i(02-ethylhexyl)4 or a mixture of these and other metal compounds such as an aluminum compound or a silicon compound may be used.

Furthermore, RTiX (R is a hydrocarbon group and J
4-J, X is a halogen, and tetravalent organic titanium compounds represented by O<j≦4) can also be exemplified. More specifically, dihalogenated titanium such as biscyclopentagenyl titanium dichloride and halogen-incompatible titanium compounds such as biscyclopentagenyl titanium 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. These trivalent titanium compounds include, for example, TIC, Il, T1(OC21-15)3, T
i(On-CH),,Ti(Oiso-C4H9)
3, Ti(02-ethylhexyl), T1(02-ethylhexyl) Cj 2, and other compounds are used.

Among the above-mentioned Ti compounds, the liquid titanium compound [III] that can be used in the present invention is preferably a tetravalent titanium compound, and particularly a halogen-containing tetravalent titanium compound.

The liquid titanium compound [II] may be used as it is if the titanium compound is in liquid form, 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, the Ti/Mg (atomic ratio) is usually -28 = greater than 0.01 and less than or equal to 1, preferably greater than 0.05 and less than or equal to 0.5. and AfJ/M(1 (atomic ratio)
is greater than 0.01 and less than or equal to 4, preferably greater than 0.03 and less than or equal to 3, particularly preferably greater than 0.04 and less than or equal to 1, and halogen/Mg (atomic ratio) is 0.5.
The weight ratio of RO group/Mg (R is a hydrocarbon group) is greater than 0.5 and less than or equal to 15, preferably greater than 1 and less than or equal to 10, It is particularly preferably greater than 1.5 and less than or equal to 3, and the specific surface area is 50 to 1000 r#/g, preferably 100 to 500 r#/g. and T1
The average valence of is usually less than 4, preferably 3.
5 to 2.5.

Further, the particle size of the titanium catalyst component is usually 5 to 200 μm.
m, preferably 10 to 100 μm, particularly preferably 20
~60 μm, and the particle size distribution is the geometric standard deviation, typically
It is in the range of 1.0 to 2.0.

In preparing the titanium catalyst component of the present invention, hydrocarbon solvents that can be used include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, dichloropentane, methyl Alicyclic hydrocarbons such as cyclopentane, 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,
A compound having a Q-carbon bond, for example, (where R 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. Halogen, m is Oh
m≦3, n is 0≦n×3, and p is 0≦p<3
, q is 0≦q3, and m + n
+ p −h q = 3), (ii) −M, IIR (where Ml is [, i, Na, and R1 is the same as above); Examples include alkylated products of the Group 1 metals shown above and aluminum.

Examples of the organoaluminum compounds belonging to (i) above include the following.

and R2 are the same as above. m is preferably 1.5≦
m < 3), general formula RAJIX (where R1 is the same as above m
3-n+. X is halogen and m is preferably 0<m
<3), general formula RAjH (where R1 is the same as above 3-IIl, m is preferably 2≦m<3), general formula RA, 1l(OR) for
nq and R2 are the same as above. X is halogen;
0<m≦3.0≦n<3.0≦q<3, and m +
Examples include those expressed by n 1 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
Dialkyl aluminum halides such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminum bromide, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butylaluminium sesquichloride, ethyl aluminum sesquipromide, ethyl aluminum dichloride, propyl aluminum dichloride , partially halogenated alkylaluminiums such as alkylaluminum cybarides such as butylaluminum dibromide, dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, alkyls such as ethylaluminum dihydritopropylaluminum dihydride Partially hydrogenated alkyl aluminums such as aluminum dihydride, partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide 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 compounds such as -33~ include (C2l-15) 2 A, o oA, o (C2R
5) 2, (C4R5) 2A,Q OAj (C4
H9)2, 6H5 can be exemplified.

Examples of compounds belonging to (ii) above include LiAj(C
H), L! Examples include A, Q (C7R15) 4, etc.

Among these compounds, the average composition is R, lX3-0 (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). Furthermore, 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, or ethylene and polyene copolymerization or ethylene and α-olefin and polyene polymerization. It can also be used for copolymerization with.

Examples of olefins that can be used for polymerization in the present invention include, in addition to ethylene, propylene, 1-butene,
Examples include 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-octene, and 1-decene. The polyenes include butadiene, isoprene, hexadiene, dicyclopentadiene, 5-ethylidene-2
- Examples include norbornene.

In the copolymerization of ethylene, especially ethylene or about 70
It is preferable to carry out the copolymerization so that the content is at least % by weight. In the present invention, ethylene and a small amount of α-olefin are copolymerized to achieve a density of 0.880 to 0.970.
A remarkable effect is produced when a low density ethylene copolymer of g/c+6, especially 0.890 to 0.940 g/-, is produced 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 polymerization include propane,
Aliphatic hydrocarbons such as butane, pentane, hexane, octane, decane, kerosene; Alicyclic hydrocarbons such as dichloropentane, 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 and selected as appropriate, but for example,
Reaction volume 1. per 1 liter of titanium catalyst component, preferably about 0.0001 to about 1 mmol in terms of titanium atoms,
- The layer is preferably used in an amount such that the aluminum/titanium (atomic ratio) is from about 0.001 to about 0.5 mmol, and the organoaluminum compound is used in an amount of from about 1 to about 2000, preferably from about 5 to about 100. It is best to use the amount such that The polymerization temperature is preferably 20 to 150°C, particularly preferably 40 to 100°C.

The polymerization pressure is from atmospheric pressure to about 100 kg/cd-c, preferably from about 2 to about 50 kg/alt-c.

In order to adjust the molecular landscape in olefin polymerization,
It is preferable to allow hydrogen to coexist in the reaction system.

Polymerization can be carried out batchwise or continuously.

It is also possible to carry out the process 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, the prepolymerization of ethylene or ethitane and α-olefin is carried out in a polymerization amount in the range of 0 to 1000 g.

Prepolymerization can be carried out in the presence or absence of an inert hydrocarbon solvent. 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 3 to 10 carbon atoms or alicyclic hydrocarbons having 5 to 10 carbon atoms are particularly preferably used.

The α-olefins used in prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, α-olefins having 10 or less carbon atoms such as 1-decene are preferred, and α-olefins having 2 to 6 carbon atoms are more preferred, with ethylene alone or a combination of ethylene and the above α-olefins being particularly preferred. 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 prefWI polymerization is generally -40 to 10
0°C, preferably -20 to 60°C, more preferably -11
It is 0-40°C. Hydrogen can also be present in the prepolymerization. - When prepolymerizing, the organoaluminum component is usually at least 0.1 gram atom, preferably 0.5 gram atom to 200 gram atom, more preferably 0.5 gram atom to 200 gram atom, per gram atom of titanium in the titanium catalyst component. is used in an amount of about 1 gram atom to 30 gram atoms.

Further, when performing prepolymerization, various electron donor components such as those described above may be present.

Example gas When trying to produce an ethylene homopolymer or a copolymer of ethylene and α-olefin using the titanium catalyst component according to the present invention, it has excellent slurry polymerization properties and gas phase polymerization properties, and the composition A polymer or copolymer with a narrow distribution can be obtained, and molded products with excellent transparency, blocking resistance, and heat sealability can be manufactured.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [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 suspended in n-decane 40+r+I, and then butyl ethyl was added to this suspension. Heptane solution containing 50 mmol of magnesium 43
After adding m1, a reaction was carried out at 90°C for 2 hours.

After the reaction was completed, the solid portion was separated from the reaction solution by filtration. This solid part contains 2.0 g of magnesium per 1 g of silica.
It contained the equivalent of 5 mmol atoms.

8 g of the solid portion thus obtained was mixed with 100 g of n-decane.
95 fl of magnesium chloride - 390 g of ethylhexanol and 355 g of 'n-decane
6.4 ml of a decane solution of magnesium chloride (corresponding to about 6.4 mmol of Mg) obtained by heating reaction at 140°C for 2 hours was added, the temperature was raised to 80°C, and after about 1 hour, diethylaluminum chloride was added. 7.7 mmol was added, and the reaction was further carried out at 80°C for 1 hour.9 Then, the solid part was separated from the reaction liquid by filtration, and this solid part was resuspended in 100 ml of n-decane. mmol things 2
- Add ethylhexoxytrichlorotitanium, 8
The reaction was carried out at 0°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 [1].

[Prepolymerization] Into a 400 ml cylindrical flask with a stirrer, 200 ml of purified hexane, 0.6 mmol of triethylaluminum, and the above titanium catalyst component [A] (0.2 mmol in terms of titanium atoms) were added. Prepolymerization of ethylene was carried out by supplying ethylene at a rate of 8N for 7 hours at °C for 3 hours. The amount of polyethylene produced is
The amount was 96 g per 1 g of catalyst.

[Ethylene polymerization] Internal volume sufficiently purged with nitrogen2. 150 tons of sodium chloride was added as a dispersant to the autoclave of Il.
The internal pressure of the autoclave is 50m while heating to 90°C.
The pressure was reduced to mHg or less using a vacuum pump for 2 hours. Next, the temperature of the autoclave was lowered to room temperature, and 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, and the temperature was raised. , 1 hydrogen at 60℃
kg/-, and while further pressurizing with ethylene, the prepolymerized titanium catalyst component was reduced to 0.0 kg/- in terms of titanium atoms.
0.005 mmol was added. During the polymerization, the temperature was 80'C and the pressure was 8 kg/cA with the addition of ethylene gas.
I kept it in G. Also, after adding titanium catalyst component, hexene-
136 ml was pumped over a 1-hour period.

Polymerization was terminated 1 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 water, with only the polymer floating on the water surface. After collecting this floating polymer and thoroughly washing it with methanol,
Drying was performed at 80° C. under reduced pressure overnight.

Table 1 shows the composition and polymerization results of the titanium catalyst component obtained.

K1侃l25 Table 1 shows the butylethylmagnesium and diethylaluminium chloride used in the preparation of the titanium catalyst in Example 1.
A titanium catalyst was prepared in the same manner as in Example 1, except that the compound shown in was used, and prepolymerization and copolymerization of ethylene, lene, and hexene-1 were performed.

The composition and polymerization results of the obtained catalyst are shown in Table 1.

A titanium catalyst was prepared in the same manner as in Example 1, except that the mono-2-ethylhexoxy-1-lichlorotitanium used in the preparation of the titanium catalyst in Example 1 was replaced with the compound shown in Table 2. was prepared, prepolymerized, and copolymerized with ethylene and hexene-1.

K. Renji J In the same manner as in Example 1, 10 g of silica and 50 mmol of butylethylmagnesium were reacted to prepare a treated carrier in which magnesium was fixed in an amount equivalent to 2.5 mmol atoms per 1 g of silica. This treated carrier was mixed with 100% n-decane.
A decane solution of magnesium obtained by heating and reacting 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 the solution in 6.4 ml of magnesium
ml was added and the temperature was raised to 80°C. After about 1 hour, the temperature was lowered to 55°C, 30ml of silicon tetrachloride was added, and the reaction was carried out at the same temperature for 2 hours. Next, the solid part was separated by filtration, and n-
After resuspending in 100 ml of decane, 7.7 mmol of diethylaluminum chloride was added, and the reaction was carried out at 80° C. 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 K1 Seal Example 8, ethoxymagnesium chloride 1
04.8g, 2-ethylhexanol 390g and n
- A magnesium decane solution obtained by heating and reacting 355 g of decane at 140°C for 2 hours,
A catalyst was prepared in the same manner as in Example 8, except that a heptane solution containing 5 mmol of -ethylhexoxide was used, 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 drawing is a flowchart showing a catalyst component for producing an ethylene polymer according to the present invention and its preparation process. Agent Patent Attorney Shunbetsu Meiki

Claims (10)

[Claims] (1) At least [I] Support (i) is made of a material other than aluminum from the periodic table.
After contacting the liquid organometallic compound (ii), which is a group II or IIIA organometallic compound and has at least two hydrocarbon groups directly bonded to a metal atom, the liquid organometallic compound (ii), which has no reducing ability, is Magnesium-containing support obtained by contact reaction of magnesium compound (iii) [II] Organic aluminum compound and [III] Magnesium, aluminum, halogen and titanium obtained by contact reaction of liquid titanium compound as essential components Support supported titanium catalyst component. (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 organometallic compound (ii) is a hydrocarbon solution of a dihydrocarbylmagnesium compound. (9) Ti/Mg (atomic ratio) in the titanium catalyst component is 0.
greater than 01 and less than or equal to 1, and Al/Mg (atomic ratio) is 0.
Claim 1, wherein the halogen/Mg (atomic ratio) is greater than 1 and 3 or less, and the weight ratio of RO group/Mg (R is a hydrocarbon group) is greater than 1 and 10 or less.
Catalyst components listed in Section. (10) [I] A magnesium-containing support is prepared by contacting the support (i) with a liquid organometallic compound (ii) in advance and then contacting a liquid magnesium compound (iii) that does not have reducing ability. Prepare the body [I],
Then, the obtained magnesium-containing support is brought into contact with [II] a reducing organometallic compound and [III] a titanium compound in a liquid state, which is a support containing magnesium, aluminum, halogen, and titanium as essential components. A method for producing a body-supported titanium catalyst component.