JPS61130310A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a polyolefin excellent in melt elasticity, melt tension and melt moldability, by polymerizing an elefin in multiple stages under a specified condition in the presence of a catalyst comprising a highly active Ti/V solid catalyst component and an organoaluminum compound. CONSTITUTION:A super-MW polyolefin of an intrinsic viscosity >=20dl/g is formed by polymerizing 0.05-1wt% of a feed olefin at -20-120 deg.C and a pressure of atmospheric - 100kg/cm<2> in the presence of a catalyst comprising a highly active Ti/V solid catalyst component obtained by reacting a Mg compound with a Ti compound, a V compound and, optionally, a halogen compound and an organoaluminum compound. The remainder of the olefin is polymerized in the presence of 1-99mol, per 100mol of the olefin, of hydrogen to obtain a polyolefin of an intrinsic viscosity of 0.1-4.5dl/g.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for multi-stage polymerization of olefins, and further relates to a method for the multistage polymerization of olefins.
Specifically, the present invention relates to a method for producing a polyolefin having excellent melt tension and melt elasticity, and excellent melt moldability.

Note that in the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and similarly, the term "polymer" is used to include not only homopolymers but also copolymers. Sometimes.

[Conventional technology]

Many proposals have already been made regarding methods for carrying out ethylene polymerization using a catalyst formed from a highly active titanium catalyst component containing magnesium, titanium, and halogen as essential components and an organoaluminum compound catalyst component. In addition, many proposals have been made regarding methods for carrying out multi-stage polymerization of two or more stages in the monopolymerization and copolymerization of olefins such as ethylene.In general, polyolefins such as polyethylene and polypropylene are lightweight, economical, and melt moldable. Due to its excellent properties, it is used for general purposes in the field of melt molding such as extrusion molding and blow molding. However, these polyolefins.

In particular, ethylene polymers containing ethylene as a main component, especially those polymerized using Ziegler type polymerization catalysts, have excellent melt moldability, but they have poor melt tension and melt elasticity, especially in the field of blow molding. As a result, there is a drawback that drawdown phenomenon easily occurs during molding, and as a result, weld lines are easily generated in molded products. Various attempts to improve physical properties have also been proposed. For example, methods that attempt to achieve the same objective by improving the catalyst, its composition, and polymerization recipe during the production of polyolefin, methods that attempt to achieve the same objective by blending a modifier into polyolefin, Alternatively, attempts have been made to achieve the same objective by partially crosslinking polyolefin, but all of these methods have drawbacks such as complicated formulations and insufficient effects, as well as problems with melt tension and There is a need for polyolefins with excellent melt elasticity.

For example, among these conventionally known multi-step polymerization methods, Japanese Patent Publication No. 59-10724 and Japanese Patent Application Laid-open No. 59-193913 use a catalyst consisting of a transition metal compound and an organometallic compound. In a multi-stage polymerization process, at least one of the polymerization processes involves a specific amount of all raw material olefins to be polymerized in all polymerization steps, for example, 1 to 10 polymerization steps in JP-B-59-10724; 59-193913 is 20
There is a method for producing polyolefins with excellent melt moldability such as blow molding and inflation molding by polymerizing 75% to 75% by weight of ultra-high molecular weight polyolefins and then polymerizing polyolefins of normal molecular weight using other polymerization techniques. Disclosed.

However, in these methods, when the proportion of polyolefin in the ultra-high molecular weight range to the polyolefin polymerized in the entire polymerization process is less than 1% by weight, when this polyolefin is used for blow molding, die swell (molten polymer is molded) The present inventors have found that the melt tension is low and the melt moldability is poor when extruded from the die of a machine. As a result of extensive research into a polymerization method that can produce polyolefins that are large and have excellent melt moldability, especially ethylene polymers, we found that
In the presence of a catalyst formed from a highly active titanium vanadium solid catalyst component and an organoaluminum compound catalyst component,
The inventors have discovered that the above object can be achieved by employing a method of polymerizing olefins using a specific multi-step polymerization recipe. In particular, by using titanium and vanadium in combination, a polyolefin, especially an ethylene polymer, can be obtained which has a higher melt tension and excellent melt moldability than when titanium is used alone.

It is an object of the present invention to provide an improved and methodical multi-step process for the polymerization of olefins. Still another object is to provide a method for producing a polyolefin, particularly an ethylene polymer, which has high melt tension and melt elasticity and excellent melt moldability. The foregoing objects and many other objects and advantages of the present invention will become apparent from the following description. Therefore, the present invention was formed by the mutual reaction of (A) a magnesium compound, a titanium compound, a vanadium compound, and optionally a nitrogen compound.

In a method of polymerizing onfin in a multi-step polymerization process in the presence of a catalyst formed from a highly active titanium-vanadium solid catalyst component containing magnesium, titanium, vanadium and halogen as essential components and an organoaluminum compound catalyst component. , (1) In at least one polymerization step of the multi-stage polymerization step, by polymerizing 0.05 to less than 1% by weight of the raw material olefin to be polymerized in all polymerization steps, the intrinsic viscosity [η] is 2CJd6/ Producing ultra-high molecular weight polyolefins of 9 or more.

(ii) In the other polymerization step, the remaining raw material olefin is polymerized in the presence of hydrogen.

The highly active titanium/vanadium solid catalyst component (2) used in the present invention essentially contains magnesium, titanium, vanadium, and halogen formed by the mutual reaction of a magnesium compound, a titanium compound, a vanadium compound, and, if necessary, a halogen compound. The highly active titanium/vanadium solid catalyst component is a highly active titanium/vanadium solid catalyst component, and at least one of the catalyst components of the magnesium compound, titanium compound, and vanadium compound used to form the highly active titanium/vanadium solid catalyst component contains a halogen. If it contains halogens, there is no need to use halogen compounds again, but if none of the catalyst components of magnesium compounds, titanium compounds, and vanadium compounds contain halogens, high activity A halogen compound is used as a component of the titanium/vanadium solid catalyst component. Although they can be formed by reacting with each other, a halogen compound of magnesium is formed regardless of the raw material magnesium compound. The highly active titanium/vanadium solid catalyst component usually does not desorb titanium compounds and vanadium compounds by simple means such as washing with hexane or the like at room temperature.The highly active titanium/vanadium solid catalyst component (c) The atomic ratio of titanium to vanadium in ) is preferably about 1 to about 9, particularly preferably about 6 to about 7, and the atomic ratio of magnesium to the sum of titanium and vanadium is preferably about 2 to about 100, especially Preferably, the atomic ratio of halogen to the sum of titanium and vanadium is from about 4 to about 200. Particularly preferably, the number is in the range of about 10 to about 100. The specific surface area is preferably about 3rrf# or more, more preferably about 40 m''
/,! i' or more, more preferably about 100 m'/g
The highly active titanium/vanadium solid catalyst component (t) may contain other metal atoms and anions in addition to the above-mentioned magnesium, titanium, vanadium, and halogen atoms. The highly active titanium/vanadium solid catalyst component may contain ligands, electron donors, etc., and may also contain other inorganic compound components or organic compound components. The preparation method is described in Japanese Patent Publication No. 50-32270, Japanese Patent Publication No. 54
-25517, JP-A-50-95384, JP-A No. 50-
No. 126590, Japanese Patent Publication No. 56-5403, Japanese Patent Publication No. 1983
-135102, 55-135103, 56-
No. 811, No. 56-67311, Special Iη 1987-18
1018, etc., by using a mixture of a titanium compound and a vanadium compound instead of a titanium compound. A method for obtaining a vanadium solid catalyst component will be exemplified.

(1) Reacting a magnesium-aluminum complex that has a reducing ability and is insoluble in hydrocarbons with a liquid titanium compound and a liquid vanadium compound. contacting the mixture with an organoaluminum compound.

Magnesium compounds that can be used to prepare the highly active titanium/vanadium solid component include magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide. , magnesium sybaride, an organomagnesium compound, or a complex (adduct) of these magnesium compounds and an electron donor.

As the organoaluminum compound that may be used in the preparation of the highly active titanium/vanadium catalyst component, those exemplified as the organoaluminum compound catalyst component ◎ used in the olefin synthesis stage can be used.

The titanium compound used for preparing the highly active titanium/vanadium catalyst component may be, for example, tetrahalogenated titanium, alkoxytitanium halide, allyloxytitanium halide, alkoxytitanium, allyloxytitanium, etc. Titanium halides, especially titanium tetrachloride, are preferred.

The vanadium compound used in the preparation of the highly active titanium-vanadium catalyst component has the general formula vo(OR)aX
b or V(OR). Xd (where R is a hydrocarbon group, 0≦a
≦3,0≦b≦3,2≦a+b≦3%0≦C≦4.0≦
d≦4.3≦C+d≦4), or these 1. Child donor adducts can be cited as a representative example. More specifically, VOCl3,v
o(oc2H1)ca2, VO(QC2H6)2CI,
VO(Oiso c, H,)(J2, VO(On-C
,H7)C10,VO(QC2)(,),, voBr
2, VCl4. voaI, VO(On-C4H,)
,.

Examples include V(J, 20G, H, OH, etc.).

Electron donors that may be used in the preparation of the highly active titanium/vanadium solid catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids,
Oxygen-containing electron donors such as organic or inorganic acid esters, ethers, amides, acid anhydrides, alkoxysilanes, nitrogen-containing electron donors such as ammonia, amines, nitriles, incyanates, etc. can be used. More specifically, methanol, ethanol, furopanol, pentanol, hexanol, octatool, dodecanol,
Octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol% Ia)a HitbAlcohols with 1 to 18 carbon atoms such as benzyl alcohol1Phenol, cresol, xylenol, ethyl C6 to C20 heptenols which may have a lower alkyl group such as phenol, flobylphenol, nonylphenol, cumylphenol, naphthol; acetone, methyl ethyl ketone,
Ketones having 5 to 15 carbon atoms, such as methylinbutylketone, acetophenone, benzophenone, and benzoquinone; aldehydes having 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and nathaldehyde; methyl formate; Methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate,
Ethyl propionate, methyl butyrate, ethyl kichimoate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl 7-chlorohexanecarboxylate, methyl benzoate.

Ethyl benzoate, propyl benzoate, butyl benzoate,
Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, cyclohexenecarboxylic acid di-n-
Hexyl, diethyl nazic acid, diisopropyne tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di2-ethylhexyl phthalate, γ-butyro→chthone, δ-valerolactone, coumarin, phthalide, ethylene carbonate Organic acids with 2 to 60 carbon atoms such as ester acids; acid halides with 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride; methyl ether, ethyl ether, inflovir ether, ether, amyl ether, tetrahydrofuran.

A2 to C20 ethers such as anisole and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine , picoline, tetramethylenediamine, and other amines; acetonitrile, pentunitrile, tolnitrile natononitrile +
) Rubles: Examples include alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. Two or more of these electron donors can be used.

Organoaluminum compound catalyst component used in the present invention■
For example, a compound having at least one AJ-carbon bond in the molecule can be used.

(1) General formula R-zuke AJ (OR2). Hp X q (where R' and R2 usually have 1 to 15 carbon atoms,
Preferably it contains 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, m is o<m≦
3. n is 0≦n<3+ p is 0≦n<3゜q is 0≦q<
3, and rn+n+p+q=3)
an organoaluminum compound represented by (ii) a complex alkylated compound of a Group 1 metal and aluminum represented by the general formula M'AzR: (where Ml is Ll, Na, and RIu is the same as above); You can benefit from such things.

As the organoaluminum compounds belonging to the above (1), all of the following can be exemplified.

General formula RQAI(OR''), -0 (wherein R1 and R2 are the same as above; m is preferably a number of 1.5≦m≦3).

General formula Rf AIX3-m (here, R1 is the same as above, X is), and rogene 1m preferably satisfies 0<m<3).

General formula RTnAIH3-m (where R1 is the same as above om is preferably 2≦m6
).

General formula RfAl (OR”).Xq (Here, R1 and R2 are the same as before.
o<m≦3.0≦n<3. O≦Q<3, m+n+q=
3) can be exemplified.

Among the aluminum compounds belonging to (1), more specifically, trialkylaluminums such as triethylaluminum and tributylaluminium; trialkenylaluminums such as triisoprenylaluminum; dialkylaluminums such as diethylaluminiumide, diptylaluminium butoxide, etc. Alkoxide: In addition to alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, %R,,,AJ (OR2).

, 5, etc.: dialkylaluminum hafides such as diethylaluminum chloride, diptylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride , alkyl aluminum sesquino S such as ethyl aluminum sesquipromide
Wide, partially halogenated alkyl aluminum such as alkyl aluminum di-rides such as ethyl aluminum dichloride, propyl aluminum dichloride, glylaluminum dipromide etc.; dialkyl aluminum hydrides such as diethylaluminum hydride, diptylaluminum hydride, etc. Ethyl aluminum dicdolide.

partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as probylaluminum dihydride; ethylaluminum ethoxy chloride;
Examples include petitsialuminum butoxychloride, ethylaluminum ethycypromide, and partially alkoxylated and nitrogenated alkylaluminums. Moreover, as a compound similar to (1), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. Examples of such compounds include (C2H,)2AJOA,! t (G2
H5')2, (Ca H9)2 Al0AJ (C4H
9)2.

Compounds belonging to (ii) include LIAl(C2H
5)4.

Examples include LiAi(C,H,5)a. Among these, it is particularly preferable to use trialkylaluminium, alkylaluminum halide, or a mixture thereof.

The olefin polymerization reaction according to the method of the present invention is carried out in a multi-stage polymerization process. This multi-stage polymerization reaction can be carried out by a batch method, a semi-continuous method, or a multi-stage continuous method in which two or more polymerization tanks are connected in series. It is necessary to produce a specific amount of ultra-high molecular weight polyolefin in at least one polymerization step of the multi-stage polymerization process. The polymerization step for producing the ultra-high molecular weight polyolefin may be a first stage polymerization step,
It may be an intermediate polymerization step, a final polymerization step, or a plurality of two or more steps, but the first step polymerization step is the polymerization step. This is suitable from the viewpoint of processing operations and control of the physical properties of the polyolefin produced. In the polymerization step, by polymerizing 0.05 to less than 1-Ik1 of the olefin polymerized in all steps, the intrinsic viscosity (value measured at 135°C in decalin solvent) is 20d179 or more. It is necessary to produce ultra-high molecular weight polyolefins, and furthermore, by polymerizing 0.2 to 0.8 weight percent of the olefins polymerized in the entire polymerization process, the intrinsic viscosity is greater than 60 to 70 dA/g. Preferably, high molecular weight polyolefins are produced. In the polymerization step, the ultra-high molecular weight polyolefin produced has an intrinsic viscosity [η] of 20
If it is less than C11/g, the effect of improving the melt tension and melt elasticity of the polyolefin will not be obtained, and even if the proportion of olefin polymerized in the polymerization process is less than 0.05% by weight, the melt tension and melt elasticity will similarly decrease. It is impossible to obtain a polyolefin with excellent elasticity, and if the weight exceeds 1 weight, fish eyes, spots, etc. will increase in the molded product, so it is necessary to keep it within the above range.

In the method of the present invention, in the polymerization step for producing an ultra-high molecular weight polyolefin, polymerization is carried out in the presence of a catalyst consisting of the highly active titanium/vanadium solid catalyst component and the organoaluminum compound catalyst component 6). Polymerization can be carried out by gas phase polymerization or liquid phase polymerization. In any case, in the polymerization step to produce ultra-high molecular weight polyion fins, the polymerization reaction is optionally carried out in the presence of an inert medium, for example in gas phase polymerization, an inert medium is optionally formed. It is carried out in the presence of a diluent, and in liquid phase polymerization, it is carried out in the presence of a solvent consisting of an inert medium if necessary.

In the polymerization process for producing the ultra-high molecular weight polyolefin, the highly active titanium/vanadium solid catalyst component is used as a catalyst to contain, for example, about 0.001 to about 100 milligram atoms per medium 11 as the total metal atoms of titanium and vanadium, especially about o, oos to about 10 milligram atoms, organoaluminum compound catalyst component ◎, and the atomic ratio of aluminum to the sum of titanium and vanadium is about 1
It is preferable to use a proportion of from about 1,000 to about 1,000, particularly from about 2 to about 500. The temperature of the polymerization step for producing the ultra-high molecular weight polyolefin is generally in the range of -20 to about 120°C, preferably in the range of about 0 to about 100°C, particularly preferably in the range of about 5 to about 80°C. The pressure at this time is within a pressure range that allows liquid phase polymerization or gas phase polymerization at the above temperature, for example, from atmospheric pressure to about 1
00 kg/eJ, preferably from atmospheric pressure to about 50 &
/CJ range. In addition, the polymerization time in the polymerization step is such that the amount of pre-polymerized polyolefin produced depends on the highly active titanium.
About 0.5.5% per gram atom of titanium and vanadium combined in the vanadium solid catalyst component. F or more, preferably about 1 g or more.In order to produce the ultra-high molecular weight polyolefin in the polymerization step, the polymerization reaction must be carried out in the absence of hydrogen. is preferred. Furthermore, after carrying out the polymerization reaction, it is also possible to temporarily isolate and store the polymer in an inert medium atmosphere.

Inert media that can be used in the polymerization process to produce the ultra-high molecular weight polyolefins include, for example, propane, butane, pentane, hexane, heptane, octane, decane, kerosene, and other fats! Hydrocarbons; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloroethane, methylene chloride and chlorobenzene; or mixtures thereof. However, it is particularly desirable to use aliphatic hydrocarbons.

Furthermore, in the method of the present invention, in the polymerization step other than the polymerization step for producing the ultra-high molecular weight polyolefin, the remaining olefin is polymerized in the presence of hydrogen. If the polymerization process for producing an ultra-high molecular weight polyolefin is a first-stage polymerization process, then the second-stage and subsequent polymerization processes correspond to the polymerization process. When the polymerization step is located after the ultra-high molecular weight polyolefin-producing polymerization step, a polyolefin containing the ultra-high molecular weight polyolefin is supplied to the polymerization step, and the polymerization step is located after the ultra-high molecular weight polyolefin-producing polymerization step. When the polymerization step is located after another polymerization step, the polyolefin produced in the previous step is fed, and in either case, the polymerization is carried out continuously or semi-continuously. At that time, the raw material olefin and hydrogen are usually supplied to the polymerization step. When the polymerization step is the first stage polymerization step, the highly active titanium/vanadium solid catalyst component and the organoaluminum compound catalyst component (
If a catalyst consisting of 81 is supplied and the polymerization process is a second or subsequent polymerization process, the catalyst contained in the polymerization product liquid produced in the previous stage can be used as is, or if necessary Depending on the situation, the highly active titanium/vanadium solid catalyst component and/or the organic aluminum compound catalyst component ◎ may be additionally replenished. The ratio of the raw material olefin to be polymerized in the polymerization step is 99 to 9995 to the total olefin components polymerized in the entire polymerization step.
% by weight, preferably in the range of 992 to 998 wt.

The hydrogen supply ratio in the polymerization steps other than the ultra-high molecular weight polyolefin production polymerization step is usually 1 to 99% per 100 moles of olefin supplied to each polymerization step.
mol, preferably in the range of 5 to 95 mol.

The concentration of each catalyst component in the polymerization solution in the polymerization tank in the polymerization step other than the ultra-high molecular weight polyolefin production polymerization step is the concentration of each catalyst component in the polymerization solution in the polymerization tank per 1 polymerization volume #'Nl. Approximately 0.00
1 to about 1 milligram atom, preferably about 0.005
It is preferable that the atomic ratio of aluminum to the sum of titanium and vanadium in the polymerization system is about 1 to about 1000, preferably about 2 to about 500. If necessary, organoaluminum compound catalyst component ◎ can be additionally used. In addition, hydrogen, an electron donor, a halogenated hydrocarbon, etc. may be present in the polymerization system for the purpose of controlling the molecular weight, molecular weight distribution, etc.

The polymerization temperature in the ultra-high molecular weight polyolefin production polymerization step is within a temperature range that allows slurry polymerization, solution polymerization, or gas phase polymerization, and is about 50°C or higher, more preferably about 60°C.
The preferred polymerization pressure is from atmospheric pressure to about 200 kg/cJ, particularly from atmospheric pressure to about 100 kg/cJ. Then, the polymerization time is set such that the amount of polymer produced is about 5 ooo, v or more, especially about 10,000 y or more per 1 milligram atom of the total metal atom of titanium and vanadium in the highly active titanium/vanadium solid catalyst component. It is better.

Similar to the ultra-high molecular weight polyolefin production polymerization step described above, it can be carried out using a gas phase polymerization method or a liquid phase polymerization method, and of course it is also possible to adopt a different polymerization method for each polymerization step. be. Among liquid phase polymerization methods, it is possible to adopt a suspension polymerization method, and it is also possible to adopt a solution polymerization method, but in either case, the polymerization reaction is usually not performed in the polymerization step. It is carried out in the presence of an active medium. For example, gas phase polymerization is carried out in the presence of an inert medium diluent, while liquid phase polymerization is carried out in the presence of an inert medium. In the method of the present invention, the [η] of the polyolefin obtained in the final polymerization step is usually 0.1 to 4.5 d.
1711. Preferably 0.5 to 4.0 dl/,
9. Particularly preferably, the polymerization reaction is carried out until it reaches 0.7 to 3.5d71#'. Excellent in melt molding processability.

The method of the present invention can be carried out in any batch, semi-continuous or continuous manner.

Olefins to which the olefin polymerization method of the present invention can be applied include ethylene, propylene% 1-butene 1
<Ntene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-, >1-thyl-1-pentene, 3-
Methyl-1-pentenonatono α-olefin can be exemplified, and it can be applied to a method for producing a homopolymer of these α-olefins, or it can be applied to a method for producing a copolymer consisting of two or more mixed components. You can also do that. Among these α-olefins, it is preferable to apply the method of the present invention to a method for producing an ethylene polymer, which is ethylene or a copolymer of ethylene and other α-olefins, and has an ethylene component as a product. Next, the present invention will be specifically explained with reference to Examples.

Example 1 [Preparation of highly active titanium/vanadium solid catalyst component 4] After replacing an autoclave with an internal volume of 51 ml with sufficient nitrogen, 1.5 ml of refined kerosene, commercially available MgCA, 7! V, 109 g of ethanol and Emazol 320 (Kao Ato W
Add 10g of sorbitan distearate (manufactured by Company 2), raise the temperature of the system with stirring, stir at 125°C and 600 rpm for 20 minutes, reduce the internal pressure of the system to 10kg/c4 gauge at 7N2, and connect directly to the autoclave. The cock of a SUS tube with an inner diameter of 3 mm kept at 125°C was opened, and the liquid was transferred to a 51 glass flask (equipped with a stirrer) filled with refined kerosene 31 previously cooled to -15°C. The amount of liquid transferred was 1E, and the required time was about 20 seconds. The produced solid was collected by filtration and thoroughly washed with hexane.

12.9 tons of the above solid was slurried with Deca 72007714, cooled to 0°C, kept at this temperature, and 125 mmol of diethylaluminium chloride was added dropwise over 30 minutes. A portion of the organoaluminum is fixed on the magnesium chloride by holding the column for a certain period of time. This slurry was allowed to stand, the supernatant liquid was removed, and the slurry was made into a slurry again using decane. After performing this operation twice, Decane 2001'rLl was added and the slurry was kept at 0°C with stirring.
A mixture of 5 mmol of vanadyl trichloride diluted with 0 ml and 5 mmol of titanium tetrachloride was added dropwise over 15 minutes. After the dropwise addition was completed, the temperature was raised to 80°C and kept at this temperature for 1 hour. Then, the solid product was collected by filtration and washed with decane until free vanadium and titanium were no longer detected in the washing solution to remove the catalyst components. Obtain [Polymerization] Purified decane 11) in an autoclave with an internal volume of 2/2) Limbutylaluminum 2. Qm mol, the catalyst component (2) is 0.0.
After charging 01 milJ gram atoms, the temperature was set to 40°C, and then ethylene gas was introduced and polymerization was carried out for 1 minute at a total pressure of 8 kg/cJ gauge. At this time, ultra-high molecular weight polyethylene with [η] 52 was .1g was produced (first stage)
Thereafter, after the ethylene gas was once depressurized, hydrogen gas was introduced and the pressure was increased to 1 kg/ca gauge. Subsequently, 70
Raise the temperature to ℃, introduce ethylene gas again, and increase the total pressure to 8 kj7
/ After restarting polymerization as a ca gauge, only ethylene gas was supplied and the total pressure was 8 kl? /c4 gauge, and polymerization was carried out at 80° C. for 80 minutes (second stage). After the polymerization was completed, the 917-bolimers were distributed from house to house, and 8
Dry under reduced pressure at 0°C overnight. The yield of polymer after drying is 3
69 g, its [η] was 2.51 dl-Ch, MFR was 0.20.9/10 m1n, melt tension (MT) was 18 g, and die swell (SR) ratio was 60. The ratio of the fc ethylene component used in the polymerization of the ultra-high molecular weight polyethylene produced in the above to the total polymerized ethylene component was 0.30% by weight.

Example 2 Polymerization was carried out in the same manner as in Example 1, except that the second stage polymerization was carried out at a hydrogen pressure of 1-5 and a 9/ca gauge for 40 minutes. The vocabulary list is shown in Table 1.

Example 3 Example 1 except that the second stage polymerization was carried out for 120 minutes.
Polymerization was carried out in the same manner as above, and the results are shown in Table 1.

Comparative Example 1 The same procedure as Example 1 was carried out except that the first stage polymerization was not carried out. The results are shown in Table 1.

Comparative Example 2 In the first stage polymerization of Example 1, hydrogen gas was added at 0.3
The same procedure as in Example 1 was carried out except that klil/CIA was added and polymerization was carried out for 1.5 minutes.

Polymer a obtained in the first stage polymerization 1.2
．． li+ and had [η] of 10.2. The results are shown in Table 1. Example 4 [Preparation of a highly active titanium/vanadium solid catalyst component] 50 mmol of magnesium chloride was slurried with 50 ml of decane, 150 mmol of 2-ethylhexyl alcohol was added, and the temperature was raised to 130°C. The solution was heated to solubilize magnesium chloride and cooled to room temperature, and 5 mmol of vanadyl trichloride and 5 mmol of titanium tetrachloride were added thereto. A mixture of Decane 2007# and 150 mmol of diethylaluminium chloride was kept at 0° C. with stirring, and the above solution was added dropwise for 30 minutes. At this time, precipitation of solid was observed.

The subsequent operations were exactly the same as in Example f111 to produce a catalyst component.

[Overlapping]

The same procedure as in Example 1 was carried out. The results are shown in Table 1.

Example 5 In an autoclave with an internal volume of 22, purified decane 11% triimbutylaluminum 2° Ommol, the total of the catalyst component (A) e-vanadium and titanium was 0 in terms of atoms.
．． 04 milligram atom loading friend. After setting the temperature to 40° C., ethylene gas was introduced and polymerization was carried out for 45 seconds at a total pressure of 7 kf/crl gauge. At this time, (ri) 49.5
1.8g of ultra-high molecular weight polyethylene was produced (?
:1 stage). After that, after depressurizing the ethylene gas,
Hydrogen gas was introduced and the pressure was increased to 2.5 to 9/d gauge. Subsequently, the temperature was raised to 70°C, ethylene gas was introduced again, the total pressure was set to 8 kli'/cA gauge, and polymerization was restarted. After that, replenish only ethylene gas and reduce the total pressure to 8 kg.
/ctl gauge and polymerization was carried out at 80°C for 60 minutes. At this time, the ethylene gas was 1.15 dJ# and 153 I of polyethylene with an MFR of 17 was produced (second stage). Ethylene gas was again depressurized and hydrogen gas was added to 2.5 dJ#. After adding Ommol, an ethylene/1-butene mixed gas with a 1-butene content of 2.0 mol% was continuously introduced, and the total pressure was 5.5.
Polymerization was carried out at 80°C for 30 minutes (third stage) at 'r<97cA gauge. After the polymerization was completed, the polymer slurry was separated and dried under reduced pressure at 80° C. overnight. The yield of the polymer after drying is 308I, [η] is 2.186A/l/, M
FR is 0.5411/10m1n, m/l/)
7' sink (MT) is 16g, dice well (S
R) ratio was 93chi, and density was 0.9569jan'. The ratio of the ethylene component used in the polymerization of the ultra-high molecular weight polyethylene produced in the first stage to the total polymerized ethylene cloud butene component was 0.58% by weight.

Comparative Example 3 Polymerization in the first stage was carried out for 2.5 minutes, and polymerization in the second stage was carried out under a hydrogen pressure of 1.1 kl? /J for 80 minutes, and the third stage polymerization was carried out in the same manner as in Example 5, except that the polymerization was carried out for 10 minutes.

The yield of polymer after drying is 188! i, [η] is 2.55C11/i, MFR is 0.24g/10m1n
There was a time. The ratio of the ethylene component used in the polymerization of the ultra-high molecular weight polyethylene produced in the first step to the total polymerized ethylene/butene component was 4.4% by weight. When measuring the melt tensile strength (MT) of this material.

Thread breakage was severe and measurement was difficult, and many bumps were observed in the threads and the skin was rough.

Comparative Example 4 A catalyst was prepared in the same manner as in Example 1, except that vanadyl I-IJ chloride was not used in the preparation of the highly active titanium/vanadium solid catalyst component in Example 1, and 10 mmol of titanium tetrachloride was used. .

〔polymerization〕

Using the above catalyst components, the same procedure as in Example 1 was carried out except that in the second stage of polymerization, hydrogen gas was pressurized to 2 kfiT/cJ gauge and polymerization was carried out for 120 minutes. The ultra-high molecular weight polyethylene produced in the first stage is 1.0. F and 26.
It had [η] of 3. After polymerization in the second stage, the amount of polymer is 479g, which is 2.48C1g.
/I, MFR is 0.2311/10m1n,
, t tension η n (MT) huff g, die swell (
SR) ratio was 50. The ratio of the ethylene component used in the polymerization of the ultra-high molecular weight polyethylene produced in the first stage to the total polymerized ethylene component was 0.21% by weight.

Claims (1)

[Claims] (1) (A) A highly active titanium/vanadium solid catalyst component containing magnesium, titanium, vanadium, and halogen as essential components, formed by the mutual reaction of a magnesium compound, a titanium compound, a vanadium compound, and, if necessary, a halogen compound; (B) a method for polymerizing an olefin in a multi-stage polymerization step in the presence of a catalyst formed from an organoaluminum compound catalyst component, and (i) polymerizing at least one of the multi-step polymerization steps. In the process, an ultra-high molecular weight polyolefin with an intrinsic viscosity [η] of 20 dl/g or more is produced by polymerizing less than 0.05 to 1% by weight of the raw material olefin polymerized in the entire polymerization process, (ii) Others A method for polymerizing olefins, comprising: polymerizing the remaining raw material olefin in the presence of hydrogen in the polymerization step.