JPS59164308A - Production of polyethylene - Google Patents

Abstract

PURPOSE:To obtain an ethylene polymer made by the use of a noncontaminative deactivator, by polymerizing ethylene or a mixture of ethylene with an alpha-olefin with the aid of a Ziegler catalyst and deactivating the catalyst by adding an organolithium compound. CONSTITUTION:Ethylene or a mixture of ethylene with a 3-18C alpha-olefin is polymerized at an average polymerization temperature >=130 deg.C with the aid of a Ziegler catalyst containing a transition metal compound and an organometallic compound in the presence or absence of an inert hydrocarbon solvent. The catalyst is deactivated by adding, to the produced polymer mixture with stirring, a deactivator of an organolithium compound in an amount sufficient to deactivate the catalyst. This organolithium compound is added in the form of a solution or suspension in an inert hydrocarbon or in the form of a solid or a melt. Unreacted monomer or both unreacted monomer and the inert hydrocarbon solvent are separated from the produced polymer mixture and then a polymer containing the deactivator and the reaction product between the deactivator and the catalyst is separated.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyethylene and ethylene-α-olefin copolymers, and the invention relates to a method for producing polyethylene and ethylene-α-olefin copolymers. Regarding.

Polyethylene and ethylene-α-olefin copolymers polymerized by Ziegler type catalysts usually have a molecular weight of 0.850
It has a wide density range of ~0.975 g/d, and is used in large quantities for a wide variety of applications, such as films, blow molded products, fibers, and extrusion molded products.

A Ziegler type catalyst is known as a catalyst for polymerizing ethylene or a mixture of ethylene and α-olefin. Ziegler-type catalysts contain transition metal compounds in the -W+I group of the periodic table, such as titanium and vanadium compounds, and metal compounds such as aluminum compounds as main components. It will be done.

Various processes are known for polymerizing ethylene or mixtures of ethylene and α-olefins, but there are solution polymerization methods that polymerize at high polymerization temperatures of 130°C or higher and high-temperature high-pressure polymerization methods that do not use solvents. It is possible to polymerize ethylene adiabatically, and unlike slurry polymerization and gas phase polymerization, it is an excellent energy-saving process because it does not require energy to remove the polymerization heat.

In recent years, highly active Ziegler-type catalysts have been developed, and the amount of catalyst residue in the polymer is extremely small, eliminating the need to extract or neutralize the catalyst residue in the polymer with alcohol or caustic soda. Compared to conventional polymers that have been subjected to catalyst removal, the stability is much more consistent. When there is a catalyst removal process, the recovered polymerization solvent and unreacted monomers come into contact with polar compounds such as alcohol, so it is impossible to use them directly for blood reaction.
It is necessary to separate these polar compounds in a purification process. On the other hand, when a highly active catalyst is used, polar compounds such as alcohols are not used, so some or all of the polymerization solvent and unreacted monomers are not purified at all, or a very simple purification process (for example, molecular sieves) is used. It can be reused simply by processing it (by passing it through water), and it is possible to save the enormous amount of energy such as steam required for distillation and purification.

However, if the catalyst removal step is omitted, the catalyst is not inactivated, so that polymerization after leaving the polymerization vessel, so-called post-polymerization, occurs. Postpolymerization generally causes the formation of undesirable low molecular weight oligomers, waxes, greases, etc., since the polymerization temperature is higher than the average temperature within the polymerization vessel. Butene
1. Oligomers such as hexene-1 cause a decrease in density during the production of ethylene homopolymers.

In addition, in the high temperature and high pressure method, the polymerization conversion rate of ethylene is 10 to 3
Since the catalyst is as low as 0%, if the catalyst is not inactivated, there will be a large amount of unreacted motumar in the reaction polymer that exits the polymerization vessel, which will polymerize and cause a runaway reaction because the reaction is not controlled. It is fraught with great risk.

When deactivating catalysts, compounds traditionally used to remove old catalysts, such as alcohols, are used as quenching agents; alcohols are volatile and can be removed from the polymer solution along with unreacted monomers and solvents. It evaporates and contaminates the monomers and solvents, eventually requiring purification of the monomers and solvents.

The present inventors have been working diligently to develop a deactivator that is not volatile itself, does not produce volatile reaction products even after reacting with a catalyst, and is free from the risk of contaminating recovered monomers and solvents. As a result of continued efforts, we have arrived at the present invention. Of course, since the quencher remains in the polymer, it goes without saying that it must not adversely affect the properties of the polymer, such as color thermal stability.

That is, the present invention provides a method for reacting ethylene or ethylene with a C3 to C18 α- a mixture of olefins,
Polymerization is carried out at an average polymerization temperature of 130° C. or higher, and a sufficient amount of a certain lithium compound is added to the resulting polymer mixture as a deactivator to inactivate the catalyst. Inactivation of the catalyst by addition and mixing in solution or suspension form, pure solid or molten state; unreacted monomers or unreacted A method for producing polyethylene, which comprises separating monomers and an inert hydrocarbon solvent, and separating the deactivating agent and a polymer containing a reaction product of the deactivating agent and the catalyst. It is.

The Ziegler type catalyst used in the present invention contains a transition metal compound and an organometallic compound as main components.

Examples of transition metal compounds include titanium halides,
Transition metal halides of Groups 1 to 2 are used, such as vanadium halides, vanadium oxyhalides, and the like. As a Nanki metal compound, alkyl aluminum 2
Aluminum compounds such as alkylaluminium chloride, or aluminum-magnesium complexes such as alkylaluminum-magnesium complexes and alkylalkoxy7 aluminum-magnesium complexes are used.

The Ziegler-type catalyst used in the present invention must have sufficiently high activity that it does not require removal of the catalyst, and must also rapidly react with the non-inventive deactivator to deactivate it. Must be. Examples of preferable catalysts used in the present invention that meet these Yasugi standards include t1i1)i4
-47409 and JP-A-56-59806, there is a medium consisting of a solid reaction product obtained by reacting a bamboo plate magnesium compound with a titanium compound or a vanadium compound, and an aluminum compound.

That is, in JP-A-56-47409, (A) (
+) General formula 14Mg1jR,%R,jX,%X; (wherein M is AA, Zn.

B, Be, Li, β is a number of 1 or more, α,
p, q.

r, s must be 0 or a number larger than 0, 1)-1-(
10r1s""mα+2βl O≦(P+s)/(α1β)≦1.0, m is the valence of M, R1
, R2 has 1 to 2 carbon atoms, which may be the same or different
o hydrocarbon group, Xi and X2 are the same or different groups, hydrogen atom, OR3,08iR'R5R', NR'
R8, SR9 shows the null M, R31R', R8, R9
represents a hydrocarbon group having 1 to 200 carbon atoms, R4, R
5, R6 represents a hydrogen atom or a hydrocarbon group having a few to 20 carbon atoms); an organic magnesium component soluble in a hydrocarbon solvent represented by the formula (11) Ti (OR10) n
-X4-nC formula, B10 is a hydrocarbon group having 1 to 2 carbon atoms, X is a halogen, O≦n≦3] is added to the organomagnesium component of (1) A catalyst comprising a solid reaction product obtained by reacting the titanium compound of 4) at a molar ratio of 1.1 to 4.0 and an organoaluminum compound of CB) is disclosed.

Moreover, in JP-A-56-59806, (A) (1) General formula M. mpqRix, x:, <
In the formula, M is A7. Zn.

B, Be, Li, β is a number greater than or equal to 1, α+P
+ q+ P+8 is 0 or a number larger than 0! '
, P+(1"r+ 8"nla+2β,0ot(r1s)/(α+β)oti,o, where m is the valence of M, and R1 and R2 are carbons that may be the same or different. A hydrocarbon group having 1 to 20 atoms, Xi and X2 are the same or different groups, a hydrogen atom, OR3,08iR'R'R
', NR' indicates a group R8, SR9, R3, R7,
Re and R9 represent a hydrocarbon group having 1 to 20 carbon atoms, and R4, R5, and R6 represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ) and (n) a titanium compound containing at least one halogen atom, a solid reaction product of the general formula Ti Xa (OR1
°) 4-a + VOXb (0R10) 3-b
Xc(OR10)4c, (wherein X is a halogen atom, R
10 represents a hydrocarbon group having 1 to 20 carbon atoms, and a
is an ore of 1 to 4, b is 1 to 3, and C is 1 to 4); (B) A catalyst comprising an aluminum compound is disclosed.

Another example of a preferable catalyst used in the present invention is
JP-A-56-26905.28206.32504゜4
5910, 47408.59805 and JP-A-57-1
Examples include the catalyst described in No. 6005.

An example of this is (1) General formula MctMg 慝R, fiX↓KariD□ (in the formula M
is a metal atom of Group II to Group II of the periodic table, αr P+ q
+ r is 0 or more than 0, S is p greater than 0 and less than 1, t
is 0 or a number larger than 0, p10q0r0s""mα+
2.0((P+s)/(α+1)≦1.0. s≦t
m is the valence of M, R1, R2 are hydrocarbon groups having from 1 to 20 carbon atoms, which may be the same or different, and X
l represents a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, X2 represents a halogen atom, and D represents an electron-donating organic compound); (II) hydrogen chloride,
To a reactant of an organic halide, a mixture of two or more electrodes or two or more electrodes selected from halides of boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, cadmium, and mercury, (l
ii) Catalyst component [A] formed by contacting a titanium compound or/and a vanadium compound and an organometallic compound CB
).

Another example is the following component CAI) and organometallic compound [B]
It is a catalyst consisting of

Component [A] Solid catalyst (1) formed by reacting (4) and (5) in the presence of (3) shown below (1) General formula - %R; ~Group ■ metal atom, α+ P+ q+
r is a number greater than or equal to 0, P+q-mα+2,0≦q/(α
+1) <2, where m is the valence of M, R' is one type or a mixture of two or more hydrocarbon groups having 1 to 20 carbon atoms, and X' is a hydrogen atom, oxygen, or nitrogen. or one or a mixture of two or more negative groups containing a sulfur atom, D represents an electron-donating organic compound) Boron, silicon, germanium, tin, phosphorus, antimony, bismuth, A mixture of one or more fc selected from /- halogenide of zinc or hydrogen chloride (a solid component (exudate) resulting from the reaction of 3) and (2), an organometallic compound (powder), and a transition metal of any of the following (a) to (b). Compound (a) titanium compound, (b) vanadium compound, (c)
Titanium compounds and vanadium compounds, (d) titanium compounds and zirconium compounds. Atom, α+ P+ q+ P+
8 is 0 or a number greater than or equal to 0, β is a number greater than 0, and p
+q+r+s=mα+2β, 0≦(P+s)/(α+β
)≦1.0, m is MCI valence, t is 0 or a number larger than 0, R' and R2 are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, x”
, x2 are the same or different groups and represent a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atoms, and D represents an electron-donating organic compound), which is soluble in a hydrocarbon solvent. and (1) hydrogen chloride, organic halides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony,
A reactant of one or a mixture of two or more selected from bismuth, zinc, cadmium, and mercury halides,
Qii) A catalyst consisting of a catalyst component [A] formed by contacting a titanium compound or/and a vanadium compound and an organometallic compound [B].

The α-olefin used in the present invention has 3 to 18 carbon atoms, such as propylene, butene-11pentene-11hexene-1,4-methylpentene-1, heptene-1, octene-1, 1, nonene-1,
Decene-1% and can be used alone or as a mixture.

The polymerization method used in the present invention is carried out under high temperature microbial conditions at a polymerization temperature of 130°C or higher, and typically includes polymerization at a polymerization temperature of 130°C to 300°C in the presence of an inert hydrocarbon solvent; A solution polymerization method in which ethylene or a mixture of ethylene and α-olefin is polymerized at a polymerization pressure of 10 to 500 atmospheres, by supplying a Chevesey-type catalyst instead of a radical catalyst to a conventional radical polymerization low-density polyethylene plant.
There is a high-temperature, high-pressure polymerization method in which ethylene or a mixture of ethylene and α-olefin is combined at a polymerization temperature of 1300 to 300°C and a polymerization pressure of 200 to 3000 atm.

As an inert hydrocarbon solvent used in solution polymerization method,
Examples include pukun, pentane, hexane, cyclohexane, heptane, octane, inoctane, nonane, decane, dodecane, and the like. These can be used alone or as a mixture.

Specific examples of the solution polymerization method include C, T, Elst
Canadian Patent No. 9804 dated December 28, 1975
There is a process described in No. 98.

The high temperature and high pressure polymerization method includes an autoclave method using an autoclave reactor, a tubular method using a tubular reactor, and various multistage polymerization methods in which an autoclave and a tubular reactor are combined for polymerization. An example of high temperature and high pressure polymerization method is BP 932.2
31SEP 1.205.635゜USP l, 16
1.737 etc.

After the polymerization is complete, the reaction mixture that comes out of the polymerization reaction vessel contains the polymer, unreacted monomers, Ziegler-type catalyst that remains partially active, and inert carbon when an inert hydrocarbon solvent is used. Contains hydrogenated solvent. A deactivator is mixed with the reaction mixture to prevent postpolymerization and to deactivate the catalyst. The deactivator and the reaction mixture may be mixed either before or after the vacuum pulp between the polymerization vessel and the polymer separator. The mixing method may be by simply merging the flows of two pipes, or by using a mixer such as a static mixer or an in-line mixer, which allows the catalyst and deactivator to come into contact quickly. Either method is fine.

The amount of deactivator added must be sufficient to ensure deactivation of the catalyst. Such deactivation of the catalyst is carried out by deactivating at least one of the constituent components of the catalyst, ie, the transition metal compound and the organometallic compound.

The amount of the quencher used in the present invention is 0.00% per 1 mmol of the total mole of the transition metal compound and the organometallic compound.
It is in the range of 1-4 mmol. If it is less than 0.1 mmol, the deactivation will not be sufficient, and if it is more than 4 mmol, the cost will increase and it is not economical.

As the deactivator used in the present invention, various organic lithium compounds such as methyllithium, ethyllithium,
n-butyllithium, 5ee-butyllithium, 1so
-butyllithium, n-globyllithium, 1so-globyllithium, heptyllithium, octyllithium, isoamyllithium, cyclohexyllithium, cisglopenyllithium, inbutynyllithium, 1-cyclopentenyllithium, phenyllithium, o-tolyllithium, m -) Lillithium, p-) Lillithium,
2-naphthyllithium, 2-pyridyllithium, 3-pyridyllithium, polymethylene-α,ω-dilithium,
Dilithium compounds such as diphenylethylene dilithium and the reaction product of diisoprenylbenzene and 8ee-butyllithium can be mentioned.

The deactivator is dissolved or suspended in an inert hydrocarbon solvent,
Alternatively, it is added to the reaction mixture in pure solid or molten state. When an inert hydrocarbon solvent is used, it is preferably the same as the polymerization solvent. If different, it must not have any adverse effect on the recycling of the polymerization solvent.

The reaction mixture to which the quencher has been added is passed through a polymer separator.
The volatile heptamers or inert hydrocarbon solvent and the polymer are separated. The volatile substances are recovered in a gaseous state from the polymer separator. The quencher and the reaction product of the quencher and the catalyst are separated. In the polymer separator, it remains in the polymer without being gasified.Additives such as antioxidants and, if necessary, catalyst neutralizers and lubricants are added to the obtained polymer, and finally is pelletized using an extruder.

By using the deactivator of the present invention, (1) the catalyst is inactivated and the polymerization reaction is promptly stopped.

This prevents uncontrolled runaway polymerization of unreacted polymers in the polymer separator, and also suppresses the formation of low molecular weight polymers (wax, grease, etc.) due to post-destruction. (2) Undesirable side reactions, such as the production of butene-1 due to dimerization of ethylene, are suppressed. The formation of butene-1 reduces the density of the ethylene homopolymer. (All or part of the monomers and inert hydrocarbon solvent recovered from the east reaction mixture are removed without a purification step.
Alternatively, it can be recycled and used by passing it through a simple purification process. (The deactivating agent remaining in the polymer or the reaction product of the deactivating agent and the catalyst does not adversely affect the properties of the polymer, and a polymer with excellent color and thermal stability can be obtained.

Of course, the ethylene copolymer of the present invention includes conventional stabilizers, ultraviolet absorbers, antistatic agents, antiblocking agents, lubricants,
Substances normally added to polyolefins can be added, such as pigments, inorganic or organic fillers, rubbers and other small amounts of polymers.

Examples of these additives include BHT, Shell Ionox 330. Gutdry made by Gridrich)
3114, Irganox 101 manufactured by Ciba Geigy
0, 1076, Tinuvin 327, Sanki Pharmaceutical LS
770, LS622. DMTP, DLTP, calcium stearate, hydrotalcite, basic magnesium carbonate, erucic acid amide, oleic acid amide, titano white, calcium carbonate, carbon black, talc, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, High-pressure polyethylene, ethylene-propylene rubber, polypropylene, etc. are available.

EXAMPLES Next, the present invention will be described in detail with reference to Examples, but these Examples are not intended to limit the present invention in any way.

(Synthesis of solid catalyst A) After removing oxygen and moisture inside the autoclave with dry nitrogen, trichlorosilane, 1°6 L of 0.5 mol/l hexane solution and 1.2 t of hexane were charged.
The temperature was raised to 70°C. Next, A4. tsMg(nBu)1.
75 (On Bu) o, y (metal humidity 0.9 mo
l/l octane solution) 0.45t and hexane 0.45t.
0.6 t of hexane containing TiC40,7 was introduced into the 0.6 t of hexane which was made equal in size over 35 t at 70°C for 1 hour, and the reaction was carried out at 70°C for 1 hour. The generated inert solid is designated as catalyst A. When the titanium (Ti) content in Catalyst A was measured, it was found to be 0.5% by weight.

In addition, A4. zsMg (n-Bu)z,ys (On
'-Bu)0.7 was produced according to JP-A-1-57-5709 (Synthesis of solid catalyst B) AI-o, xsMg (nBu)0.
ys (On-Bu)o, 7400 mmol, trichlorosilane 400 mmol, and vanadyl trichloride 8°8
The synthesis was performed using 12 mmol of titanium tetrachloride. Nadium (■) and titanium (Ti) in catalyst B
) The total content was 230.

(Synthesis of solid catalyst C) Oxygen and moisture inside a 500-capacity flask equipped with two dropping funnels were removed by dry nitrogen replacement, and 1
60 d of hexane was added and the mixture was cooled to -10°C. Next A
4Mg3.3 (n C4Hc+)x4. s”(On
40 mmo of organomagnesium φ aluminum compound with the composition of C4Ho) o, a as the organomanesicum component.
A heptane solution containing 80 mnol of n-butoxytitanium trichloride and 80 mn of a hexane solution containing 60 mrnol of n-butoxytitanium trichloride were weighed into each dropping funnel, and both components were simultaneously added dropwise with stirring at -io°C over a period of 1 hour. The mixture was further aged and reacted at this temperature for 3 hours. The resulting hydrocarbon-insoluble solid was isolated, washed with n-hexane, dried and 11
．． A 2F solid product was obtained. Ti content is 21%
It's f9. Note that AjMg5. B (n-C4Hg
), 5a (On C4H9) 0.4 is JP-A+1E
Synthesized according to Example 1 of No. 56-47409.

(Synthesis of solid catalyst) klMgs (C2us) 1.5 (n C4H(
1) s (O8iH・CH3・C2H5h, s) A heptane bath solution 80 me containing 40 mmol of a heavy machinery magnesium component and a heptane bath solution 80 me containing 40 mmol of titanium tetrachloride was used as a heavy machinery magnesium component. Weigh it into each dropping funnel,
Both components were added dropwise at the same time over 1 hour while stirring in a 500-volume nitrogen-substituted flask containing 160-hexane at vcO°C, and the mixture was further aged at this temperature for 3 hours. The product was filtered and washed with heptane to give a solid product. Subsequently, an octane slurry containing this solid reaction product of 100 dK composition Ti Ct3,5(On -C4)
300 rnmol of a titanium compound of I, ) o, s was added and reacted at 130° C. for 3 hours to obtain a solid catalyst CD of 12.2 f. The Ti content was 19.8N. The above organomagnesium-aluminum compound was synthesized according to the example of JP-A-56-59806.

Examples 1 to 7, Comparative Examples to 4 Solid catalyst A was placed in a polymerization vessel with a stirrer having a capacity of 100 t.
1. Or/Hr, temperature g, cyclohexane solution of 1 mmol/L triethylaluminum at 200 A/Hr
Hr, (triethylaluminum 20 mmo17'H
r), ethylene was continuously supplied at 25 Kg/Hr, hydrogen was continuously supplied at I Kg/Hr, and the polymerization temperature was set at 20 Kg/Hr.
Polymerization was carried out at 0°C and a pressure of 80 Kg/a+f. The polymerization conversion rate of ethylene was about 80%, and the amount of polyethylene produced was about 20 Kg/Hr.

The quencher was a 2.wt% solution or slurry solution of cyclohexane and was added continuously after the reaction mixture exited the polymerization vessel. The deactivated reaction mixture was once heated to 250 t: using a heat exchanger, and then lowered to a pressure of IKf/- using a stainless steel needle valve.
This was poured into a separator. Gaseous unreacted ethylene and cyclohexane were continuously collected from the upper part of the separator, and a polymer cyclohexane slurry cooled to room temperature was continuously extracted from the bottom part 2 of the separator. The polymer slurry was separated into polymer and cyclohexane using a centrifuge, and then fed into a vented extruder and pelletized. The pellets obtained were crushed and dried under vacuum to completely remove volatile components, and then the basic percentage of the polymer was measured.

Once the polymerization started and stabilized, the amount of Ml was increased.

Continuous circulation of the ethylene and cyclohexane recovered from the vessel for use in polymerization was started without distillation and purification, and this was continued for 4 hours.

To compensate for the insufficient amount of recovered ethylene and cyclohexane, we made up fresh ethylene and cyclohexane.

The groductivity (polymer production amount (1) per 12 solid catalysts) of the solid catalyst A was measured when the polymerization was stabilized after the start of the polymerization and after 4 hours.

This makes it possible to determine how much the quenching agent adversely affects the circulation of ethylene and cyclohexane.

In addition, the density of the polyethylene was measured when the polymerization was stable and after 4 hours. When butene-1 is produced due to a side reaction, the density decreases, so the degree of by-production of butene-1 can be determined from the change in density. Test results for seven quenchers are shown in Table 1.

As is clear from the results in Table 1, when no deactivator is used (Comparative Example 1), the amount of low polymer produced increases and the molecular weight distribution (R7fW/MN) is wide. In addition, when methanol was used as a quenching agent (Comparative Example 2),
When polymerization is stable, a polymer with normal properties can be obtained, but
When circulation of unreacted ethylene and solvent cyclohexane was started, the activity rapidly decreased, and polymerization completely stopped after 4 hours of circulation.

On the other hand, when the organolithium compound of the present invention was used as a deactivator (Examples 1 to 7), a polymer with a sharp molecular weight distribution and good color was obtained, and even after the unreacted ethylene and the solvent cyclohegisane were circulated, However, no decrease in density or gloductivity was observed. Also, if there is less quenching agent (
Comparative Example 3), the molecular weight distribution becomes broader.

Example 8 Solid catalyst A was placed in a polymerization vessel with a stirrer having a capacity of 100 t.
1.3 r/Hr,, @ W Oll rnmo
1/A cyclohexane solution of triethylaluminum at 200/! /I(r(triethylaluminum 20m
mo1//)Tr), ethylene at 20 Kg/Hr, and butene-1 at 10 to 7/Hr, respectively, were continuously supplied, and polymerization was carried out at a chassis temperature of 200° C. and a pressure of 80 K7/cm. The positive conversion rate of ethylene was approximately 85%, and the amount of ethylene-butene-1 copolymer produced was approximately 18 Ky/I.
The polymerized reaction mixture was treated in the same manner as in Example 1.

The results obtained are shown in Table 2.

Example 9 Ethylene-octene-1 co-coalescence was obtained in the same manner as in Example 8 except that a 12ψ can of octene-1 was supplied instead of butene-1. The results obtained are shown in Table 2.

Example Process 0 Polyethylene was obtained by polymerization in the same manner as in Example 1 except that solid catalyst B was used instead of the solid catalyst. The results obtained are shown in Table 2.

Example 11 Polymerization was carried out in the same manner as in Example 8 except that solid catalyst C was used instead of solid catalyst A to obtain an ethylene-butene-1 copolymer. The results obtained are shown in Table 2.

Example 12 Same as Example 9 except that solid catalyst glue is used for glue 9 of solid catalyst A. : was polymerized to obtain an ethylene-octene-1 copolymer. The results obtained are shown in Table 2.

Example 13 Ethylene polymerization was carried out using an autoclave equipped with a stirrer and having an inner Y product of 2 tons. 1 combined pressure 1,200 K9/l:t
A.

At a reaction temperature of 220°C, ethylene was fed at 40 Kg/Hz,
The solid catalyst [:A) deprivation of 0.15 f/klx,) ethylaluminum was fed to the reactor at a feed rate of 3.0 m m)l/'Hr, respectively. The amount of polyethylene produced was 3.8 Kq/Hr'''C in the form of a liquid in which a deactivator was mixed with mineral oil with an average boiling point of 150°C.
It was added continuously after the reaction mixture left the polymerization vessel. The deactivated reaction mixture was 250%/cr! The mixture was introduced into a separation system in which a medium pressure separator maintained at a pressure of 10 Kg/cni and a low pressure separator maintained at a pressure of 10 Kg/cni were connected in series to separate unreacted ethylene and polymer.

Table 2 shows the properties of the polyethylene obtained when the polymerization was stable and after 4 hours of circulating unreacted ethylene.

Comparative Example 4 Polyethylene was obtained in the same manner as Example 3 except that no deactivating agent was used. The properties of the obtained polyethylene are shown in Table 2.

Large Example 14 Using a tubular reactor with an inner diameter of 51 nM and a length of 40 m, the test was carried out at a pressure of 1000 koji and a temperature of 260°C.

Ethylene to 16 4/I (r, butene - 124Kg/I
(r, solid catalyst [B] was supplied to the reactor at a supply rate of 0.15?/Hr, and ethylaluminum was supplied at a supply rate of 3.0 mmol/Hr, respectively. The amount of polyethylene produced was 3.5 Kr. The steps after addition of the deactivator were performed in the same manner as in Example 13. The results obtained are shown in Table 2.

The meanings of terms used in the examples are as follows.

(1) MI: represents melt index, AST
M D-1238K Therefore, temperature 190℃, load 2
．． The measurement was carried out under the condition of 16 kg.

■ Density: Measured according to JIS K-6760.

(3MW/MN: Measured with Waters GPC-150C.

(Ratio of small molecules t 5+000 or less: Measured with Waters GPC-150C.

(0 Resin Color: Measured the Hunter method L value, b1h using a color difference needle made by Color Machine Co., Ltd. Addressed to the 0 or less Eihaku Procedures Correction Officer) January 24, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office , Indication of the case ■ gf 口 58 り [raw potato 3 mockery 37288 No. 2, name of the invention Process for producing ethylene polymer (after amendment) 3, person making the amendment 4, subject of the amendment.

(3) Fill out the column for detailed explanation of the invention in the specification as shown below.
Canceled.

that's all Scope of claims

Claims (1)

[Scope of Claims] (1) In the presence or absence of an inert hydrocarbon solvent, using a transition metal compound and an organometallic compound Kanakura-type Ziegler catalyst, ethylene or ethylene and α of 3 to 18 carbon atoms are combined. - Total mixture of olefins, average platform temperature 13
polymerizing at a temperature of 0° C. or higher, adding a strong deactivator sufficient to inactivate the catalyst to the resulting polymer mixture;
adding the organolithium compound in solution or suspension in an inert hydrocarbon, or in pure solid or molten state;
deactivating the catalyst used for mixing; separating unreacted monomers or unreacted monomers and an inert hydrocarbon solvent from the resulting polymer mixture;
and a method for producing polyethylene, characterized in that the polymer containing the deactivating agent and the reaction product of the deactivating agent and the catalyst is completely separated. A method for producing polyethylene according to claim 1, characterized in that the amount is 0-1 to 4 mmol per 1 mmol of the total number of moles of the compound (3) As a Ziegler type catalyst (A) (+) General formula M. M2 Instigation NX Nsa (M in the ceremony
is At. Zn, B, Be, Lj, β is a number of 1 or more, and α. p+ q+ L S is 0 or a number greater than 0. p+q+r+s=mα+2β, 0≦(r+s)/(α+
β)≦1.0, 1m is the valence of M, R1゜R
2 is a hydrocarbon group having 1 to 20 carbon atoms which may be the same or different %XI, X! are the same or different groups,
Hydrogen atom, OR", 08iR'R5R'. Indicates a group NR, 7R, 8, SR', R11, R7,
l(,8', l(, l represents a hydrocarbon group having 1 to 20 carbon atoms, R4, 1%s, g6 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) and an organomagnesium component soluble in a hydrocarbon solvent represented by: (11) Formula Ti (""')n -Xa-n is a halogen. 0≦n≦3] is a solid reaction obtained by reacting the titanium compound (11) with the organomagnesium component (1) at a molar ratio of 1.1 to 4.0. (4) As a Ziegler type catalyst (A) (1) General Formula MaMgβRB”HX:XHC
In the formula, M is At. Zn, B+ Be, Li, β is a number of 1 or more,
α. P.
Valence of R1 and R2 are hydrocarbon groups having 1 to 20 carbon atoms which may be the same or different, Xl and X2 are the same but different groups, hydrogen atom, OR3, O8i R' R5
R', NR' represents the group R8, SR9, R3, R
7, R8, RQ represents a hydrocarbon group having 1 to 20 carbon atoms, and R4゜R5, R6 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). The solid reaction product of an organomagnesium component soluble in (11) a titanium compound containing at least one halogen atom is prepared by (III) the general formula %VXc(OR'')4-c (formula In the middle, a solid catalyst obtained by reacting at least one compound selected from titanium and vanadium compounds; and (B) an organoaluminum compound. The method for producing polyethylene according to claims 1 and 2 (5) As the catalyst, (1) the general formula MczMgRjRj metal atom, α+p+qw
r is 0 or greater than 0, 8 is greater than 0 and less than or equal to 1, t is 0
Or a number larger than O, p+q+r+g=mα+2.
O((r+s)/(α+1)≦1.0.s≦t, where m is the valence of M, and R1 and R2 are hydrocarbon groups having 1 to 2 carbon atoms, which may be the same or different. represents a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom; ) one or a mixture of two or more selected from hydrogen chloride, organic halides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, cadmium, and mercury halides; Claim 1, characterized in that a catalyst component formed by contacting a reactant with (iit) a titanium compound or/and a vanadium compound (a catalyst consisting of Al and an organometallic compound [B]) is used.
7. The method for producing polyethylene according to item 2 (6), the following component [A] as the F--gla catalyst
Component [A] in the presence of (3) shown below (4) Solid catalyst formed by reacting (5) with General formula -Mg 'p'q・D, (where M is a metal atom of Groups ■ to ■ of the synchronous table, α+ p+ q+ r
is a number greater than or equal to 0, and p+q=mα+2. O≦q/(α+
1) It has the relationship of <2, where m is the valence of M, R' is one or a mixture of two or more hydrocarbon groups having 1 to 20 carbon atoms, and da is a hydrogen atom, an acid drug, or nitrogen or one or a mixture of two or more negative groups containing a sulfur atom, D represents an electron-donating organic compound) Boron, silicon, germanium, tin, phosphorus, antimony, bismuth, One or more mixtures selected from zinc halides or hydrogen chloride (solid component (4) by reaction of ω and ■) Organometallic compound (5) Ti1e Any transition of (a) to (d) Metal compounds (a) titanium compounds, (b) vanadium compounds, (C) titanium compounds and vanadium compounds, (d
) for titanium compounds and zirconium compounds (as a Ziegler f independent medium, (+) general formula M. MgβRI) q+
r+ S is a number greater than or equal to 0, β is a number greater than 0, and p + q + r+ B = mα+2β, 0≦(
r”s)/(α+β)≦1.0, and ln is M
valence, t is O or a number greater than 0, R1,
R2 is a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different; Xl; X2 is the same or different group, hydrogen atom or oxygen,
a negative group containing a nitrogen or sulfur atom, and D represents an electron-donating organic compound) soluble in a hydrocarbon solvent; and (11) hydrogen chloride, organic/logenide, boron. , a reactant K, (lit ) The scope of patent claims described in Items 1 and 2 is characterized in that a catalyst consisting of a catalyst component (A) formed by contacting a titanium compound or/and a vanadium compound and an organometallic compound (B) is used. Polyethylene manufacturing method