JPS6060116A - Production of ethylene polymer - Google Patents

Abstract

PURPOSE:To facilitate the recovery of a polymerization solvent and residual monomers without any risk of contamination, by using a specified titanate compound as a catalyst deactivator in the polymerization of ethylene or the like in the process of a Ziegler-Natta co-ordination catalyst. CONSTITUTION:A titanate compound of the formula (wherein R<1> and R<2> are each a 1-30C hydrocarbon group, m and n are each 0-4 and m+n=3 or 4) e.g., methyltritoluenesulfonyl titanate is used as a deactivator in the polymerization of ethylene (optionally, together with a 3-18C alpha-olefin) at 130 deg.C or above in the presence of a co-ordination catalyst. The catalyst is deactivated by adding the deactivator in an amount of about 0.1-6mmol per mmol of the total of the number of moles of transition metal compound and organometallic compound in the catalyst. The solvent, unreacted monomers, etc., are separated and recovered from the obtained polymer mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyethylene and ethylene-α-olefin co-polymerization, and the present invention relates to the production of polyethylene and ethylene-α-olefin co-polymerized catalysts, which are used in the polymerization of ethylene and α-olefins. Regarding inactivation.

PJ-,t also combines polyethylene and hyethylene to α-olefin i1 polymerized by contact, usually at 0.
It has a wide density range of 850 to 0.975 y/crn', and is used in large quantities for a wide variety of applications, such as films, blow molded products, fibers, and extrusion molded products.

As a catalyst for polymerizing ethylene or a mixture of ethylene and α-olefin, the most common catalyst is a conventional catalyst. [Phase] Chiite 16 associate medium mainly contains transition metal compounds belonging to groups ■ to ■ of the Shumingjin table, represented by compounds of titanium and d-nadium, and organometallic compounds such as organoaluminum compounds. Contained as an ingredient.

As a method for preparing ethylene or mixtures of ethylene and α-olefins, a step-by-step process has been used.
; ■ Combine at a high temperature of 130°C or higher (8. Night polymerization method: High-temperature, high-pressure polymerization method that does not use a vine medium). Unlike legal and gas-phase polymerization methods, this method is an excellent energy-saving method as it does not require energy to remove fleas.

In recent years, a highly active Okashin Okago Shichi catalyst has been developed, and the catalyst residue in the polymer is extracted with alcohol or caustic soda.
・Even without neutralization, the amount of catalyst residue in the polymer is very small, and the color and thermal stability are similar to that of conventional polymers that have been subjected to catalyst removal. You're getting something you don't have. If there is a catalyst removal process, the recovered combined solvent and unreacted monomers are in contact with polar compounds such as alcohols, so it is impossible to use them in the polymerization process. There are several flights that separate alloys and metals. On the other hand, when a highly active catalyst is used, since polar compounds such as alcohols are not used, part or all of the combined solvent and unreacted monomers are not purified at all, or a very simple f17 manufacturing process ( For example, it can be reused simply by processing it through a molecular sieve (for example, by passing it through a molecular sieve), making it possible to save a huge amount of energy such as steam required for distillation and purification.

However, if the catalyst removal step is omitted, the catalyst will not be inactivated, resulting in polymerization after leaving the singeer, so-called post-polymerization. In post-polymerization, the polymerization temperature is generally higher than the average temperature in the polymerization vessel, which causes the formation of undesirable low-molecular-weight oligomers, waxes, greases, and the like. Butene
Oligomers such as 11-hexene-1 cause a decrease in density during the production of ethylene homopolymers.

Father, in the high temperature and high pressure method, the polymerization conversion rate of ethylene is 10-3.
Since the monomer content is as low as 0%, if the catalyst is not inactivated, there will be a large amount of unreacted monomer in the reaction polymer that exits the tray.
Because this polymerizes and the reaction is not controlled, 5
Be aware of the serious danger of triggering an A-tactic reaction.

When cod is used as a quenching agent for the inactivation of conventional compounds such as alcohol (+h'), since alcohol is volatile, unreacted -
It evaporates from the polymer solution together with the polymers and solvent, contaminates the monomers and solvent, and eventually monomers j, +, 'i
or purification of the solvent may be required.

Kinoe Akika et al.-1 developed a deactivator that is not volatile itself, does not produce volatile reaction products even after reacting with a catalyst, and does not cause the risk of contaminating the solvent or other substances during recovery. As a result of continued efforts, we have arrived at the present invention. Of course, it goes without saying that the quencher must remain in the polymer and must not have any effect on the properties of the polymer, such as color and heat stability.

That is, the present invention provides a method for treating transition metals [including arsenic metals and organometallic compounds] in the presence or absence of an inert hydrocarbon solution, and in the presence or absence of ethylene or A mixture of ethylene and an α-olefin having 3.f to 18 carbon atoms is polymerized at an average polymerization temperature of t3o'c or higher, and the resulting polymer mixture is injected with a sufficient amount of inert f to keep the catalyst inactive. Beast quencher, general formula (R'
-0% Ti (-o-s0R2).

I (R1 and R2 are hydrocarbons having 1 to 30 carbon atoms, I, ¥, m
and n is an integer between θ and 4, and nt and n are 3 or 4. )
The catalyst is rendered inactive by adding the thiinated metal compound represented by the inert hydrocarbon solution or in the open state, or in the pure solid or molten state, and mixing to inactivate the catalyst. separating the unreacted monomers and the inert hydrocarbon solvent from the resulting polymer mixture; The present invention relates to a method for producing an ethylene polymer, which is characterized by separating a polymer containing a reaction product.

The sand BH-V'15 catalyst used in the present invention contains a transition metal compound and a so-called compound as the main component.The transition metal compound includes Ir, halogen Hokutentan, etc. The t'lJ transfer metal halide proboscis such as vanadium halide, )ζnanium ogishihalai r, etc. is directed northward. As the organometallic compound, organoaluminum compounds such as alkylaluminum, alkylaluminum chloride, etc., or organoaluminum-magnesium complexes such as alkylaluminum-magnesium complex, alkylalkoxyaluminum-machinium complex, etc. are used. be done.

The [phase] B to 1 catalyst used in the present invention must have sufficiently high activity that it does not require the removal of the catalyst, and it must react rapidly with the deactivating agent of the invention to deactivate it. ”- An example of a preferable catalyst used in the present invention that meets these requirements is disclosed in JP-A-56-47.
There is a catalyst comprising a solid reaction product obtained by reacting an organomagnesium compound with a titanium compound or a titanium compound, and an organoaluminum compound, as shown in No. 409 and JP-A-56-59806.

That is, in JP-A-56-47409, (A) (i
) General formula MaMg7R'pR2qX'rX2s (wherein M is Ap, , Zn.

B, Be, Li, β is a number greater than or equal to 1,
+T'+q+r, s is O or a number larger than 0,
p+q+r+s = mα+2β, 0≦(r+8)/(σ
+β)-=l, to, m is the valence of M, R
', R2 has 1 to 1 carbon atoms, which may be the same or different
20 hydrocarbon groups, XI and X2 are the same or different groups, hydrogen atom, OR3,08iR'R'R', NR7
R', SR9 represents a group, R", Rf R8
, R9 represents a hydrocarbon group having 1 to 20 carbon atoms;
', R5, R' represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms);
” ) n-x4-nC In the formula, R10 has 1 to 20 carbon atoms.
is a hydrocarbon group, X is /.rogen, 0≦n≦3], and the titanium compound of (11) is added to the organomagnesium component of (1) in a molar ratio of 1.1. -4
．． A catalyst comprising a solid reaction product obtained by reacting at 0 and (B) an organic aluminide is disclosed.

Also, Tokukai Akira! ;7 to G-59806, (A) (i)
General formula MaMg7R'pR2qX'rX2s (in the formula M
is Afi, Zn.

11, Be, Li, and β is a number greater than or equal to 1.
jpIqlr, s is 0 or a number smaller than 0, p
+q+r+ s==mα+2β, 0≦(r+a)/(α
+β)≦1.0, m is the valence of M, R',
R2 has 1 to 20 carbon atoms, which may be the same or different
hydrocarbon group, XI, X2 are the same or different groups, hydrogen atom, OR', 03iR'R'R', NR7
R8, SR' represents a group, R3, R', R',
R' represents a hydrocarbon group having 1 to 20 carbon atoms,
(11) at least one halogen; The solid reaction product with a titanium compound containing atoms (il) has the general formula TiXa (OR10
) 4-a, VOXb (OR” ”) 3-b and VXc (ORIO) 4-C (in the formula, ~4, b is a number from 1 to 3, and C is a number from 1 to 4), and a solid catalyst obtained by reacting with at least one compound selected from titanium and nonodium compounds; (B) a catalyst comprising an organoaluminum compound.

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.

Examples thereof are: (1) General formula M, MgR'pR2qX'rX2sDt
(In the formula, M is a metal atom of Groups ■ to ■ of the periodic table, α+
P+Q+r is 0 or greater than 0, S is greater than O and less than or equal to 1, t is 0 or a number greater than 0, and p + q + r
+ s = mα+2,0ku(r+s)/(α+1)
, 41.0, has the relationship s≦t, where m is the valence of M, and R' and R'' are the number of carbon atoms 1, which may be the same or different.
~20 hydrocarbon groups, Xl 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) (11) Hydrogen chloride, organic halides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, chromium,
A reactant of one or a mixture of two or more selected from mercury halides is contacted with a titanium compound and/or a sodium compound! Catalyst component C consisting of
h'3 and an organometallic compound CB).

Another example is a catalyst consisting of the following component [A] and organometallic compound [B].

Component [A] Solid catalyst (1) formed by reacting (4) and (5) in the presence of (3) shown below (1) with the general formula igR'pX'q-D r (in the formula M
is a metal atom of ME m-s in periodic table 1~, α+
pr q+r is a number on θμ, 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 hydrogen. organomagnesium compound (2) boron, silicon, germanium, tin , phosphorus, antimony, bismuth, zinc... or a mixture of one or more selected from hydrogen chloride (3) Solid component (4) resulting from the reaction of (1) and (2)
) Organometallic compound (5) Any of the following transition metal compounds (a) to (d) (a) titanium compound, (b) sodium compound, (C
) titanium compounds and gunadium compounds; (d) titanium compounds and zirconium compounds; (1) General formula ΔlaMgβR'pR24X'rX''s
Dt (in the formula, M is a metal atom of Groups ■ to ■ of the periodic table,
α1plqlrl! 4 is 0 or a number greater than 0, β is a number equal to O, and p 1q + r 1s = mα+2
β, 0≦(r+a)/(α+β) has a relationship of 1.0, m is the valence of M, t is a number greater than 0 or 0, and R' and R2 may be the same or different. A hydrocarbon group having 1 to 2 carbon atoms, X' and X2 are the same or different groups and represent a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom; and (11) hydrogen chloride, organic halides, boron, aluminum, silicon, kermanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, A catalyst component [A] obtained by contacting a reactant of one or a mixture of two or more selected from mercury halides and mercury halides with (iii) a titanium compound or/and a nonadium compound; and This is a catalyst consisting of an organometallic compound [B].

The α-olefins used in this study have 3 to 18 carbon atoms, such as propylene, butene-11pentene-11hexene-114-methylpentene-1, hezotene-1, octene-11nonene. -1,
Decene-1, etc., and can be used alone or as a mixture.

The polymerization method used in the present invention is carried out at a high temperature of 130°C or higher, and typically includes 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, and a conventional radical polymerization low-density polyethylene plant is supplied with a radical catalyst to reduce the power of radical catalysts. Then, ethylene or a mixture of ethylene and α-olefin was heated at a temperature of 130 to 300°C, and the combined temperature was 200 to 3000°C.
There is a high-temperature, high-pressure polymerization method in which polymerization is performed at atmospheric pressure.

As an inert hydrocarbon solvent used in solution polymerization method,
Examples include butane, pentane, hexane, cyclohexane, hezotane, octane, isooctane, 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 to
Process 75E, S Le described in No. 98.

Examples of the high temperature and high pressure polymerization method include 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
31. BP 1,205,635, USP 1,16
1,737 etc. are mentioned.

After the completion of the combination, the reaction mixture that comes out of the reaction vessel contains the polymer, unreacted monomers, and partially active monomers.
Until the body Ll (3LIiL inferior catalyst, and inert H
When a 1 hydrocarbon solvent is used, an inert 1 hydrocarbon solvent is used. A deactivator is mixed with the reaction mixture to prevent postpolymerization and to deactivate the catalyst. The places where the deactivator and the reaction mixture are mixed are the polymerization vessel and l'
It may be placed either before or after the reduced pressure A loop in the middle of the remer separator. As for the mixing method, it is possible to simply combine the flows of two pipes, or to mix them using a mixer such as a static mixer or an in-line mixer, as long as the catalyst and the deactivator 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 gold kn compound and the organometallic compound. Preferably, however, the amount of deactivator used is sufficient to react with both catalyst components.

The amount of the quencher used in the present invention is such that the amount of the quencher is 0 mmol per 1 mmol of the total mole of the I-transfer metallized metal compound and the organometallic compound.
．． It is in the range of 1 to 6 mmol. o.If the amount is less than 1 mmol, the deactivation will not be sufficient, and if it is used more than 6 mmol, the cost will increase and it is uneconomical.

The deactivator used in the present invention is a hydrocarbon group of the general formula % 1 to 3 o, m and n are integers of θ to 4, m
+ n = 3 or t, x 4. ) is a titanate compound represented by One row of titanate compounds is 1
, Methyl tritoluenesulfonyl titanate, Methyltriethylbenzenesulfonyl titanate, Methyltriditylbenzenesulfonyl titanate, Methyltriotylbenzenesulfonyl-y-tanate, Notyltrirdecylbenzenesulfonyl ftanate, Methyltrioctadecylbenzenesulfonyl Titane-1., Methyltriophtacosyl pensensulfonyl titanate, Ethyl tritoluenesulfonyl titanate, Ethyltriethylbenzenesulfonyl titanate, Ethyl tributylbenzenesulfonyl titanate, Ethyltrioctylbenzenesulfonyl titanate, Ethyl triF” tesylbenzenesulfonyl titanate, Ethyl Trioctadecyl titanate/sulfonyl titanate, ethyltrioctaconlebenzenesulfonyl titanate, isopropyl tritoluenesulfonyl titanate, inzolopyltriethylbenzenesulfonyl titanate, isopropyltributylbenzenesulfonyl titanate, isopropyltrioctylbenzenesulfonyl titanate, isozolobil tridodecylbenzenesulfonyl titanate titanate, isopropyltrioctadecylbenzenesulfonyl titanate, isopropyltrioctadecylbenzenesulfonyl titanate)
, hexyl tritetracosyl benzene sulfonyl titanate, hexyl tritetracosyl benzene sulfonyl titanate, hexyl tritetracosyl benzene sulfonyl titanate, octadecyl triethyl benzene sulfonyl titanate, occtate/ru tritetracosyl benzene sulfonyl titanate, hexacocyl triethyl benzene sulfonyl titanate, Hexacosyl tri-P-decylbenzenesulfonyl titanate, diinzolopyrnoethylbenzenesulfonyl titanate, cyinoprobil dirdecylbenzenesulfonyl titanate, )7'solcitoluenesulfonyl titanate, 2-tecyldioctagylbenzenesulfonyl titanate, triisozolobyl ethylbenzenesulfonyl titanate, triisopropylene Bildetracosylbenzenesulfonyl titanate, etc. are on the rise.

The deactivator is dissolved or suspended in an inert hydrocarbon solvent,
Alternatively, it is added to the reaction mixture in pure solid or bath molten form. When using an inert hydrocarbon solvent, it must be the same as the polymerization solvent. 'I-tshii. If different, it must not have any adverse effect on the recycling of the polymerization solvent.

The reaction mixture to which the deactivator has been added is separated into volatile monomers or an inert hydrocarbon solvent and the polymer in a polymer separator. Volatile substances are recovered in gaseous form from the polymer separator. The deactivator and the reaction product of the deactivator and the catalyst are not gasified in the polymer separator and remain in the polymer. 71 obtained? Additives such as an antioxidant and, if necessary, a catalyst neutralizer and a lubricant are added to the remer, and the remer is finally pelletized using an extrusion reed.

By using the deactivator of the present invention, (1) the catalyst is deactivated and heavy reactions are promptly stopped;

? The uncontrolled runaway polymerization reaction of h kr roll-II -y -8Me onfuhatoF;'; 實w t -- is prevented, and the formation of low molecular weight polymers (wax, grease, etc.) due to post-polymerization is suppressed. be done. (
2) Undesirable side reactions, such as the formation of zothene-1 due to 2@ conversion of ethylene, are suppressed. The formation of butene-1 reduces the density of the ethylene homopolymer. (3)
All or a portion of the monomers and inert hydrocarbon solvent recovered from the reaction mixture can be recycled without a purification step or in a simple ('8) production step.4) In the polymer. The remaining quencher particles or the reaction product of the quencher and the catalyst do not adversely affect the properties of the polymer, and a polymer with excellent color and thermal stability can be obtained.

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

Examples of these additives include BHT, Shell Co., Ltd.'s Isennotsu IQl'l-, PI Reso P Luso Hand Pregnancy Side Metsuto Light 3114, and Chino ζ Geigy's Irganox 1.
010.1076, Tinuvin 327, Nil Kuwasha LS
770, LS 622, DMTP, DLTP, calcium stearate, High 1: Lotalcite, basic magnesium carbonate, erucic acid amide, oleic acid amide, titanium white, calcium carbonate, carbon black, talc, styrene-butadiene lano etc. , ethylene-vinyl acetate copolymer, high-pressure polyethylene, ethylene-propylene rubber, 110 pyrene, etc.

The present invention will be described in detail by referring to actual examples νq, but these actual examples are not intended to limit the present invention in any way.

(Synthesis to solid catalyst) Oxygen and moisture inside the autocube were removed with dry nitrogen /C, then trichlorosilane, 0.5mQQ/I1
．． Pour 1.6 u of Hex → J's liquid and 1.2 u of hexane, raise the temperature to 70°C, and then add O, +s Mg.
(n-Bu)+, ts (0n-Bu)Q, 7 (octane solution with metal concentration 0.9 mol/It) 0.4
sl, hexane o, and asx were introduced at 70°C over 1 hour.

Further, 0.62 ml of hexane containing 40.7 F of TiCE was introduced, and the reaction was carried out at 70° C. for 1 hour. The resulting inert solid is used as a catalyst. When the titanium (Ti) content in catalyst A was measured, it was found to be 0.5%.

Note that Afio, ts IAg (n-Bu) 1.
75 (On -BLI) 0.7 was manufactured in Japanese Patent Application Laid-open No. 1983.
-5709.

(Synthesis of solid catalyst B) In the same manner as A, AI'0,15(g(n-Bu)+,
Synthesis was carried out using 7s (On-Bu) o7400 m+nofi, 400 mmon of trichlorosilane, 8.8 m(3) of trichlorosilane, and 12 mmoJ' of titanium tetrachloride. The total content of pananium (V) and titanium (Ti) in catalyst B was 2.0%.

(Synthesis of Solid Catalyst C) Oxygen and moisture inside a flask with a capacity of 500+rg equipped with two dropping funnels were removed by purging with dry nitrogen, and 160 d of hexane was added thereto and the flask was cooled to -10°C. Next, AlMg5. s(n C4H9)n, s・(On-(
4H9) O, + composition magnesium aluminum compound as the organomagnesium component 40 mmoj!
80 mmol of heptane solution containing 80 mmol of n-butoxytitanium trichloride, 8 mmol of hexane solution containing 9 mmol of n-butoxytitanium trichloride
0.0% was weighed into each dropping funnel, and both components were added dropwise at the same time over 1 hour while stirring at -10°C, and the 7 grades were further aged for 3 hours. The resulting hydrocarbon-insoluble solid was isolated, washed with n-hexane, dried and heated to 11.2F.
A solid product was obtained. The content of 'ri was 21 layers. Furthermore, AJ! Mgs, 5(n-C4H*)+(s
・(On-C4H9)o, 4 is JP-A-56-4740
Synthesized according to Actual Example 1 of 9.

(Synthesis of solid catalyst) AQMg3 (C2H5)+, s (nc4H9)e
(O3iH-CH3・C2H5) Z to create a composition of 1.5
) 80d of heptane solution containing 40ml of organomagnesium aluminum compound I as the organomagnesium component and 80ml of heptane solution containing 40mmol of titanium tetrachloride were weighed into each dropping funnel, and 160ml of hexane was added. Both components were added at the same time in a nitrogen-substituted flask with a volume of 560 t at 0°C under stirring.
Dropwise addition over time and further washing with the hot butane gave a solid product. followed by an octane solution IJ-1o containing this solid reaction product.

composition TiC4,5(Or+-C4I(9)0.ynl).
300 mrnoQ of the titanium compound No. 5 was added, and the reaction was continued at 130° C. for 3 hours to obtain a solid catalyst CD) No. 12.21. '[' Containing ttt (-1: t 9. B weight 1
It was only one person. Magnesium-aluminum compound (d) Synthesized according to the example of JP-A-56-59806.

Practical Examples 1 to 7, Comparative Examples 1 to 4 Solid contact was carried out in a mixer with a capacity of 100°C.
14 A at 1.0 y/IIr, concentration 0, 1 nu
nofi/n triethylaluminum cyclohexane M solution 200Q/14r, (triethylaluminum 20 mmoR/Hr), ethylene to 25 to 9/[r
, -1 hydrogen is continuously supplied at I Kg/Hr, respectively,
Polymerization was carried out at a polymerization temperature of 200° C. and a pressure of 80 fcp/cm 2 . The polymerization conversion rate of ethylene was about 80%, and the production rate of polyethylene was about 20:5+/Hr.

The quencher is a 2 wt solution of cyclohexane or
- Scissor gain F l I Manso stay, Spring Bin Kinuta Zekakai 9 is I +
Continuously added 1 ton to 1 fu. The inactivated reaction mixture is
Once heated to 2501°C using a heat exchanger, the pressure was increased to 1kg/kg using a stainless steel lubricant.
cm2 and introduced into the separator. minnI
Gaseous unreacted ethylene and cyclohexane were continuously recovered from the h section of the vessel, and a polymer cyclohexane slurry cooled to room temperature was continuously extracted from the bottom of the separator. The polymer slurry was separated into Ie reamer and cyclohexane using a centrifugal separator, and then fed into a vented extruder and pelletized. , measuring the basic properties of polymers.

Also, once the polymerization has started and the polymerization has stabilized, a continuous circulation cycle is started in which the ethylene and cyclohexane recovered from the separator are used again for polymerization without distillation and purification.
This was done continuously for 4 hours.

As for the insufficient amount of recovered ethylene and cyclohexane, use fresh ethylene and cyclohexane in the required amount for Makeup 1. is.

Productivity (polymer production per liter of solid catalyst!=1.9)) of solid catalyst A was measured when the polymerization was stable after the start of polymerization and after 4 hours.

This allows it to be determined to what extent the quenching agent adversely affects the cyclic use of ethylene and cyclohexane.

In addition, the density of the polyethylene was measured when the bonding was stable and after 4 hours. When Zoden-1 is produced due to a side reaction, the density decreases, so the degree of Zoden-1 by-product can be determined from the change in density. Test results for six 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, the molecular weight distribution (yw/MN) becomes broader, and after 4 hours of cyclic use. Productivity and density have decreased.

In addition, Comparative Example 2) using methanol as a deactivator,
When the polymerization is stable, a nail union 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, f-
In the cases (runs I to 7), a polymer with a sharp molecular weight distribution and good color was obtained, and no decrease in density and productivity was observed even after the unreacted ethylene and the solvent cyclohexane were recycled. Also, if there is less quenching agent (
Comparative Example 3), the molecular weight distribution becomes wider and the amount of quencher increases (
Comparative Example 4) Lennon's color deteriorates.

Actual Example 8 Solid catalyst A was placed in a 100-ton polymerization vessel with a stirrer.
200R of a cyclohexane solution of triethylaluminum with a concentration of 1.3 l/Ir and a concentration of 0.1 mmjL/R.
/Hr (triethylaluminum 20 mmoJ!/H
r), ethylene at 20Kq/Hr, butene-1 at t
o Kg/Hr were each continuously supplied, and the polymerization temperature was 20
Polymerization was carried out at 0°C and a pressure of 80 Kg/cm''. The polymerization conversion rate of ethylene was about 85%, and the production of ethylene-butene-1 copolymer (11 was about 18 Kp/++r). The treatment was carried out in the same manner as in Example 1. (1
The results are shown in Table 2.

Example 9 An ethylene-octene-1 copolymer was obtained in the same manner as in Example 1118 except that octene-1 was supplied at a rate of 12/Hr instead of butene-1. Table 2 shows the results obtained using 1().

Example 10 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-Latin-1 copolymer. The results obtained are shown in Table 2.

Example 12 Polymerization was carried out in the same manner as in Example 9 except that solid catalyst A was used instead of solid catalyst A to produce ethylene-octene-1.
A copolymer was obtained. The results obtained are shown in Table 2.

Example 13 Using an autoclave with a stirrer as specified in Table 22, ethyl
/ton polymerization was carried out. Polymerization pressure 1.200 Kg/1y
n2, reaction temperature 220℃, ethylene 40Kf/Hr
-, the solid catalyst [A] was supplied to the reactor at a supply rate of 0.15y/Hr1 triethylaluminum fLI OmmoN/Ilr, respectively. 4? Liethylene production bag 3
．． sl (Li/Hr), the quenching agent had an average boiling point of 150
The reaction mixture was added continuously after it left the polymerization vessel in the form of a liquid mixed in mineral oil at . The deactivated reaction mixture and the proboscis were connected in series to a medium-pressure sealer maintained at 250 Kg/ctn and a low-pressure separator maintained at a pressure of 10 Kg/17 cm2, and led to a separation system to separate unreacted ethylene. The polymer was separated. The properties of the polyethylene obtained when the polymerization was stable and after 4 hours of circulating unreacted ethylene are shown in Part 2.

Comparative Example 5 Polyethylene was obtained in the same manner as in Example 13'll13 except that no deactivator was used. The properties of the obtained polyethylene are shown in Table 2.

Example 14 A tubular reaction i) with an inner diameter of 5 mm and a length of 4 Q ffl was carried out at a pressure of 1000 Kf/, t and a temperature of 260°C.

Ethylene at 16 Kq/Hr, butene-124+Cq
/Ilr.

Solid catalyst [B) was supplied to triethylaluminum at a rate of 0.15 y/rrr. ,I? IJ ethylene production i run is 3.5
Ky/I(r) The steps after addition of the deactivator were carried out in the same manner as in Example 13. (-) The results are shown in Table 2.

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

(1) Δ(■: represents melt index, AS
According to TMD-1238, temperature 190°C, load 2.
It was measured under 7 out of 16 disputes.

(2) Density: Measured according to JIS r (-6760).

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

(4) Proportion of molecular weight of 5,000 or less: Determined with Waters GPC-150C [611].

(5) Resin color: Color difference meter manufactured by Color Machine Co., Ltd.: The L value and L value were measured using the Hunter method.

The following margin procedural amendment (voluntary) January 1982...? Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office on C-day, 1, Indication of the case: 1982 Patent Application No. 168382
No. 2 Name of the invention Process for producing ethylene polymer a Relationship with the case of the person making the amendment Patent applicant 1-2-6-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture 4 Subject of the amendment ``Scope of Claims'' in Meishi 171 ``and [it of the invention] Ilj 5 of ``Detailed Explanation'', 1 of the amendments''.

fi) 'JJ sword 1jσIs! N, + request for permission 71
Correct the box B on the attached sheet) jjjsu Nr 0 (2) 明i;iiH store: 0 '1 invention A'f'
1ilfl fl Correct 4+::, : in the explanation as follows.

that's all! 1' Claims (1) In the presence or absence of an inert hydrocarbon solubilizer, a transition total bending compound and a coordination Σ containing a heavy metal compound (ζ
i Using a financial medium, ethylene or ethylene and carbon number 3
1) Polymerizing the α-olefin polymerization product of fl, I-18 at a temperature of 41z at a temperature of 41°C or higher, l) Adding the general formula

Claims (1)

[Scope of Claims] (1) In the presence or absence of an inert raw hydrocarbon bath medium, ethylene or ethylene and carbon number 3
to 18 α-olefins are polymerized at an average polymerization temperature of 130° C. or higher, and a deactivating agent sufficient to inactivate the catalyst is added to the resulting polymer mixture, -〇〇 is a hydrocarbon group having 1 to 30 carbon atoms, m and n are integers of θ to 4, and +n+n is 3 or 4. ) is a titatotate compound represented by. solution or suspension of inert hydrocarbons;
Alternatively, the catalyst is inactivated by adding and mixing pure solid or a molten part, and unreacted monomers or unreacted monomers are inertly carbonized from the resulting polymer mixture. A method for producing an ethylene polymer, characterized by separating a hydrogen solvent, and separating the deactivating agent and a polymer containing a reaction product of the deactivating agent and the catalyst (2) of the deactivating agent. The amount is 0.1 to 6 per mmol of the total number of moles of the transition metal compound and the organometallic compound.
Method for producing an ethylene polymer according to claim 1, characterized in that the amount is mmol (3)
As Ikutani catalyst (A) (i) General formula M, MgβR'pR2qX'rX
"s (in the formula, M is Al1, Zn, B, Be
, Li, β is a number greater than or equal to 1, α1plqlrl
s is 0 or a number greater than 0, and p + q +
r + s = mα + 2β r 04 (r-1s ) / (
α”−β)≦1.0, and the valence of m times M,
R' and R2 have 1 carbon atom, which may be the same or different
~20 hydrocarbon groups, x', x'' are the same or different groups, hydrogen atoms 10R3.03iR'R'R', NR
7R', SR'fx represents a group, R3゜R'
, R', and Ro represent a hydrocarbon group having 1 to 2 carbon atoms, and R', R', and R' represent a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. an organomagnesium component soluble in a hydrocarbon solvent, and (11) formula T i (OR")rlHX4-nC, where RIG is a hydrocarbon group having 1 to 2 carbon atoms, X is a halogen,
A solid reaction product obtained by reacting the titanium compound (0≦n≦3) with the organomagnesium component (i) and the titanium compound (ii) at a molar ratio of 1.1 to 4.0. 4Il of the ethylene-based polymer according to claim 1 or 2, characterized in that a catalyst consisting of (B) organoaluminated 17 is used.
Production method (4) As a catalyst for ip+8f (A) (i) General formula M, Mg/R'pR"qX'rX"
o (In the formula, 1 is A, fL. zn + B r Be r Lt, β is a number of 1 or more, α. ppq + r, si is a number larger than oi, p
+q+r+s-=mα+2β, 0≦(r+s)/(α+
β)≦1.0, mjd valence of M, R'
. R2 is the number of carbon atoms, which may be the same or different, from 1 to 20
The hydrocarbons 'LX', x'' are the same or different groups, hydrogen atoms, ORs, 08iR'R5R'. NR'R8,SR'
, R7, R8, R'i, i are hydrocarbon groups having 1 to 2 carbon atoms, and R4, R5, flQ are hydrogen atoms or carbon X atoms, so they are not 1 to 20 hydrocarbon groups). an organomagnesium component dissolved in the indicated hydrocarbon solvent and (11) at least! Oka's solid reaction product with a titanium compound containing a halogen atom is expressed as (iii) general formula % formula %) (wherein X is a halogen atom, RIO is a carbon atom number of 1 to 20)
a hydrocarbon group, a is 1 to 4, b is 1 to 3, C
is a number from 1 to 4); and (B) an organoaluminated compound, A method (s) for producing an ethylene polymer according to claim 1 or 2, characterized in that fB is also used as a 4-Kofukuromachi catalyst) (1) General formula A (, MgR'pR'qX'rX2r, D
t (into the formula, ( is an atom in gold/r of Group I to Shimane group of the periodic table, α + pr q + r is 0 or greater than 0, S is greater than 0 and less than or equal to 1, t ( is greater than 0 or O In number, p
+ q + r 10s = mri+2, 0<(r10a
)/(α+1), jt, o, sat as ・1
f, In is the valence of M, and even though R1 and R2 are the same, 'l!
4: A hydrocarbon group with one or more carbon atoms and 1 to 2 carbon atoms. Organomagnesium compounds soluble in hydrocarbon solvents represented by (11) hydrogen chloride, halogenated compounds, boron, aluminum,
(iii) titanium as a reactant selected from silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, lead, cadmium, and aqueous halides; Compound ゛or/and?
A method for producing an ethylene-based polymer according to claim 1 or 2, characterized in that a catalyst comprising a catalyst component [A) formed by contacting a nanoram compound and a metalized compound CB) is used. (6) The ethylene polymer according to claim 1 or 2, wherein a catalyst comprising the following component [A] and right rear metal compound [B] is used as the celebration catalyst. Component [A] A solid catalyst obtained by reacting (4) and (5) in the presence of (3) shown below (1) General formula MaMgR'pX'q -Dr (in the formula M
is a metal atom of Groups 1 to 2 of the periodic table, α+p+q+r
is a number greater than or equal to 0, and I)+q=mα+2,0 and q/(α+
1) It has the relationship of <2, m is the valence of M, R' is one kind or a mixture of two or more kinds of hydrocarbon groups having 1 to 20 carbon atoms, and X' is a hydrogen atom, oxygen, or nitrogen. (2) Organomagnesium compounds represented by one or a mixture of two or more negative groups containing a sulfur atom (D represents an electron-donating organic compound) (2) boron, silicon, germanium, tin, phosphorus,
A mixture of one or more selected antimony, bismuth, zinc halides or hydrogen chloride (a) (1) and (2) solid components (
4) Organo-gold quaternide (5) Any of the following transition metal compounds (a) = (d) (a) titanium compound tl, (b) -nadium compound, (C) titanium compound and ζ-nadium compound, (d
) titanium compound”? and zirconium compound (7) with ribs 1 and 4 as catalysts, (1) general formula NiaMgβR'pR24X'rX"sD
t (in the formula, M is a metal atom of Groups ■ to ■ of the periodic table, α
, p, q. r, s are 0'-'r, a number greater than or equal to 0 β is a number greater than 0, p + q + r + s = mσ + 2β, 0≦(
r+s)/(α+β)≦1.0, m is the valence of M, t is a number larger than 0, and R1, R
2 is a hydrocarbon group having 1 to 20 carbon atoms which may be the same or different, XI and X2 are the same or different groups and represent a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, and D is an electron (11) Hydrogen chloride, organic halogen, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth , zinc, mercury halogenation, of course one or a mixture of two or more selected reactants IC, (iii) a titanium compound or/
Claim 1 or 2, characterized in that a catalyst consisting of a catalyst made by contacting a sodium compound [C, I] and an organometallic compound [B] is used.
Method for producing ethylene polymers described in section