JPS5998107A - Production of ethylenic polymer - Google Patents

Abstract

PURPOSE:To suppress the formation of oligomers and obtain the titled polymer without a deashing step, by (co)polymerizing ethylene under specific conditions in the presence of a Ziegler catalyst, and adding a copolymer, e.g. ethylene and acrylic acid, etc. as a deactivating agent to the resultant polymer mixture to remove the unreacted monomer and solvent. CONSTITUTION:Ethylene or a mixture thereof with a 3-18C alpha-olefin is polymerized or copolymerized in the presence of a Ziegler catalyst containing a transition metallic compound and an organometallic compound in the presence or absence of an inert hydrocarbon solvent under conditions of >=130 deg.C average polymerization temperature, and an ethylenic multicomponent copolymer containing 10-95wt% ethylene content, 0-60wt% (meth)acrylic acid content and 5- 80wt% metallic (meth)acrylate content in a solution or suspension state in an inert hydrocarbon or pure solid or molten state as a deactivating agent is added to the resultant polymer mixture to deactivate the catalyst and separate the unreacted monomers and solvent. Thus, the aimed polymer is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyethylene and ethylene-α-olefin copolymers, and in particular to the inactivation of Ziegler-type catalysts used in the polymerization of ethylene and α-olefins.

Polyethylene and hyethylene to α-olefin copolymer polymerized by Ziegler type catalyst C, usually 0.850
It has a wide density range of ~0.975'i/C1n3, and is used in large quantities in 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. The Ziegler-type catalyst contains transition metal compounds belonging to Groups 1-2 of the periodic table, such as titanium and nonadium compounds, and organometallic compounds such as organoaluminium compounds as main constituents.

Various processes are known for the polymerization of ethylene or ethylene and α-olefin, but the polymerization temperature is 13.
Solution polymerization, which polymerizes at a high temperature of 0°C or higher, and high-temperature, high-pressure polymerization, which does not use a solvent, can polymerize ethylene adiabatically, and unlike slurry polymerization and gas phase polymerization, they are effective in removing the heat of polymerization. It is an excellent energy-saving process as it does not require energy.

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 from which the catalyst has been removed, 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 polymerization.
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 7 It can be reused by simply processing it (by passing it through a tube), and it becomes 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 section, 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 monomer in the reaction chamber 8 after exiting the polymerization vessel, which will polymerize and cause a runaway reaction because the reaction is not controlled. There is a huge risk of this.

When a compound conventionally used to remove old catalysts, such as alcohol, is used as a quenching agent to deactivate the catalyst, alcohol is volatile and may leave the polymer solution together with unreacted substances and solvents. The monomers and solvents are then evaporated, contaminating the monomers and solvents, and 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 arrived at the present invention. Of course, it is a matter of course that the quencher remains in the polymer and must not adversely affect the properties of the polymer, such as electrothermal stability.

That is, the present invention provides ethylene or ethylene and a C3 to C18 α- a mixture of olefins,
Polymerization is carried out at an average polymerization temperature of 130°C or higher, and the resulting polymer mixture is added with an ethylene content of 1 as a deactivator.
Inert carbonization of an ethylene-based multi-component copolymer with a content of 0 to 95% by weight, an acrylic acid or methacrylic acid content of 0 to 60% by weight, and an acrylic acid metal salt or methacrylic acid metal salt content of 5 to 80% by weight. deactivating the catalyst by adding and mixing hydrogen in solution or suspension form, or in pure solid or molten form, in an amount sufficient to deactivate the catalyst; Separating unreacted monomers or unreacted monomers and an inert hydrocarbon solvent from a polymer mixture, and separating a polymer containing the deactivating agent and a reaction product of the deactivating agent and the catalyst. The present invention relates to a method for producing an ethylene polymer, characterized in that:

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

As the transition metal compound, halides of transition metals of groups 1 to 2 are used, such as titanium halides, vanadium halides, and sodium oxyhalides. As the organometallic compound, an organoaluminum compound such as an alkyl aluminum or an alkyl aluminum chloride, or an organoaluminum-magnesium complex such as an alkyl aluminum-magnesium complex or an alkyl alkoxy aluminum-magnesium complex is 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 not react rapidly with the deactivator of the present invention to be inactivated. There must be. An example of a preferred medium used in the present invention that meets these requirements is disclosed in Japanese Patent Application Laid-Open No. 56-474.
09 and JP-A-56-59806, there is a catalyst comprising a solid reaction product obtained by reacting an organomagnesium compound with a titanium compound or a vanadium compound and an organoaluminum compound.

That is, in JP-A-56-47409, (A) (
i) General formula MaMg p R'p R"q X"rX2
s (where M is At, Zn, B.

Be, Li, β is a number greater than or equal to 1, "+f'+Qtr
+8 is a number greater than 0 or O, p+q+r+s
-mα+2β, 0≦(r+s)/(α+β)≦1.0, where m is the valence of M, and B2 is a hydrocarbon having 1 to 20 carbon atoms, which may be the same or different. The groups XI and X2 are the same or different groups, and hydrogen atoms, 0
几3゜os；FL'RsR"lNFl?a'+
8n9su;':rNshowL,"3+"+&"+R
' represents a hydrocarbon group having 1 to 20 carbon atoms, FL4
, R5, B6 are hydrogen atoms or have 1 to 20 carbon atoms
b) in a hydrocarbon solvent denoted by
The organomagnesium component of the solution and the formula (11) T;
o) n-X4-n C where BIO has 1-20 carbon atoms
is a hydrocarbon group, X is norogen, and O≦n≦3], and the titanium compound (ii) is added to the organomagnesium component (1) in a molar ratio of 1.1 to 4. ．．
A catalyst is disclosed that comprises a solid reaction product obtained by reacting with 0 and (B) an octa-aluminum compound.

Moreover, in JP-A-56-59806, (A) (i) General formula MdMg/R1, crosspiece X1rX"
s (where M is At, zn, B.

Be, Li, β is a number greater than or equal to 1, "+P+Q+'+
8 is 0 or a number greater than 0, p + q +
r + s=mα+2β, o<(r+s)/(a+
β) < 1.0, m is the valence of M Bl
, 1 (2 is the number of carbon atoms 1 to 1, which may be the same or different)
20 hydrocarbon groups, Xl and Xl are the same or different groups, hydrogen atoms, 0几3゜08iR'几5R6, N几7B
8. B represents a group R9, R3, R7, R8, R9
represents a hydrocarbon group having 1 to 20 carbon atoms;
(11) titanium containing at least one halogen atom; The solid reaction product with the compound (having the general formula TiXa(OalO)4-a.

VOXb(OR”)3-b and VXc(O几凰')4
-c (in the formula, X is a halogen atom, FLIG has 1 carbon atom
-20 hydrocarbon groups, a is 1-4, b is 1-4
3, C is a number from 1 to 4); and (B) an organoaluminum compound; A catalyst is disclosed.

Another example of a preferable catalyst used in the present invention is
JP-A-56-26905, 28206, 32504
.

45910, 47408, 59805 and JP-A-5
Examples include the catalyst described in 7-16005.

Examples are: (1) General formula MaMgR1, crosspiece X'rX2. Dt (in the formula, M is a metal atom of Group 1 to Group II of the periodic table, α + p + Q
*r is 0 or greater than 0, S is greater than 0 and less than or equal to 1, t is 0 or a number greater than 0, p + q + r + s
= mα+2, O<(r+s)/(α+1)≦1
．． 0. There is a relationship of s≦t, where m is the valence of M, Bl, F
L2 is a hydrocarbon group having 1 to 20 carbon atoms which may be the same or different, XI is a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, Xl is a halogen atom, and D is an electron donating group. An organomagnesium compound soluble in a hydrocarbon solvent represented by (representing an organic compound) and (11
) One or more halides selected from hydrogen chloride, organic halides, boron, aluminum, silicon, dalmanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, cadmium, and mercury halides. (iii) a titanium compound or/and a vanadium compound and an organometallic compound CB).

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

Component [A] Solid catalyst (1) formed by reacting (4) and (5) in the presence of (3) shown below (1) General formula Ma Mg R'pX'q ・D r
(In the formula, M is a metal atom of Groups ■ to ■ of the periodic table, α+
f) +Q+r is a number greater than or equal to 0, and p + q = mα+
2,0≦q/(a+t)<2, m is the valence of M, B/ is one type or a mixture of two or more hydrocarbon groups having 1 to 20 carbon atoms, and X' is Organomagnesium compound (2) represented by one or a mixture of two or more negative groups containing a hydrogen atom or an oxygen, nitrogen or sulfur atom, D represents an electron-donating organic compound (2) boron, silicon, germanium, A mixture of one or more selected from tin, phosphorus, antimony, bismuth, zinc chloride or hydrogen chloride (3) The solid component obtained by the reaction of (1) and (2) (
4) Organometallic compound (5) Any of the following transition metal compounds (,) to (d) (a) titanium compound, (b) vanadium compound, (C)
Other examples of titanium compounds and vanadium compounds, (d) titanium compounds and zirconium compounds are (1) general formula MaM gβFLl, a2qxirxl,
D t (In the formula, M is a metal atom of Group Ⅰ to Group M of the periodic table, α + p + (1 + r, S is 0 or a number of 0 or more, β is O
A dog number, p + q + r+s = mα+
2βlO≦(r+8)/(”+β)≦1.0, m is the valence of (, t is 0 or a number larger than 0, and 1 and fL2 may be the same or different. a hydrocarbon group having 1 to 20 carbon atoms; Organomagnesium compounds soluble in the indicated hydrocarbon solvents and (11) halogens of hydrogen chloride, organohalides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, cadmium, and mercury. (iii) a titanium compound or/and a nonadium compound, and an organometallic compound [B]. It is a catalyst.

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

The polymerization method used in the present invention is carried out outside the yarn at a high temperature of 130°C or higher, typically at a polymerization temperature of 130 to 300°C in the presence of an inert hydrocarbon solvent. A solution polymerization method in which ethylene or a mixture of ethylene and a-olefin is polymerized at a polymerization pressure of ~SOO atmosphere,
By supplying a Ziegler type catalyst instead of a radical catalyst to a conventional low-density ethylene plant for radical polymerization, ethylene or a mixture of ethylene and α-olefin can be
There is a high-temperature, high-pressure polymerization method in which polymerization is performed at a polymerization temperature of 30 to 300°C and a polymerization pressure of 500 to 3000 atm.

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.

A specific example of the solution polymerization method is 0. T, B15to
Canadian Patent No. 98049 dated December 28, 1975
There is a process described in No. 8.

High temperature and high pressure polymerization methods include the autoclave method using an autoclave reactor, the tubular method using a tubular reactor, or the autoclave and tubular method.
It includes various multi-stage polymerization methods in which reactors are combined for polymerization. As an example of high temperature and high pressure polymerization method, BP932,231
．． IIPI, 205,635. , USPl, 161.
737 etc. can be opened.

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 quenching agent and the reaction mixture may be mixed either before or after the pressure reducing valve between the polymerization vessel and the polymer 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 metal compound and the organometallic compound. However, preferably the amount of deactivator used is sufficient to react with both catalyst components.

The amount of the ethylene-based multicomponent copolymer that is the deactivator used in the present invention is such that the number of carboxylic acid groups or carboxylic acid metal bases is 0.4 to 20 times the total number of molecules of the transition metal compound and the organometallic compound. It must contain If it is less than 0.4 times, the deactivation will not be sufficient, and if it is more than 20 times, the density of the ethylene polymer will be reduced and a large amount of deactivating agent will be used, which is not economical.

The ethylene-based multicomponent copolymer used in the present invention includes ethylene content of 10 to 95 layers, acrylic acid or methacrylic acid content of 0 to 60% by weight, acrylic acid metal salt or methacrylic acid gold rice. It is a binary or ternary copolymer with a salt content of 5 to 80% by weight. The metals used for acrylic acid metal salts or methacrylic acid metal salts include metals from Groups ■ to ■ of the periodic table, such as lithium, sodium, potassium, calcium, magnesium, ζlium, and zinc. be. The ethylene-based multi-component copolymer of the present invention is known as an ionomer, and is usually produced by copolymerizing ethylene and acrylic acid or methacrylic acid by high-pressure radical polymerization, and metal hydroxylating the carboxylic acid groups of the resulting copolymer. Manufactured by reacting with substances and neutralizing them. In order to obtain an ethylene-based multicomponent copolymer without free carboxylic acid groups, a method of directly copolymerizing ethylene with sodium acrylate or sodium methacrylate can also be adopted.

Specific examples of the ethylene-based multicomponent copolymer of the present invention include ethylene/sodium methacrylate copolymer, ethylene/sodium methacrylate copolymer, and ethylene/sodium methacrylate copolymer.
Methacrylic acid/sodium methacrylate copolymer, ethylene/potassium methacrylate copolymer, ethylene/methacrylic acid/potassium methacrylate copolymer, ethylene/potassium methacrylate copolymer,
Methacrylic acid/magnesium methacrylate copolymer, ethylene/methacrylic acid/calcium methacrylate copolymer, ethylene/methacrylic acid/zinc methacrylate copolymer, ethylene/sodium acrylate copolymer, ethylene/acrylic acid/acrylic acid Sodium copolymer, ethylene/potassium acrylate copolymer, ethylene/acrylic acid/potassium acrylate copolymer, ethylene/acrylic acid/calcium acrylate copolymer, ethylene/acrylic acid/zinc acrylate copolymer, etc. can be mentioned.

Preferably, the content (number of moles) of the metal salt of acrylic acid or methacrylic acid in the ethylene-based multi-component copolymer of the present invention is 0.5 of the content (number of moles) of acrylic acid or methacrylic acid. That's more than double that.

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 monomers or inert hydrocarbon solvent and the polymer are separated. 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. Additives such as an antioxidant and, if necessary, a catalyst neutralizer and a lubricant are added to the obtained polymer, and the polymer is finally pelletized using an extruder.

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

This prevents uncontrolled runaway polymerization of unreacted upper polymers in the polymer separator, and also suppresses the formation of low molecular weight polymers (wax, grease, etc.) due to post-polymerization. (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. (3) The monomers and inert hydrocarbon solvent recovered from the reaction mixture can be recycled and used without a purification step or by passing them through a simple purification step.

(4) The deactivator remaining in the polymer or the reaction product of the deactivator 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,
Materials commonly added to polyolefins such as pigments, inorganic or organic fillers, rubbers and other small amounts of polymers can be added.

Examples of these additives include BHT, Shell Ionox 330, Gridlich Goodlite 3114, and Chino Geigy Illanox 101.
0.1076 Tinuvin 327, L8770 manufactured by Sankyo Pharmaceutical Co., Ltd.
・.

LS622. DMTP, DLTP, calcium stearate, hydrotalcite, basic magnesium carbonate,
Erucic acid amide, oleic acid amide, titanium white,
Calcium carbonate, carbon black, talc, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, high-pressure polyethylene, ethylene-zoropylene rubber polypropylene, etc. are available.

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 t of 0.5 mo 1μ hexane solution and 1.2 t of hexane were charged.
The temperature was raised to 0°C. Next, Ato-tsMg(n-Bu)1
．． ys(On Bu)o,y (metal concentration 0.9 m
ol/l octane solution) 0.451 and hex"j:
10.35 t was introduced over 1 hour at 70°C.

Further, 0.6 t of hexane containing TiO40,79- was introduced and the reaction was carried out at 70°C for 1 hour. The generated inert solid is used as a catalyst. The titanium (Ti) content in catalyst A was measured and found to be 0.5% by weight.

In addition, A/-o, tsMg(n Bu)x, ys(On
Bu) o, 7o was manufactured in JP-A-57-. According to No. 5709.

(Synthesis of solid catalyst B) In the same manner as A, Ato)6Mg(nBu)1.7s(
Synthesis was carried out using 7,400 mmol of On Bu)o, 400 mmol of trichlorosilane, 8.8 mmol of vanadyl trichloride, and 12 mmol of titanium tetrachloride. The total content of Nadium (V) and Titanium (Ti) in Catalyst B was 2.0%.

(Synthesis of solid catalyst C) Oxygen and moisture inside a 500 d flask equipped with two dropping funnels were removed by dry nitrogen substitution, and 1
60 d of hexane was added and the mixture was cooled to -1θ°C. Next, At
Mgsog(n 04H9)+4.5(On 04H9
) 80 ml of heptane solution containing 40 mmol as the total organomagnesium component of the organomagnesium/aluminum compound having the composition O-4 and 80 d of hexane solution containing 60 mmol of n-butoxytitanium trichloride.
was weighed into each dropping funnel, and both components were simultaneously added dropwise over 1 hour while stirring at -10°C, and the mixture was further aged and reacted at this temperature for 3 hours. The resulting hydrocarbon-insoluble solid was isolated, washed with n-hexane, and dried to yield 11.2 i of solid product. The Ti content was 21% by weight. Note that AtMg5. s(n 04H9)14.5・(O
n O4Hg ) (1,4 was synthesized according to Example 1 of JP-A-56-47409.

(Synthesis of solid catalyst) AtMg3(OzHs)t,s (n04Hg)6(O
8iH-OH3・02H6) A heptane solution containing 40 mmol of an organomagnesium aluminum compound having a composition of 1-s as an organomagnesium component 80
Weigh out 8 o- of a heptane solution containing 40 mmol of titanium tetrachloride and 40 mmol of titanium tetrachloride into each dropping funnel, and add both components to a 500 ml nitrogen-purged flask containing 160 m/h of hexane at 0°C with stirring. At the same time, it was added dropwise over 1 hour, and the mixture was further aged at this temperature for 3 hours. The product was filtered and washed with heptane to obtain a solid product. Subsequently, 100 octane slurry containing this solid reaction product
+d composition Tl043.5(On 04Hg)6.5
300 mmol of titanium compound was added thereto, and the mixture was reacted at 130°C for 3 hours to obtain 12.2% solid catalyst CD). The Ti content was 19.8% by weight. The above organomagnesium/aluminum compound is disclosed in JP-A-56-598.
Synthesized according to Example 06.

Table 1 shows the performance of the quenchers used in the examples.

Examples 1 to 7, Comparative Examples 1 to 4 A cyclohexane solution of triethylminiram at a concentration of 0.1 mmol/l and solid catalyst A at 1.0 f/Hr was added to a polymerization vessel with a stirrer having a capacity of ioot. 2001/H
r.

(triethylaluminum 20 mmol/Hr), ethylene at 25 Kf/Hr, and hydrogen at I K9/Hr, respectively, at a polymerization temperature of 20oC and a pressure of 80K.
Polymerization was carried out at y/cm. The polymerization conversion rate of ethylene is approximately 8
The amount of polyethylene produced was approximately 20 to 9/Hr.

The quencher was made into 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"C using a heat exchanger, and then lowered to a pressure of 11 Ky/cm2 using a stainless steel Knee Le Parzot.
This was introduced into the 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 of the separator. After the polymer slurry is separated into polymer and cyclohexane using a centrifuge,
It was fed into a vented extruder and pelletized. The obtained pellets were pulverized and vacuum dried to completely remove volatile components, and then the basic properties of the polymer were measured.

Furthermore, once the polymerization has started and the polymerization has stabilized, continuous circulation of the ethylene and cyclohexane recovered from the separator and centrifugal separator to be used for precious polymerization without distillation purification is started, and this is continued for 4 hours. I went to To compensate for the insufficient amount of recovered ethylene and cyclohexane, we made up the necessary amount of fresh ethylene and cyclohexane.

Productivity (polymer production amount (y) per 11 solid catalysts) of solid catalyst A was measured when the polymerization was stabilized after the start of polymerization and 4 hours thereafter.

This makes it possible to determine how much the deactivator adversely affects the cyclic use of ethylene and cyclohexane.

In addition, the density of the polyethylene was measured when the polymerization was stable and after 4 hours. When zothene-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. Table 1 shows the test results for 7Maki's quencher.

As is clear from the results in Table 2, when no deactivator is used (Comparative Example 1), the amount of low polymer produced increases, the molecular weight distribution (MW/MN) becomes broader, and 4 hours after the start of polymerization. The subsequent productivity and density decreased.

Also, when methanol is used as a deactivator (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 ethylene-based multi-component copolymer of the present invention is used as a deactivator (Examples 1 to 7), a polymer with a sharp molecular weight distribution and good color can be obtained, and unreacted ethylene and solvent cyclohexane can be recycled. Even after this, no decrease in density or productivity was observed. Moreover, when the amount of quencher is small (Comparative Example 3), the molecular weight distribution becomes wide, and when the amount of quencher is large (Comparative Example 4), the density of the resin decreases.

Example 8 1.3'? /Hr, 9 degrees 0.1 mmol/
L cyclohexane solution of triethylaluminum 200L/Hr () 20 mm of ethylaluminum
ol/Hr), ethylene at 20 KP/H, and 1-butene-1 at 10 K5J/Hr, respectively, and polymerization was carried out at a polymerization temperature of 200°C and a pressure of s OKt/cm2. Ethylene polymerization conversion rate u approximately 85%, ethylene-
The amount of butene-1 copolymer produced was about 18 K9/Hr. The polymerized reaction mixture was treated in the same manner as in Example 1. The results obtained are shown in Table 3.

Example 9 Ethylene-
An octene-1 copolymer was obtained. The results obtained are shown in Table 3.

Example 10 Polyethylene was obtained by polymerization in the same manner as in Example 1 except that solid catalyst B was used instead of solid catalyst A. The results obtained are shown in Table 3.

Example 11 An ethylene-butene-1 copolymer was obtained by polymerization in the same manner as in Example 8 except that solid catalyst C was used instead of the solid catalyst. The results obtained are shown in Table 3.

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 3.

Example 13 Ethylene polymerization was carried out using an autoclave with an internal volume of 2 tons and equipped with a stirrer. Polymerization pressure 1, 200 Ky/cm
2. At a reaction temperature of 220°C, 40 Kg/H of ethylene
r, the solid catalyst (A) was supplied to the reactor at a supply rate of 0.15 ff/Hr, and triethylaluminum was supplied to the reactor at a supply rate of 3.0 mmol and 17 Hr. The amount of polyethylene produced was a,s Ky/Hr. The quencher has an average boiling point of 1
The reaction mixture was added continuously after it left the polymerization vessel in the form of a liquid mixed in mineral oil at 50°C. The deactivated reaction mixture was introduced into a separation system in which a medium pressure separator maintained at 250 Ky/c1n2 and a low pressure separator maintained at 10 P were connected in series to separate unreacted ethylene and polymer.

Table 3 shows the properties of the polyethylene obtained during stable polymerization and after 4 hours of circulating unreacted ethylene.

Comparative Example 5 Polyethylene was obtained in the same manner as in Example 13 except that no deactivator was used. The properties of the obtained polyethylene are shown in Part 3.

Example 14 Pressure LOO using a tubular reactor with an inner diameter of 5 mm and a length of 40 m
OKy/cm2, temperature 260℃.

Ethylene 16K9/H, butene 124Ky/H
r.

Solid catalyst CB] was fed to the reactor at a feed rate of 0.15 f/Hr 1) ethylaluminum 3 + Ommo I/Hr, respectively. The polyethylene production pattern was 3.5 K9/14r. The steps after addition of the deactivator were performed in the same manner as in Example 13. The results obtained are shown in Table 3.

The α taste of gFF used in the Examples is as follows.

(1) MI: represents the Tort index,
Measurements were made in accordance with A8TMD-1238 under conditions of temperature 190°C and load 2.16.

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

(3) MW/MN + '7 Oakes GPO-
Measured at 1500.

(4) Percentage of molecular weight 5,000 or less: Waters G
Measured with PO-1500.

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

] Table 1 Name of deactivator Structure of copolymer Melt index 2 () Composition (mol%) A Ethylene/methacrylic acid/methacrylic acid 5.0 (92 inches) (4 cups)
(Touge) B Ethylene/methacrylate 4t/sodium methacrylate 5.2 (95t) (3.2%)
(1,8th)C ethylene sodium methacrylate 4.3(91th) (
9%) D Ethylene/methacrylic acid/zinc methacrylate
3.5 (92 inches) (4%) (4%) E Ethylene/methacrylate 4/methacrylic acid dredged calcium 3.0 (92 inches) (4th section)
(4%) F Ethylene/acrylic acid/sodium acrylate 5.0 (92%) (4%)
(4%) Fumiko J.1'1n1 Co. Procedural amendment (voluntary) October 7, 1980 Director-General of the Patent Office Kazuo Wakasugi 1, Indication of case Patent application No. 207762 of 1988
No. 2 Name of the invention Process for producing an ethylene polymer a Relationship with the case of the person making the amendment Patent applicant 1-2-6 Tun Dojima, Kita-ku, Osaka-shi, Osaka Prefecture "Scope of Claims" of the specification to be amended and “detailed description of the invention”
Translation 5, Contents of amendment (1) The scope of claims in the specification is amended as shown in the attached sheet.

(2) The detailed description of the invention column in the specification is amended as follows.

(3) Specification page 39, Section 3, Section 8, Productivity section [5, oooJ respectively [4, o OOJ
I am corrected.

Claims (1) In the presence or absence of an inert hydrocarbon solvent, using a coordination polymerization catalyst containing a transition metal compound and an organometallic compound, ethylene or ethylene with a carbon number of 3 to 1
A mixture of 8 α-olefins was prepared at an average polymerization temperature of 130°C.
Polymerization is carried out under the above conditions, and the obtained polymer mixture has an ethylene content of 10 to 95% by weight and an acrylic acid or methacrylic acid content of 0 to 60% by weight as a deactivator.
, content of acrylic acid metal salt or methacrylic acid metal salt 5
~80% by weight of ethylene-based multi-component copolymer with 5r%'1
1 (1” J-) to inactivate the catalyst;
Method for producing an ethylene polymer (2) characterized by separating unreacted monomers from the obtained polymer mixture
A patent characterized in that the total number of carboxylic acid groups and carboxylic acid metal bases in the added deactivator is in the range of 0.4 to 20 times the total number of molecules of the transition compound and the organometallic compound. Method for producing an ethylene polymer according to claim 1 (3) As a coordination polymerization catalyst (A) (1) General formula M4MgβR'pR2qX"r
X2s (where M &'l kl.

Zn, B, Be, Li, β is a number of 1 or more, ” +
p * q * r, s is O or a number larger than O, p ten (10 r ten s = ma + 2 β, o = Cr ten g
) / (a + β), g l, Q, m is M O) valence, R1 and R2 are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, xi
, xt are the same or different groups, hydrogen atom, OR''
, O8i R4R5R6, NR'R', SR", R3HR7+R5, BQ has 1 to 1 carbon atoms
20 hydrocarbon groups, and R4, R5, and R6 are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms); Ti(OR10)n-X4-n [in the formula R
10 is a hydrocarbon group having 1 to 20 carbon atoms, and X&'
i) ~logen, 04n43] titanium compound,
It is preferable to use a catalyst consisting of a solid reaction product obtained by reacting the organomagnesium component of (1) with a titanium compound at a molar ratio of 1.1 to 4.0 and an organoaluminum compound. A method for producing an ethylene polymer according to claim 1 or 2 (4) tAl tl as a coordination polymerization catalyst) General formula MaMgβR'pR2qX'r
X2s (where M is Al.

Zn, B, Be, Li, β is a number of 1 or more, (
'+p+q+r, s is O or a number larger than O,
p+q±r 10g=ma +2β, 0<, (r10g)/
(a + β) qt, o, where m is the valence of M, R1 and R2 may be the same or different (-hydrocarbon group having 1 to zO carbon atoms, xi and x2 are the same) or a different group, hydrogen atom, 0R310Si R4R5R6
, NR7R', SR", and R31R71R
8. BQ is a hydrocarbon group having 1 to 20 carbon atoms, and R4, R5, and RO are hydrogen atoms or 1 to 2 carbon atoms.
A solid reaction product of an organomagnesium component soluble in a hydrocarbon solvent represented by (0 hydrocarbon groups) and (1) a titanium compound containing at least one halogen atom, (m) General formula % formula %) (In the formula, X is a halogen atom, RIO has 1 to 20 carbon atoms.
hydrocarbon group, a is 1-4, b is 1-3, C
is a number from 1 to 4); and (B) an organoaluminum compound. (5) As a coordination polymerization catalyst, (1) General formula MaMgR'pR''qX'rX2sDt
(In the formula, M is a metal atom of Group 1 to Group II of the periodic table, α,
plq, r is 0 or greater than 0, 8 is greater than O and less than or equal to 1, t is a number greater than 0 or O, p±q 10r 10a
=mα+2.0<(r×B)/(cl+1)41
．． 0, s≦t, m is the valence of M, R''
, R2 has 1 to 2 carbon atoms, which may be the same or different
0 hydrocarbon, Xl represents a hydrogen atom or a negative group containing oxygen, crab, or sulfur atom, X2 represents a halogen atom, and D represents an electron-donating organic compound) organomagnesium compounds and (
1υ Hydrogen chloride, organic halides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, cadmium, mercury) or a mixture of two or more selected from halogenides. ,
(iii) a titanium compound or/and a vanadium compound, or a catalyst consisting of a medium component [A) and an organometallic compound [B] is used. A method for producing an ethylene polymer according to item 1 or 2 (6) Claims characterized in that a catalyst consisting of the following components [A) and an organometallic compound [B] is used as a coordination polymerization catalyst. Component [A] Solid catalyst obtained by reacting (4) and (5) in the presence of (3) shown below (1) General formula: MaMgR' p X'q −D r
(In the formula, M is a metal atom of Groups ■ to Group ■ of the synchronous table, ar
p + q + r is a number greater than or equal to 0, and p 10q = m
α+2.0! has the relationship q/(α+1)<2, and m is M
valence, K is 1 of a hydrocarbon group having 1 to 20 carbon atoms
X is a hydrogen atom or a mixture of one or more negative groups containing oxygen, nitrogen or sulfur atoms; D is an electron-donating organic compound) Compound (2) A mixture of one or more selected from boron, silicon, germanium, tin, phosphorus, antimony, bismuth, zinc halide or hydrogen chloride (3) By reaction of (1) and (2) Solid component (
4) Organometallic compound (5) Any of the following transition metal compounds (a) to (d) (a) titanium compound, (b) vanadium compound, IC)
Titanium compound and vanadium compound, (d) F-tan compound and zirconium compound '11 (7) As a coordination polymerization catalyst,

Claims (1)

Scope of Claims: (1) In the presence or absence of an inert hydrocarbon solvent, using a Ziegler type catalyst containing a transition metal compound and an organometallic compound, ethylene or ethylene and α of 3 to 18 carbon atoms are combined. - A mixture of olefins is prepared at an average polymerization temperature of 13
Polymerization is carried out at a temperature of 0°C or higher, and the resulting polymer mixture is added with an ethylene content of 10 to 95% by weight as a deactivator.
, acrylic acid or methacrylic acid content 0-60
An ethylene-based multi-component copolymer containing 5 to 80% by weight of metal acrylate or metal methacrylate in a solution or suspension state of an inert hydrocarbon, or in a pure solid or molten state. Inactivating the catalyst by adding and mixing a sufficient amount to inactivate the catalyst, and removing unreacted monomers or unreacted monomers and an inert hydrocarbon solvent from the resulting polymer mixture. (2) A method for producing an ethylene polymer characterized by separating the deactivating agent and a polymer containing the reaction product of the deactivating agent and the catalyst (2) in which the deactivating agent is added. Claim 1, wherein the total number of carboxylic acid groups and carbo/sheet metal bases is in the range of 0.4 to 20 times the total number of molecules of the transition metal compound and the organometallic compound. Manufacturing method of the ethylene polymer described (3) As a Ziegler type catalyst (A) (i) General formula MaMg/R'pR2qX'r
X''++ (in the formula, M is At, Zn. B, Be, Li, β is a number of 1 or more, α + I' + q
+r+@ is 0 or a number larger than 0, and l' +
Q + r + s=mα+2β, 0≦(r+a)/(
α+β)≦1,0, m is the valence of M, R'
, R2 has 1 to 2 carbon atoms, which may be the same or different
0 hydrocarbon group, Xi. X2 is the same or different group, hydrogen atom, 0 几3゜08
iR' reactor R6, N-7R8, a total of 9 groups, and R3.
7. 8. R9 represents a hydrocarbon group having 1 to 20 carbon atoms;几5. 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms); an organomagnesium component soluble in a hydrocarbon solvent represented by formula (11) T
i (ORIO) ((・X4-nC In the formula, BIO is a hydrocarbon group having 1 to 20 carbon atoms, and X is]・Rogon,
0≦1≦3] with a solid reaction product obtained by reacting the titanium compound of (11) with the organomagnesium component of (i) at a molar ratio of 1.1 to 4.0. (B) A method for producing an ethylene polymer according to claims 1 or 2, characterized in that a catalyst comprising an i-organic aluminum compound is used (4) As a Ziegler type catalyst (A) (D General Formula Ma MgβR'p %XI,X
', (in the formula, M is At, Zn + B, Be, Li, β is a number of 1 or more, " + I) + ', + '
+ S is 0 or a number greater than 0, p + q
+ r + s=mα+2β, O<(r+s)/
(a+β)<1.0, m is the valence of M, and approximately 1. B2 has 1 or more carbon atoms, which may be the same or different;
20 hydrocarbon groups, Xi. X' is the same or different group, hydrogen atom, OR3゜08
iR'R'R6,NruaR11,8ru9, ft3, B? , l also has 8 and 9 carbon atoms from 1 to
20 hydrocarbon groups, 几4.几5. R6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms); and (11) at least one 7-rogen atom. The titanium compound tono solid reaction product containing the solid reaction product (iii) has the general formula 1'1Xa (OR") 4-, I TVOXb (ORI
O) 3-b and '/X c (OR10) 4- c
(In the formula, X is /・rogen atom, FLIO has 1 to 1 carbon atoms
20 hydrocarbon groups, a is 1-4, b is 1-3
, C is a number from 1 to 4); and (B) an organoaluminum compound. (5) As the Ziegler catalyst, (1) the general formula MaMga'pR2QX' (X2sDt
(In the formula, M is a metal atom of Groups ■ to ■ of the periodic table, α + p
+q+r is 0 or more than 0, S is greater than 0 and less than 1,
Electricity is 0 or a number greater than 0, p + q + r +
s = mα+2, 0<(r+s)/(α+1)≦
1.0. has the relationship s≦t, m is the valence of M, FLl
, B2 has 1 to 2 carbon atoms, which may be the same or different
0 hydrocarbon, Xi represents a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, X' represents a halogen atom, D represents an electron-donating organic compound) Soluble in a hydrocarbon solvent organomagnesium compounds and (
11) Hydrogen chloride, organic halides, boron, aluminum, silicon, germanium, soot, lead, phosphorus, arsenic,
one or more admixtures selected from antimony, bismuth, zinc, cadmium, and mercury halides;
Claim 1, characterized in that a catalyst consisting of a catalyst component [CA'l] formed by contacting the reactant with (iii) a titanium compound or/and a vanadium compound] and an organometallic compound [B] is used. Process for producing an ethylene polymer according to claims 1 to 2 (6), characterized in that a catalyst comprising the following component [A] and an organometallic compound CB) is used as the Ziegler catalyst. Component CA) A solid catalyst obtained by reacting (4) and (5) in the presence of (3) shown below (1) General formula Md M g a7X'q・Dr (M in the formula
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=ma+2. O≦q/(α+1
)<2, 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 or oxygen, nitrogen or Organomagnesium compound (2) boron, silicon, germanium, tin, phosphorus, antimony , bismuth, zinc halide, or a mixture of two or more selected from hydrogen chloride (3) A solid component resulting from the reaction of (1) and (2) (
4) Organometallic compound (5) Any of the following transition metal compounds (a) to (d) (a) titanium compound, (b) nonadium compound, (C
) titanium compound and vanadium compound, (d) titanium compound and zirconium compound (7) As a Ziegler catalyst, (1) General formula MaMgβR', Hanawa X1rX2sDt (
In the formula, M is a metal atom from Group 1 to Group 1 of the periodic table, αII)
IQl'15 is 0 or a number β greater than 0, p+ Q 10r + s=mα+2β, O≦(r+
s ) / (a + β) ≦ 1.0, m is M
valence, t is 0 or a number larger than 0, 几l,
几2 is a hydrocarbon solvent Xi having 1 to 20 carbon atoms which may be the same or different, X2 is the same or different group and represents a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, and D is an electron representing a donating organic compound) and an organomagnesium compound soluble in a hydrocarbon solvent represented by U*)S = hydrogen hydride, organic halide, boron,
(iii) a titanium compound or /
and a catalyst component made by contacting a nonadium compound [
A method for producing an ethylene polymer according to claim 1 or 2, characterized in that a catalyst comprising A) and an organometallic compound [B] is used.