JPS621645B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyethylene and an ethylene-α-olefin copolymer, and particularly to inactivation of a coordination polymerization catalyst used in the polymerization of ethylene and α-olefins. Polyethylene and ethylene-α-olefin copolymers polymerized using coordination polymerization catalysts are usually
It has a wide density range of 0.850 to 0.975g/ ^cm3 ,
For example, they are used in large quantities in a wide variety of applications, such as films, blow molded products, fibers, and extrusion molded products. Coordination polymerization catalysts are known as catalysts for polymerizing ethylene or a mixture of ethylene and α-olefin. The coordination polymerization catalyst contains as main constituents a transition metal compound belonging to group - of the periodic table, such as titanium and vanadium compounds, and an organometallic compound such as an organoaluminum compound. Various processes are known for the polymerization of ethylene or mixtures of ethylene and α-olefins, but the solvent polymerization method that polymerizes at a high polymerization temperature of 130°C or higher and the high-temperature high-pressure polymerization method that does not use a solvent are known.
It is an excellent energy-saving process because it is possible to polymerize ethylene adiabatically and, unlike slurry polymerization and gas phase polymerization, no energy is required to remove the polymerization heat. In recent years, highly active coordination polymerization catalysts have been developed, and the amount of catalyst residue in the polymer is extremely small, without the need to extract or neutralize the catalyst residue in the polymer with alcohol or caustic soda, and the color and color of the polymer can be improved. The thermal stability of this polymer is similar to that of conventional polymers from which the catalyst has been removed. If there is a catalyst removal process, the recovered polymerization solvent and unreacted monomers are in contact with polar compounds such as alcohol, so it is impossible to use them as is for polymerization, and it is necessary to separate these polar compounds in the purification process. There is. On the other hand, when a highly active catalyst is used, since polar compounds such as alcohols are not used, some or all of the polymerization solvent and unreacted monomers are not purified at all, or only a very simple purification process (for example, molecular It can be reused simply by processing it (by passing it through a sieve), 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 results in the formation of undesirable low molecular weight oligomers, waxes, greases, etc., since the polymerization temperature is generally higher than the average temperature within the polymerization vessel. Oligomers such as butene-1 and hexene-1 cause a decrease in density during the production of ethylene homopolymer. In addition, in the high temperature and high pressure method, the polymerization conversion rate of ethylene is
If the catalyst is not inactivated, there will be a large amount of unreacted monomer in the reaction polymer that exits the polymerization vessel, which will polymerize and cause a runaway reaction because the reaction is not controlled. There is a huge risk of this happening. 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 developed a deactivation method that is not volatile itself, does not produce volatile reaction products that adversely affect the polymerization system even after reacting with the catalyst, and does not cause the risk of contaminating recovered monomers or solvents. Regarding the development of the agent,
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 relates to ethylene or ethylene and an α-olefin having 3 to 18 carbon atoms using a coordination polymerization catalyst containing a transition metal compound and an organometallic compound in the presence or absence of an inert hydrocarbon solvent. polymerizing the mixture at an average polymerization temperature of 130°C or higher, the resulting polymer mixture
As a deactivator, a copolymer of ethylene and methacrylic esters or a terpolymer of ethylene, methacrylic esters and acrylic esters is used in the form of a solution or suspension in an inert hydrocarbon. The presence of unreacted monomers or unreacted monomers and an inert hydrocarbon solvent is determined from the resulting polymer mixture. A method for producing an ethylene polymer, which comprises separating the solvent from the subpolymerization to obtain a polymer containing the deactivating agent and a reaction product of the deactivating agent and the catalyst. This is related. The coordination polymerization catalyst used in the present invention contains a transition metal compound and an organometallic compound as main components. As the transition metal compound, use is made of transition metal halides of groups 1 to 3, such as titanium halides, vanadium halides, vanadium oxyhalides, and the like. 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 coordination polymerization catalyst used in the present invention must have sufficiently high activity that it does not require removal of the catalyst, and must not rapidly react with the deactivating agent of the present invention to be inactivated. There must be. Examples of preferred catalysts used in the present invention that meet these requirements include JP-A-56-47409 and JP-A-56-59806.
There is a catalyst consisting of a solid reaction product obtained by reacting an organomagnesium compound shown in the following with a titanium compound or a vanadium compound, and an organoaluminum compound. That is, in JP-A-56-47409, (A) (i) General formula MαMgβR ¹ _p R ² _q X ¹ _r X ² _s (where M is
Al, Zn, B, Be, Li, β is a number greater than or equal to 1, α, p, q, r, s are 0 or a number greater than 0, p+q+r+s=mα+2β,0
≦(r+s)/(α+β)≦1.0,
m is the valence of M, R ¹ and R ² are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different;
X ¹ and X ² are the same or different groups, hydrogen atom,
OR ³ , OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ groups, R ³ , R ⁷ , R ⁸ , R ⁹ represent hydrocarbon groups having 1 to 20 carbon atoms, R ⁴ , (R ⁵ , R ⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms); an organomagnesium component soluble in a hydrocarbon solvent; and (ii) a formula Ti (OR ¹⁰ ) _o・X _{4 -o} [In the formula, R ¹⁰ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and 0≦n≦3] is added to the organomagnesium component (i) in (ii) A catalyst comprising a solid reaction product obtained by reacting titanium compounds (B) at a molar ratio of 1.1 to 4.0 and (B) an organoaluminum compound is disclosed. Moreover, in JP-A-56-59806, (A) (i) General formula MαMgβR ¹ _p R ² _q X ¹ _r X ² _s (where M is
Al, Zn, B, Be, Li, β is a number greater than or equal to 1, α, p, q, r, s are 0 or a number greater than 0, p+q+r+s=mα+2β,0
(r+s)/(α+β) 1.0, m is the valence of M, R ¹ and R ² are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different, X ¹ and X ² is the same or different group and represents a hydrogen atom, OR ³ , OSiR ⁴ R ⁵ R ⁶ , NR ⁷ R ⁸ , SR ⁹ group, and R ³ , R ⁷ , R ⁸ , R ⁹ have 1 to 1 carbon atoms. 20 hydrocarbon groups, R ⁴ , R ⁵ , and R ⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), an organomagnesium component soluble in a hydrocarbon solvent; ) a solid reaction product with a titanium compound containing at least one halogen atom, (iii) a solid reaction product with the general formula TiXa (OR ¹⁰ ) _4-a , VOXb
(OR ¹⁰ ) _3-b and VXc (OR ¹⁰ ) _4-c (in the formula, X represents a halogen atom, R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, a represents 1 to 4, and b represents 1 to 3, c
is a number from 1 to 4); and (B) an organoaluminum compound. has been done. Other examples of preferable catalysts used in the present invention include JP-A-56-26905, 28206, 32504,
45910, 47408, 59805 and the catalysts described in JP-A-57-16005. An example _is (i) ^the general formula M〓M _g R ¹ _{p R} ² _{q X} ¹ _r
r is 0 or more than 0, s is greater than 0 and less than 1,
t is 0 or a number larger than 0, p+q+r+s=
mα+2,0<(r+s)/(α+1)≦1.0,s
≦t, m is the valence of M, R ¹ and R ² are hydrocarbon groups having 1 to 20 carbon atoms which may be the same or different, and X ¹ is a hydrogen atom, oxygen, nitrogen or sulfur atom. ( ^X2 is a halogen atom, D is an electron-donating organic compound) which is soluble in a hydrocarbon solvent, and (ii) hydrogen chloride, an organic halide, boron. (iii) a titanium compound; or/and a catalyst comprising a catalyst component [A] and an organometallic compound [B] in contact with a vanadium compound. Another example is a catalyst consisting of the following component [A] and organometallic compound [B]. Component [A] Solid catalyst made by reacting (4) and (5) in the presence of (3) shown below (1) General formula M〓MgR' _p X' _q・D _r (where M is a periodic law Table group to group metal atoms, α, p, q, r
is a number greater than or equal to 0, p+q=mα+2, 0≦q/
It has the relationship (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; mixture, D represents an electron-donating organic compound) (2) One or two selected from halides of boron, silicon, germanium, tin, phosphorus, antimony, bismuth, zinc, or hydrogen chloride
Mixture of more than one species (3) 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) Vanadium compound, (c) Titanium compound and vanadium compound, (d) Titanium compound and zirconium compound Another example is (i) General formula M〓MgβR ¹ _p R ² _q X ¹ _r X ² _s D _t (Formula M in the middle is a metal atom from group to group of the periodic table, α, p,
q, r, s are 0 or a number greater than 0, β is a number greater than 0, p+q+r+s=mα+2β, 0≦
(r+s)/(α+β)≦1.0, m is the valence of M, t is 0 or a number larger than 0, and R ¹ and R ² have a carbon atom number of 1 to 1, which may be the same or different. 20 hydrocarbon groups, X ¹ and X ² are the same or different groups and represent a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, D represents an electron-donating organic compound) Organomagnesium compounds soluble in hydrogen solvents and (ii) hydrogen chloride, organic halides, boron, aluminum,
silicon, germanium, tin, lead, phosphorus, arsenic,
Catalyst component [A] formed by contacting a reactant of one or a mixture of two or more selected from antimony, bismuth, zinc, cadmium, and mercury halides with (iii) a titanium compound or/and a vanadium compound. and a catalyst consisting of an organometallic compound [B]. As the α-olefin used in the present invention,
Those having 3 to 18 carbon atoms, such as propylene, 1-butene, 1-pentene, and hexene-1.
1,4-methylpentene-1, heptene-1, octene-1, nonene-1, decene-1, etc.
They can be used alone or in mixtures. The polymerization method used in the present invention has a polymerization temperature of 130
It is carried out under high temperature conditions of ℃ or higher. Typically, ethylene or ethylene and α- A solution polymerization method for polymerizing a mixture of olefins, in which a Ziegler type catalyst is supplied instead of a radical catalyst to a conventional radical polymerization low-density polyethylene plant, to produce ethylene or a mixture of ethylene and α-olefins at
There is a high-temperature, high-pressure polymerization method in which polymerization is performed at a polymerization temperature of 300°C and a polymerization pressure of 200 to 3000 atmospheres. Examples of the inert hydrocarbon solvent used in the solution polymerization method include butane, pentane, hexane, cyclohexane, heptane, octane, isooctane, nonane, decane, dodecane, and the like. These can be used alone or as a mixture. A specific example of solution polymerization method is CT
There is a process described in Elston, Canadian Patent No. 980,498, dated December 28, 1975. 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. Examples of high temperature and high pressure polymerization methods include BP932231, BP1205635,
Examples include USP1161737. After the polymerization is complete, the reaction mixture that comes out of the polymerization reaction vessel contains the polymer, unreacted monomers, coordination polymerization catalyst that remains partially active, and inactive when an inert hydrocarbon solvent is used. Contains an activated hydrocarbon 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. 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 brings the catalyst and deactivator into quick contact. 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 quencher used in the present invention is defined by having the number of ester groups from 0.4 to 20 times the total number of molecules of the transition metal compound and the organometallic compound, and the specific amount of the quencher is Naturally, it depends on the methacrylic ester content or the total content of methacrylic ester and acrylic ester in the deactivator. If the number of ester groups is less than 0.4 times the number of catalyst molecules, deactivation will not be sufficient, and if the number is more than 20 times the number of catalyst molecules, it is not economical. Since the deactivator of the present invention is an ethylene copolymer, it has excellent compatibility with polyethylene polymers, and has the feature that even if it remains in polyethylene, it does not adversely affect its performance. The deactivator used in the present invention is a copolymer of ethylene and methacrylic esters or a copolymer of ethylene and methacrylic esters and acrylic esters. Methacrylic esters and acrylic esters are H ₂ C=CCH ₃ COOR, H ₂ C, respectively.
=CHCOOR, where R is 1 carbon number
~30 aliphatic, alicyclic, or aromatic hydrocarbons. These are copolymerized with ethylene either alone or as a mixture. Examples of copolymers of ethylene and methacrylic acid esters include ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, and ethylene/isobutyl methacrylate copolymer. , ethylene/pentyl methacrylate copolymer, ethylene/heptyl methacrylate copolymer, ethylene/octyl methacrylate copolymer, ethylene/nonyl methacrylate copolymer, ethylene/decyl methacrylate copolymer, ethylene/dodecyl methacrylate copolymer Examples include acrylate copolymers, ethylene/cyclohexyl methacrylate copolymers, ethylene/benzyl methacrylate copolymers, ethylene/tolyl methacrylate copolymers, and ethylene/methyl methacrylate/ethyl methacrylate copolymers. Of these, ethylene and
Methyl methacrylate copolymers are industrially preferred. The content of methacrylic ester in the ethylene/methacrylic ester copolymer is 3% by weight.
The above is preferable. If it is less than 3% by weight, the amount of the deactivator increases, which may lead to a decrease in density during production of high-density polyethylene. Examples of terpolymers of ethylene, methacrylic esters, and acrylic esters include ethylene/methyl methacrylate/ethyl acrylate terpolymers, and ethylene/ethyl methacrylate/methyl acrylate ternary copolymers. , ethylene/ethyl methacrylate/ethyl acrylate terpolymer. The contents of methacrylic esters and acrylic esters in the terpolymer are each 2
It is preferably at least % by weight. If it is less than 2% by weight, the amount of deactivator increases, which is uneconomical, and may lead to a decrease in density during production of high-density polyethylene. All known methods can be used to produce the above copolymers or terpolymers. For example, a mixture of ethylene and methacrylic ester or acrylic ester is supplied to a high-pressure polyethylene polymerization apparatus, and the polymerization pressure is 1000 to 4000.
A method for obtaining the copolymer by radical polymerization under conditions of atmospheric pressure and 150° to 300°C is mentioned. A method of radical polymerization using an emulsion polymerization method at a pressure lower than the above can also be used. The quencher is added to the reaction mixture dissolved or suspended in an inert hydrocarbon solvent or 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 deactivator has been added is separated into volatile monomers or inert hydrocarbon solvent and polymer in a polymer separator. Volatile substances are recovered in gaseous form from the polymer separator. The quencher is not gasified in the polymer separator and remains 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 deactivated and the polymerization reaction is promptly stopped. This prevents uncontrolled runaway polymerization of unreacted monomers 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 formation 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. The ethylene copolymer of the present invention contains, of course, the usual stabilizers, ultraviolet absorbers, antistatic agents, antiblocking agents, lubricants, pigments, inorganic or organic fillers, rubbers and small amounts of other polymers usually added to polyolefins. Substances that can be used can be added. Examples of these additives include BHT, Ionox 330 manufactured by Ciel, Gutudrite 3114 manufactured by Gutdoritsi, Irganox 1010, 1076 manufactured by Ciba Geigy, Tinuvin 327 manufactured by Sankyo Pharmaceutical Co., Ltd.
LS770, 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 Examples include coalescence, high-pressure polyethylene, ethylene-propylene rubber, and polypropylene. Next, the method of the present invention will be explained 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,
0.5mol/hexane solution 1.6 and hexane
1.2 was added and the temperature was raised to 70°C. Then Al _{0.15 Mg}
(n-Bu) _1.75 (On-Bu) _0.7 (metal _{concentration} 0.9mol _/
Octane solution) 0.45 and hexane 0.35 70
The introduction was carried out over a period of 1 hour at ℃. Furthermore, 0.6 hexane containing 0.7 g of TiCl ₄ was introduced.
The reaction was carried out at 70°C for 1 hour. The generated inert solid is designated as catalyst A. The titanium (Ti) content in Catalyst A was measured and found to be 0.5% by weight. The production of Al _0.15 Mg(n-Bu _{) 1.75 (} On-Bu) _0.7 was according to Japanese Patent Application Laid _{- open} No. 5709-1983. (Synthesis of solid catalyst B) Al _0.15 Mg(n-Bu _{) 1.75} ( _On-
Synthesis was carried out using 400 mmol of Bu) _{0.7 ,} 400 mmol of trichlorosilane, 8.8 mmol of vanadyl trichloride, and 12 mmol of titanium tetrachloride. The total content of vanadium (V) and titanium (Ti) in catalyst B was 2.0%. (Synthesis of Solid Catalyst C) Oxygen and moisture inside a 500 ml flask equipped with two dropping funnels were removed by replacing the flask with dry nitrogen, and 160 ml of hexane was added thereto, followed by cooling to -10°C. Next, AlMg _5.8 (n− _{C 4} H ₉ ) _14.5・₍ On−
40 mmol _of an organomagnesium aluminum compound with a composition of C ₄ H ₉ ) _0.4 as an organomagnesium component
80 ml of a heptane solution containing n-butoxytitanium trichloride and 80 ml of a hexane solution containing 60 mmol of n-butoxytitanium trichloride were weighed into each dropping funnel, and both components were simultaneously added dropwise over 1 hour while stirring at -10°C. The mixture was aged for 3 hours at the same temperature. The resulting hydrocarbon-insoluble solid was isolated, washed with n-hexane, and dried to yield 11.2 g of solid product. The Ti content was 21% by weight. Note that AlMg _{5.8 (} n-
_{C4H9 ) 14.5 .} (On- _C4H9 ) _0.4 was synthesized according to Example 1 _of JP-A _- 56-47409. (Synthesis of solid catalyst D) AlMg ₃ (C ₂ H ₅ ) _1.5 ( _{nC 4} H ₉ ) ₆ (OSiH・CH ₃・
C ₂ H ₅ ) An organomagnesium aluminum compound having a composition of _1.5 as an organomagnesium component _.
80 ml of a heptane solution containing 40 mmol of titanium tetrachloride and 80 ml of a heptane solution containing 40 mmol of titanium tetrachloride were weighed into each dropping funnel, and both were added to a 500 ml nitrogen-purged flask containing 160 ml of hexane at 0°C with stirring. The components were added dropwise at the same time over a period of 1 hour, and the mixture was further aged and reacted at this temperature for 3 hours. The product was filtered and washed with heptane to give a solid product.
Subsequently, 300 mmol of a titanium compound having a composition of TiCl _3.5 (On- _{C 4} H ₉ ) _0.5 was added to ₁₀₀ ml of octane slurry containing this solid reaction product, and the mixture was reacted at 130°C for 3 hours to produce 12.2 g of solid catalyst. Obtained [D]. The Ti content was 19.8% by weight. The above organomagnesium-aluminum compound was synthesized according to the example of JP-A-56-59806. (Deactivating agent) Table 1 shows the characteristics of the used deactivating agent. Examples 1 to 7, Comparative Examples 1 to 4 A cyclohexane solution of triethylaluminum at a concentration of 0.1 mmol/h and solid catalyst A at 1.0 g/Hr was placed in a polymerization reactor with a stirrer having a capacity of 200 ml.
/Hr, (triethylaluminum 20mmol/
), ethylene was continuously supplied at 25 Kg/Hr, and hydrogen was continuously supplied at 1 Kg/Hr, at a polymerization temperature of 200°C and a pressure of 80°C.
Polymerization was carried out at Kg/cm ² . The polymerization conversion rate of ethylene was about 80%, and the amount of polyethylene produced was about 20 Kg/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 inactivated reaction mixture was heated to 250°C using a heat exchanger and then heated to 100°C using a stainless steel needle valve.
Kg/cm ² and 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 was 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. Once the polymerization had started and the polymerization was stabilized, continuous circulation of the ethylene and cyclohexane recovered from the separator to be used in the polymerization again without distillation purification was started, and this was continued for 4 hours.
To compensate for the insufficient amount of recovered ethylene and cyclohexane, we made up the necessary amount of fresh ethylene and cyclohexane. The productivity (polymer production amount (g) per 1 g of solid catalyst) of solid catalyst A was measured when the polymerization was stable after the start of polymerization and 4 hours later. 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 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. The test results for seven quenchers are shown in Table 2. As is clear from the results in Table 2, if no deactivator is used (Comparative Example 1), the amount of low polymer produced increases, the molecular weight distribution (MW/MN) becomes broader, and after 4 hours of cyclic use, Productivity and density have decreased. Furthermore, when methanol is used as a quenching agent (Comparative Example 2), a polymer with normal properties can be obtained when polymerization is stable, but when circulation of unreacted ethylene and solvent cyclohexane is started, the activity rapidly decreases. ,
After 4 hours of circulating use, polymerization had completely stopped. On the other hand, when the copolymer of ethylene and methacrylic esters of the present invention or the copolymer of ethylene, methacrylic ester, and acrylic ester of the present invention is used as a deactivator (Examples 1 to 7), the molecular weight distribution A polymer with good color was obtained with a sharp sharpness of 100 mL, and no decrease in density and productivity was observed even after the unreacted ethylene and the solvent cyclohexane were recycled. Moreover, when the amount of quencher is small (Comparative Example 3), the molecular weight distribution becomes broad, and when the amount of quencher is large (Comparative Example 4), the density of the resin becomes low. Example 8 A cyclohexane solution of triethylaluminum with a concentration of 0.1 mmol/h and 1.3 g/Hr of solid catalyst A was placed in a polymerization reactor with a stirrer having a capacity of 200
/Hr (triethylaluminum 20mmol/
Hr), ethylene 20Kg/Hr, butene-1 10Kg/Hr
The polymerization was carried out at a polymerization temperature of 200° C. and a pressure of 80 Kg/cm ² by continuously supplying Hr. The polymerization conversion rate of ethylene was about 85%, and the amount of ethylene-butene-1 copolymer produced was about 18 kg/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 12Kg/octene-1 instead of butene-1
An ethylene-octene-1 copolymer was obtained in the same manner as in Example 8 except that Hr was supplied. 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 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 3. Example 12 Polymerization was carried out in the same manner as in Example 9 except that solid catalyst D was used instead of solid catalyst A to obtain an ethylene-octene-1 copolymer. The results obtained are shown in Table 3. Example 13 Ethylene polymerization was carried out using an autoclave with an internal volume of 2 and equipped with a stirrer. Polymerization pressure 1200Kg/
cm ² and a reaction temperature of 220° C., ethylene was supplied to the reactor at a rate of 40 Kg/Hr, solid catalyst [A] at 0.15 g/Hr, and triethylaluminum at 3.0 mmol/Hr, respectively. The amount of polyethylene produced is 3.8
It was Kg/Hr. The quencher was added continuously after the reaction mixture left the polymerization vessel, in the form of a liquid mixed in mineral oil with an average boiling point of 150°C. The deactivated reaction mixture is led to a separation system in which a medium pressure separator maintained at 250 kg/cm ² and a low pressure separator maintained at 10 kg/cm ² are connected in series to separate unreacted ethylene and polymer. did. 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 Table 3. Example 14 Using a tubular reactor with an inner diameter of 5 mm and a length of 40 m, pressure was
The test was carried out at 1000Kg/cm ² and at a temperature of 260°C. Ethylene 16Kg/Hr, Butene-1 24Kg/Hr
The solid catalyst [B] was supplied to the reactor at a supply rate of 0.15 g/Hr and triethylaluminum 3.0 mmol/Hr, respectively. The amount of polyethylene produced is
It was 3.5Kg/Hr. The steps after adding the quencher were performed in the same manner as in Example 13. The results obtained are shown in Table 3. The meanings of terms used in the examples are as follows. (1) MI: stands for melt index,
Measurements were made in accordance with ASTM D-1238 at a temperature of 190°C and a load of 2.16 kg. (2) Density: Measured according to JIS K-6760. (3) MW/MN: Measured with Waters GPC-150C. (4) Percentage of molecular weight below 5000: Waters Co.
Measured with GPC-150C. (5) Resin color: The L value and b value of Hunter method were measured using a color difference meter manufactured by Color Machine Co., Ltd.

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Claims (1)

[Scope of 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 and a C3-C18 α- a mixture of olefins,
Polymerization is carried out at an average polymerization temperature of 130°C or higher, and a copolymer of ethylene and methacrylic ester, or ethylene, methacrylic ester, and acrylic ester is added to the resulting polymer mixture as a deactivator. A method for producing an ethylene polymer, comprising: inactivating the catalyst by adding a terpolymer; and separating unreacted monomers from the resulting polymer mixture. 2 The number of ester groups in the added deactivator is 0.4 to 0.4 of the total number of molecules of the transition metal compound and organometallic compound.
Claim 1 characterized in that it is 20 times
A method for producing an ethylene polymer as described in Section 1.