JPS6060117A - 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 phosphate ester compound as a catalyst deactivator in the polymerization of ethylene or the like in the presence of a Ziegler-Natta co-ordination catalyst. CONSTITUTION:A phosphate ester compound of the formula (wherein R<1>, R<2> and R<3> are each a 1-20C hydrocarbon group), e.g., trimethyl phosphate or triphenyl phosphate 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 0.1-8mmol 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 a method for producing polyethylene and an ethylene-α-olefin copolymer, and in particular to a method for producing polyethylene and an ethylene-α-olefin copolymer. Regarding activation.

Polyethylene and ethylene-α-olefin copolymer polymerized by a catalyst usually have a wide density range of θ, θ to θ, 97.9 f/a/l. However, it 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, Ichiotsu 4Lv Catalyst is known. Heavy color ("L-X'15") Catalysts include metal compounds in group (V~) 1 of the periodic table, such as compounds of titanium, panasonic, and '-4, and organic aluminum compounds. Organometallic compounds of bamboo are included as main constituents.

Various processes are known for the polymerization of mixtures of 1-ethylene or ethylene and α-olefins, but there are bath liquid polymerization methods that involve polymerization at a high temperature of 3θ°C or higher, and methods that do not use solvents. The high-temperature, high-pressure polymerization method allows ethylene to be polymerized adiabatically, and unlike the slurry polymerization method and gas phase polymerization method, it is an excellent energy-saving and energy-saving process because it does not require energy to remove the polymerization heat. .

In recent years, highly active catalysts such as Hiroshi Meru1 and others have been developed, and the catalyst residues in the polymers have very little charge, even if the catalyst residues in the polymers are not extracted or neutralized with alcohol or caustic soda. Compared to conventional polymers from which the catalyst has been removed, the color and thermal stability are much more consistent. If there is a catalyst removal process, it is impossible to use the recovered polymerization solvent and unreacted 7mers as they are in the polymerization because they are in contact with polar compounds such as alcohol, so these polar compounds must be separated in the purification process. There is a need to.

On the other hand, when a bacterially activated catalyst is used, since no polar compounds such as alcohol are used, the polymerization solvent and some or all of the unreacted polymers are not purified at all or are purified very easily.
It can be reused by simply processing it through 11 purification steps (for example, passing it through a molecular sieve), and the enormous amount of energy such as steam required for distillation purification can be saved.
It becomes possible to save money.

However, if the catalyst removal step is omitted, the catalyst is not inactivated, so that polymerization after leaving the polymerization vessel, so-called post-polymerization, occurs. Postpolymerization generally causes the formation of undesirable low molecular weight oligomers, waxes, greases, etc., since the polymerization temperature is higher than the average temperature within the polymerization vessel. Butene
7. Oligomers such as hexene-7 cause low density F during the production of ethylene homopolymer.

In addition, in the high temperature surface pressure method, the combined conversion rate of ethylene is 70 to 3.
If the catalyst is not inactivated, there will be unreacted 1:nomer of polyi71 in the reaction polymer that exits the polymerization vessel, and this will polymerize and the reaction will not be controlled. There is a huge risk of triggering a runaway reaction.

For the deactivation of catalysts, conventional deactivators such as alcohols and compounds used to remove qφ molecules are used.
Since the alcohol is volatile, it evaporates from the polymer solution along with the reaction monomers and solvent, contaminating the heptamers and solvent, eventually requiring purification of the monomers and solvent.

The present inventors have developed a deactivating agent 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 the solvent or other substances during recovery. 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 have an adverse effect on the TI of the polymer, such as peritectic stability.

That is, the present invention provides ethylene or ethylene and carbon@ A mixture of α-olefins of 3 N L, /♂ is polymerized under conditions of an average polymerization of 7 IIh degree/3θ°C or less, and the resulting polymer mixture is added with sufficient amount to inactivate the catalyst. loss of tit (in the formula R1, R2
, R3 is active 7.-Fune Q,,,t: nl. -2-81,3 Represents a hydrocarbon having 7 to 20 carbon atoms, either the same or different. ), in the form of a solution of an inert hydrocarbon or in the form of a cloud, or in the pure solid or molten state, and inactivating the catalyst by mixing; separating unreacted monomers or unreacted polymers from the inert hydrocarbon solvent from the polymer mixture containing the deactivating agent and the reaction product of the deactivating agent and the catalyst; The present invention relates to a method for producing an ethylene-based polymer, which is characterized by separating a polymer that is

The mt-it catalyst used in the present invention contains a transition metal compound and an organometallic compound as main components. As the transition metal compound, for example, transition metal halides of groups 1 to 2, such as titanium halide, vanadium halide, and panadium oxyhalide, are used. Elephant metal compounds include monoaluminum compounds such as alkylaluminium, alkyl/l/fluminiram chloride, etc., or alkylaluminum-lgnesium complexes, and argylalkoxyaluminium-7-mumagnesium complexes. Organoaluminium-Magnesi-Kum complex etc. are used.

The catalyst used in the present invention must be sufficiently commercially active that it does not require removal of the catalyst, and must be capable of rapidly reacting with the deactivating agent of the present invention to inactivate it. It has to be something. An example of a preferable catalyst used in the present invention that meets these requirements is
There is a catalyst consisting of a solid reaction product obtained by reacting an organomagnesium compound with a titanium compound or a vanadium compound, and an organoaluminum compound, as shown in W and JP-A No. 2002-11219.

In other words, in JP-A-Sho tg-gua 4t09, (AHi)
General formula M, 11't4gβR", R", X', Xt (where M is AL, Zn, B, Be, Li, β is a number of 7 or more, α, 11.q, r, S is θ or θ
is a larger number, l) + q −4−r −1−
s == mα ten flood β, θ≦(r+s)/(α+β)≦
/, θ, m is the valence of M, R1, R2 are hydrocarbon groups with the number of carbon atoms/~λθ which may be the same or different, x'', X2 are the same or different groups, and hydrogen atom,
01ζ3, O8i R'R5R6, NH4I-8R9, 1<3, R7, R8, R9 are the number of carbon atoms/
~λθ represents a hydrocarbon group, R4, R5, I<a are hydrogen atoms or hydrocarbon crystals having 7 to λθ carbon atoms), an organomagnesium component soluble in a hydrocarbon solvent; 11) Formula Ti(OR”)n・Gi-1 [in the formula R
IG is a hydrocarbon group with carbon atoms/~λθ, X is a halogen, and θ≦n≦3]. , (1
) for the organomagnesium component of (11)
A catalyst is disclosed which comprises a solid reaction product obtained by reacting compounds in a molar ratio of /, /~g, θ and a percussion aluminum compound.

For my father, Tokukai Showa-Tawosao, (8) (1) General formula MctMgβ R', X', X',
, (where M is At, Zn, B, Be, Li, β is a number of 7 or more, α, p, q, ", S is θ or θ
is a larger number, p+q+r+s=+i+α+λβ
, 0≦(r-4-s)/(α+β)≦/, θ, m); Hydrocarbon group of flood θ,
XI and x2 are the same or different groups, hydrogen atom, OR3
, O8i R'l<5R6, NR'R8, SR", R3, R7, ■(8,1 (9 is the number of carbon atoms) ~
A hydrocarbon thread of λθ is poured into a hydrocarbon solvent represented by R4, R5, and R6 are hydrogen atoms or hydrocarbon groups having a carbon atom number of 1 - λθ. ) a solid reaction product with a titanium compound containing at least 7 halogen atoms, with the general formula TiXa(OR”)4-a, VOXb(OR1O)3
-b, and VXC(OR10)4-C (in the formula, X is a halogen atom, RIG is a hydrocarbon group having 7 to 2θ carbon atoms, a is /~g, b is /~3, C is / A solid catalyst obtained by reacting a solid catalyst with at least a compound selected from titanium and vanadium compounds represented by (a number of ~) and (B) an organic aluminum compound is disclosed. There is.

Another example of a preferable catalyst used in the present invention is
JP-A Shoj+-, 2g9θ5, 2F2θotsu, 362riθg, 11. Examples include catalysts described in F910, G7G OJ', JSozaθY, and JP-A-57-7Otsu00Y.

Examples are: (1) General formula MaMgR', R'', X', X2SDt
(In the formula, M is a metal atom of Group I to [Group
, p, q, r are 0 or greater than or equal to 0, S is greater than/less than O, t is a number greater than 0 or θ, l) + Q +
r 10s = mα+2, θ<(r+s)/(α+7)
≦/, θ, S≦electricity, m is the valence of M, R1
, R2 is carbon 1f, which may be the same or different (7 steps to
λθ hydrocarbon group, XI represents a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, X2 is) 1
0 gene atom, D represents an electron-donating organic compound) and (11)! (Hydrogen quantifier, 41 units) ＼7 types selected from halides of logefide, boron, aluminum, aluminum, germanium, tin, lead, phosphorus, arsenic, amp-7, bismuth, zinc, cadmium, and mercury fttt) a titanium compound or/and a vanadium compound and an organometallic compound CB].

Another example is the following component (A) and a metal compound (B
It is a catalyst consisting of 3.

Ingredients [1 to] (4) and (5) in the presence of (3) shown below
A solid catalyst formed by reacting +l'l with the general formula MαMgR'pX'q"Dr (in the formula, M is from periphery) metal atoms of Groups 1 to 3 of the Table of Laws, α, p,
q and r have the relationship θ and yu, m is the valence of M, and n
' is a hydrocarbon of carbon atoms Vi/~λθ. (of / 澾 or a mixture of two or more, XI is a hydrogen atom or a negative containing oxygen, nitrogen or sulfur atom) 1 (a mixture of seven or two or more of, D represents an electron-donating organic compound) Magnencum compound (2) Boron, silicon, germanium, tin, phosphorus,
A solid component (4
) Organometallic compound (5) Any of the following transition metal compounds (a) to td) la) titanium compound, (b) vanadium compound, fc
) titanium compounds and vanadium compounds, (d) butane compounds and zirconium compounds An example of bending is (1) general formula MαMg, yR'pR-x', x'5L)
t (where M is a number from the periodic table or θ or less, β is a number greater than 0, p + q + r + s; mα+
λβ, θ≦(r+s)/(α+β)≦/, θ, where m is the valence of M, t is 0 or a number greater than θ, and R1, I (even if 2 are the same) A hydrocarbon group having a carbon atom number/~2θ which may be different, XlX2 is the same or different group and represents a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, and D is a Hydrocarbon water represented by (representing a chemical compound): 1 magnesium compound soluble in a solvent and 3'7u: hydrogen hydride, a primary halide, boron, aluminium 1, gyro,
(iii) titanium compound or tJ/ and a vanadium compound (A) and an organometallic compound (B3).

The α-olefin used in the present invention has 3 or more carbon atoms, such as propylene, butene, pentene, hexene, comethylpentene, and heftene.

These include octene-7, nonene-7, decene-7, 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 7300 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 by iltl normalization at θ to θθ atmospheric pressure, by supplying an it+ catalyst instead of a radical catalyst to a conventional radical polymerization low-density polyethylene plant. , ethylene or a mixture of ethylene and α-olefin at a polymerization temperature of 7300 to 300°C, )θθ to 3θθ
There is a high-temperature crystal pressure method that polymerizes at a polymerization pressure of θ atmosphere.

Examples of the inert hydrocarbon F6 medium 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.

As a specific example of the melt polymerization method, 1st
There is a process described in Canadian Pat.

High d11 (High-pressure polymerization methods include autoclave methods using autoclave reactors, tubular methods using tubular reactors, and various multistage polymerization methods in which autoclaves and tubular reactors are combined for polymerization. High temperature An example of a high pressure polymerization method is [3P93
2. ．． 23/, BP/, 2θ Yu, Otsu 33. U8P/,/
Otsu/, 737 etc. can be seen.

After the polymerization is completed, the reaction mixture skewered from the polymerization reaction teapot contains the polymer, 1,6 monomer 4.0%, and a portion of the final product.
+ 1'l remains as it is! When using catalyst and inert carbonization tJ<element 1t+ir7, inert carbonization) 1 (contains elementary solvent.To prevent post-polymerization and inactivate the catalyst) , the deactivator is mixed with the reaction mixture.The place where the deactivator 1111 and the reaction mixture are mixed may be at the end of the pressure reducing valve between the polymerization vessel and the polymer separator.The mixing method is L+ city. ni-/-1lha1marktha9淋]1rusa1silkwormfunkonsuke1. However, it is recommended that the catalyst and deactivator be mixed quickly (such as mixing with a mixer such as a static mixer or an in-line mixer). Any method may be used as long as the two contact each other.

The amount of deactivator added must be sufficient to ensure deactivation of the catalyst. Such deactivation of the catalyst is achieved by deactivating at least seven of the constituent components of the catalyst, namely transition metal compounds and organometallic compounds. Preferably, however, sufficient quenching agent 1-11 is used to react with both catalyst components.

The Nil of the deactivator used in the present invention is in the range of θ,/~1-mmol per total mole/mmol of the transition metal compound and organometallic compound. If the amount is less than θ,/mmol, the deactivation will not be sufficient, and if the amount is more than ♂ mmol, the cost will increase and it will be uneconomical.

It is a phosphoric acid ester compound represented by the following formula (1<1, RZ, 1<3 represents a hydrocarbon group having the same or different number of carbon atoms/~-0).

Examples of the phosphoric acid costel compound include tributyl phosphate, tributyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, tributyl phosphate, trihequinulfonuphate, tripropyl phosphate, tricleryl phosphate, and linonyl. Phosphate, tridecyl phosphate, tridodecyl phosphate, trite-radecyl fonuphat, trihexadecyl phos-7
ate, triotadecyl phosphate, trieicosyl phosphate, triphenyl phosphate, tricresyl phosphate, trisisoprobyl fecol phosphate, octyldiphenyl phosphate, and the like.

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

The reaction mixture to which the quencher has been added is passed through a polymer separator.
The volatile heptamers or inert hydrocarbon solvent and the polymer are separated. 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. The resulting polymer is added with additives such as antioxidants and, if necessary, catalyst neutralizers and lubricants.
Finally, it is pelletized using an extruder.

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

This prevents uncontrolled runaway polymerization of unreacted upper polymers in the polymer separator, and suppresses the production of low molecular weight polymers (wax, grease, etc.) due to post-polymerization. (2) Undesirable side reactions, such as the formation of butene due to dimerization of ethylene, are suppressed.

When butene// is formed, the density of the ethylene homopolymer decreases. (3) By passing all or part of the monomers and inert hydrocarbons recovered from the reaction mixture without a purification process or through a simple purification process, it is possible to recycle the paste. (4) The deactivator remaining in the polymer or the reaction compound 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, i'f
Materials normally added to polyolefins can be added, such as k-agents, pigments, inorganic or organic fillers, rubbers and other small amounts of polymers.

Examples of these additives include BHT, Shern 1
Ionoknu 33θ, Gridlich Gutudrite 3//g, Ciba Geigy Irganox 10/θ
, /θ76, Tinupin 327, Nil Kuwasha LS77θ
, LS≦,22, ■) is also 1TI), +11. 'I'
Examples include P-stearic acid potassium hydrodarcite, basic magnesium carbonate, erucic acid amide, oleic acid amide, titanium white, calcium carbonate, carbon black, talc, styrene-butadiene rubber, ethylene-propylene rubber, polypropylene, and the like.

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

(Synthesis of solid catalyst A) After removing oxygen and moisture inside the autoclave with dry nitrogen, trichlorosilane, θ9.5'mat/l
~xane+'l solution 1. Otori and Heginan/, 2t
was charged and the temperature was raised to 70°C. Next h16,15Mg
(n-Bu)1.75(On-Bu)(1,7(
Metal concentration θ, octane solution of 9 mot/l) 0.
3 t of hexane and 0.3 t of hexane were mixed at 7θ°C over 7 hours.

Furthermore, '1'1C44θ, 7? Hexane θ and t containing hexane were added and reacted at 7θ°C for 7 hours. The generated inert solid is designated as catalyst A. When the titanium (Ti) content in catalyst A was measured, it was found to be θ and evening weight ft%.

In addition, At0.15Mg (n-Bu)1.75(
On-Bu ) o, 7 was manufactured according to the Japanese Patent Application Laid-Open No. 2003-100003.

(Synthesis of solid catalyst B) In the same manner as A, A/-o, +sMg(n-131)+,
7s (On-Bu) o, y gθθm r, +o L and trichlorne rung θθmmot and parsyl trichloride♂,
! mmot, titanium tetrachloride/, 2 mmot by i
) was completed. The total content of vanadium (Vl and titanium ('I'i)) in catalyst B was 11 in the ratio of λ and θ.

(Synthesis of solid catalyst (゛)) Capacity containing two dropping funnels; Oxygen and moisture inside a 11jθθml flask were removed by dry nitrogen replacement, 160ml of hechitin was added, and the mixture was cooled to -/θ℃. .

Next, AtMg5. s(n-C4H4g) +4-5
・(0n-C4H8)o, an organomagnesium aluminum compound with a composition of 4 is used as a fr PJt magnesium component, and 1 liquid lθ is added to heptane containing 0 m mo L.
- and n-butoxytitanium trichloride with 0 m mo
The hexane solution IθmA containing L was weighed into each dropping funnel, and both components were simultaneously added dropwise over 7 hours at -7θ℃ while pressing 41゛, and the mixture was further aged at this temperature for 3 hours. . The resulting hydrocarbon insoluble solid was isolated, washed with n-hexane, and dried to yield 2 r of solid product. The content of i'i was 27% by weight. Note that AtMg5. s(n-C4■9)+4. s・(O
n-C411,). .

(Synthesis of solid catalyst) AzMg3 (C21t, ), 5 (nC4Hg)
s (os i H-CH3-C2H3) , 5 H
Heptane solution ♂θml containing organomagnesium aluminum compound having 11 components as organic red sea bream and sium component θmmo L and titanium tetrachloride θmmo
Weigh out the heptane bath solution ♂θml containing L into each dropping funnel, and calculate the volume h (jθ
Both components were simultaneously added dropwise over 7 hours to a θ-nitrogen-substituted flask at 0° C. with stirring, and further aged at this temperature for 3 hours. Filter the product, wash with heptane,
A solid product was obtained. Subsequently, the composition TiCt3.5(O
n-C4H9)os titanium compound 3θθm+not
and reacted at 730°C for 3 hours/ , 2.2
A solid catalyst CD) of f was obtained. The Ti content is I9. It was the weight clerk. The above organomagnesium-aluminum compound was synthesized according to the example of JP-A-KOKAI Publication No. 2003-100002.

Example / To 7, Comparative Example 7 ~ To a polymerization vessel equipped with a stirrer having a capacity of
l! l! l! W A /, Or, I4r, 'Ir
% degree θ, / mmo/-/, λθOa,
,j,, () Leaf-chi/L/aluminum, 20
mmot/l(r), ethylene - yy, ren,
Hydrogen was continuously supplied at /h/F-1t, respectively, and polymerization l! Polymerization was carried out at +A degree λθθ°C and pressure ♂0” IAr&. The polymerization conversion rate of ethylene was approximately θ, and the production of polyethylene was 1 (I was approximately λθKrzFlr).

The quencher was a 7wt4 bath or slurry solution of cyclohexane and was added continuously after the reaction mixture exited the chassis. The deactivated reaction mixture was once heated to 2° C. using a heat exchanger, then lowered to a pressure of /i<q/iJ using a stainless steel needle valve, and introduced into a separator. Gaseous unreacted ethylene and cyclohexane were continuously collected from a part of the separator, and a polymer cyclohexane slurry cooled to room temperature was continuously extracted from the male part of the separator I. The polymer slurry is separated into polymer and cyclohexane in a centrifuge.
After heating, it was fed to a vented extruded panicle and pelletized.

The obtained pellets were crushed and dried to completely remove volatile components, and then the basic properties of the polymer were measured.

Once the polymerization has started and the polymerization has stabilized, the ethylene and cyclohechitin recovered from the bone white 1 [vessel] are used again for polymerization without distillation and purification. I went to

To make up for the insufficient amount of recovered ethylene and cyclohexane, fresh ethylene and cyclohexane were needed.

Productivity (polymer production amount (f) per solid catalyst/f) of solid catalyst A was measured when the polymerization was stabilized after the start of polymerization and 9 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 stabilized and after a period of time. When butene is produced due to a side reaction, the density decreases, so the degree of by-production of butene can be determined from the density change.
Shown in the table.

From the results in Table 7, it is clear that using a quenching agent, 4c
In the comparative example, the amount of low polymer produced increased17, the molecular weight distribution (MW/MN) became broader, and the density decreased due to lack of productivity after cyclic use.

When used as a deactivating agent such as methanol (Comparative Example, 7)
When the polymerization is stable, a polymer with normal properties is produced, but when the circulation of unreacted ethylene and the solvent cyclohexane is started, the activity decreases rapidly, and the activity decreases rapidly. After 3 hours, the polymerization stopped completely.

On the other hand, when the phosphoric acid ester compound of the present invention is used as a deactivator (Examples/~7), a polymer with a sharp molecular weight distribution and good color can be obtained, and a polymer with a sharp molecular weight distribution and good color can be obtained. Even after use, no decrease in density or product performance was observed. Moreover, when the amount of the quencher is small (Comparative Example 3), the molecular weight distribution becomes broad, and when the amount of the quencher is too large (Comparative Example 3), the color of the resin becomes poor.

Example ♂ Solid catalyst A was placed in a polymerization vessel with a stirrer having a capacity of /θθt.
/, 3 f/f-5, concentration θ, / mmot/l triethylaluminum cyclohexane solution λθθt
/Fir () Lithyl aluminum = +7 mm20 mm
ojJ-1y), ethylene was continuously supplied at 10Kf, and butene was continuously supplied at /θKpJtr, respectively, and polymerization was carried out at a polymerization temperature of 2θθ°C and a pressure of θKy/cJ. The polymerization ratio of ethylene is approximately 1.f%, ethylene-butene-
/ The amount of copolymer produced was approximately / Kpmr. The polymerized reaction mixture was treated in the same manner as in Example 1. The results obtained are shown in Table 2.

EXAMPLE Ethylene-
An octene/copolymer was obtained. Obtained conclusion! 41. are shown in Table 2.

Example / /7 Polyethylene was obtained by polymerizing in the same manner as in Example / except that solid catalyst B was used instead of solid catalyst A. The results obtained are shown in Table 2.

Example // An ethylene-butene/copolymer was obtained by polymerizing in the same manner as in Example except that solid catalyst C was used instead of the solid catalyst. The results obtained are shown in Table 2.

Example/2 Polymerization was carried out in the same manner as in Example except that solid catalyst A was used instead of solid catalyst A to produce ethylene-octene-/
A copolymer was obtained. The obtained results are shown in the 5λ table.

Actual) Other side/-9 1. Using an autoclave with a stirrer and a capacity of 2 tons,
Polymerization of ethylene was carried out. Polymerization pressure/,,,7 in 2θθ
%J.

Reaction warm polishing 2. At 2.0℃, ethylene is θKy/Hr
, solid catalyst [8J wo0. /, f f/F-1r, triethylaluminum 3. Each was fed to the reactor at a feed rate of θH1 mo LA+. The amount of polyethylene produced is 3. It was e5'K9A-1r. a quenching agent,
Average boiling point/. The reaction mixture was added continuously after it left the polymerization vessel in the form of a liquid mixed in mineral oil at 3-θ°C. The deactivated reaction mixture was led to a separation system in which a medium-pressure separator maintained at 9Δd at 2jθ and a low-pressure separator maintained at a pressure of /θ were connected in series to separate unreacted ethylene and polymer. . Table 2 shows the properties of the polyethylene obtained during stable polymerization and after the unreacted ethylene was recycled.

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

Example: Using a tubular reactor with an inner diameter of jmm and a length of θm, a pressure of 10
The test was carried out at θθ”9Ani1 temperature 2≦θ°C.

Ethylene 7 ot Kvf4r, buti 7-/, 2 y
: Ky, 4(r, solid catalyst (B) θ./s fy+
1r, triethylaluminum 3. θm mo z/r
-Ir were respectively fed to the reactor at a feed rate. The amount of polyethylene produced was 3,j KpJlr. The steps after addition of inactivated necrosis were performed in the same manner as in Example 3. The results obtained are shown in Table 2.

Note that the terms used in the examples have the following meanings.

(t) MI: stands for melt index, AST
According to M D-/23♂, l crystallinity 790℃, load 2
．． /<K9.

(2) Density: Measured according to JISK-Otsu 7 Otsu θ.

+81 MW/MN: Waters GPC-/3r
Measured at θC.

(4) Molecular weight j, ratio of θθ0 to: Waters G
Measured by PC-/fOc.

(5) Resin color: Hunter method 1 value and b value were measured using a color difference meter manufactured by Color Machine Co., Ltd.

Procedural amendment (spontaneous) January 1981 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1, Indication of the case Patent application No. 168383 of 1983
No. 2 Name of the invention Process for producing ethylene bomber (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 Mei 1) Book 11 “Patent claims Mark 5 of "Scope" and "Detailed Description of the Invention," Contents of Amendment (1) The scope of claims in the specification is corrected as shown in the attached sheet.

(2) Akira δ, 1.1 of the detailed description of the invention (j':
Correct i as below).

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.
By polymerizing under the above conditions, a deactivator was added to the resulting polymer mixture.

1; General formula R”0-P-OR3 (in the formula R1, R2, R30
R2 are the same or different, and each represents a hydrocarbon group having 1 to 20 carbon atoms. ) is used to deactivate the catalyst by quenching the phosphoric acid ester compound represented by ), and to separate unreacted heptamers from the resulting polymer mixture. manufacturing method

Claims (1)

[Claims] (1) mt3L4 containing a transition metal compound and an organometallic compound in the presence or absence of an inert hydrocarbon thermal medium;
Using 1 as a catalyst, ethylene or a mixture of ethylene and an α-olefin having 3 to 3 carbon atoms is heated at an average polymerization temperature of
Neutralize under conditions of 30° C. or higher → 1: Then, to the obtained polymer mixture, ii. a deactivator sufficient to inactivate the 1911 medium, 1; general formula 1 (10-P -0R3 (in the formula R', ■<2.
A phosphoric acid ester compound represented by 1 (3 represents the same (ν)■ (2 or different hydrocarbon threads having a carbon number of 7 to -θ) is in an S liquid state or suspension state of an inert hydrocarbon, Alternatively, by adding pure solid or molten state and mixing, 4.61QI
By inactivating 6, the unreacted hexamer-f11:F,7,l,NLF mo#1 was extracted from the f14 polymer mixture.
5+,,”: Konozu-i J+!iJ-Kurumii jl:
I:i:II'7 Ethylene, characterized in that it separates the salt bath and the polymer containing the deactivating agent and the reaction product of the deactivating agent and the catalyst. Method for producing a system polymer (2) A patented polymer characterized in that the amount of the deactivator is θ,/~ mmol per total mole/mmol of the transition metal compound and 10,000 1,12 gold compound. 1< range 1st
Manufacturing method of ethylene polymer described in section (3) Convex Otsu, body electric name 1! +11 medium (AH+1 general formula M(zA41<
7jR', R", X1rX", (4 in the formula is At, Z
n. B5Be, , Li, β is a number of 7 or more, α, p,
q, r, s are θ or a change larger than θ, and p+
q+r+s=mα+sβ, θ≦(r1s)/(α+β
)≦7. θ] is the valence of M, R1, R
2 is the number of carbon atoms that may be the same or different/~! The hydrocarbon group of θ, Xl and X2 are the same or different, and hydrogen atom, OR3, O8i R'R51(', NR7R8
, SR9, nj, ■<7, R8,1(9
is a hydrocarbon yarn with carbon atoms/~λθ, R4,
1 (5, R6 is a hydrogen atom or the number of carbon atoms/~, 20 hydrocarbons can be used as a hot medium), and an organomagnesium component of the formula (11) Ti (
ORIO).・X4-4 C In the formula, R1G is the number of carbon atoms/
~λθ hydrocarbon group, X is halogen, 0≦n≦3
molar ratio of the titanium compound of (11) to the organomagnesium component of (1) /, / ~
The solid b obtained by reacting with g, θ and (II) consists of a product and (II) an aluminum compound j! l・) (Patent claim 1iit characterized in that a medium is used < Ethylene-based polymer according to item 7 or item 2. Manufacturing method (4) Using a song as a catalyst) Bifurcated j+ : M, hig7n', I<", x'
rx”, (where M is At, Zn, ■3, Be, L
i, β is a number of 7 or more, α, p, q, r, s are θ or a number larger than θ, +1 + Q + r
-1-s = mα + λβ, θ≦(r+s)/(α
1β)≦to〇, m is the valence of M, R', R
2 is a hydrocarbon group having 7 to 5 carbon atoms which may be the same or different; Xl and X2 are the same or different groups; hydrogen atom, OR3, os I R'R5R', NR7R8,
SR9 represents a group, R3, 17, R8, R9 represents a hydrocarbon group having carbon atoms/~2θ, R4, R5,
1 and 6 represent a hydrogen atom or a hydrocarbon group having 7 to 5 carbon atoms, and (II) any number of magnesium components soluble in a hydrocarbon thermal medium, and (II) at least 7 halogen atoms. The solid reaction product with a titanium compound containing (
::+)General formula%Formula% VXC(OnIO)4-, (in the formula X hahaO'/'
titanium and vanadium represented by 19, ■<10 represents a hydrocarbon group with the number of carbon atoms/~λθ, a is the number of /~3, b is the number of /~3, and C is the number of /~ A solid catalyst obtained by reacting at least seven types of compounds selected from compounds; and tB) an organoaluminum compound. (5) As a bleaching medium (1) General formula MaMglq, R%X1rX%Dt (wherein M is a metal atom of Group 1 to Group 1 of the periodic table, α, p,
q, r is θ or t) or more, S is greater than/less than θ, t is a number greater than θ or 6, p+q+r-1-s=
mα-t flood, 0<'(r+s)/(α+7)≦7. θ,
S≦t, m is the valence of M, RI, I2 are hydrocarbon groups with the number of carbon atoms/~2θ, which may be the same or different, and Xl is a hydrogen atom or oxygen, nitrogen or sulfur. Indicates a negative group containing atoms, X2 is halogen j prince, D
represents an electron-donating organic compound) and an organomagnesium component soluble in a hydrocarbon thermal medium, and (11)
Hydrogen chloride, organic halides, boron, aluminum,
7 types or a mixture of 2 or more selected from silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, a + < lead, cadmium, mercury halides,
Catalyst component (A) formed by contacting the reactant with (iit) a titanium compound or/and a vanadium compound
7-cho IQk/, 1. ; Silureno > Nrxr mouth) 41.1
-J-'7-'ir, Yamano blind soup 4.ノ;l++T, +J
(6) A method for producing an ethylene polymer according to claim 7 or 2, characterized in that the catalyst comprises the following components (Al and an organometallic compound (13)). to the scope of claims characterized in that 'S/item to: (g, component (A) of the method for producing an ethylene polymer according to item 2) in the presence of (3) shown below (4) and (5). ) with the general formula (1) 7 ~ 1aMgR'pχ'9・D, (where M is a metal atom of Group 1 to Group II of the periodic table, α, p, q,
r is a number greater than or equal to 0, p+q=mα+2, θ≦q/(α−
1-/)〈2, where n is the valence of M, R' is a hydrocarbon having 7 to θ carbon atoms/J4) i or a mixture of two or more, and X' is hydrogen atom or oxygen,
Organomagnesium compound (2) represented by seven or more types of negative threads containing nitrogen or sulfur atoms, where D represents an electron-donating organic compound (2) boron, silicon, germanium, tin, Rin,
A mixture of seven or two or more selected from antimony, bismuth, bent lead halide, or hydrogen chloride (solid component (4) resulting from the reaction of 31 (1) and (2))
Organometallic Compound (5) The following (,1) to (dl) 1 -Ei transferable compound (al titanium compound, fl-, 1 vanadium compound 1 cly-tan compound and vanadium compound,
(d) Titanium compound and zirconium compound (7) As a catalyst (J-based catalyst, (1) general formula M
aMgβR', R",,
S is 0 or a number of 4210 or more β is a number larger than θ, and p
+ Q + r + s = mα+)β, θ≦(r+
What is the relationship between s)/(α+β)winter/, θ, and ■1 is j of M
t is a large number, 1 (1
, 1<2 is a hydrocarbon group with the number of carbon atoms/~-0 which may be the same or different; (D represents an electron-donating axial compound)
Organomagnesium compounds soluble in hydrocarbon solvents represented by (11) hydrogen chloride, organic halides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, lead, cadmium,
7 types selected from mercury halides or 2 a
:: A patent characterized in that a catalyst consisting of (a catalyst component [A] formed by contacting a titanium compound or/and a vanadium compound and an organometallic compound CB) is used in the reaction product of a mixture of t< or more A method for producing an ethylene polymer according to item 1 or 2 of the scope of the results.