JPS5968310A - Production of ethylene polymer - Google Patents

Abstract

PURPOSE:To short-stop a polymerization reaction quickly and eliminate adverse effects caused by post-polymerization, by (co)polymerizing ethylene with the aid of a Ziegler type highly active coordination polymerization catalyst, and then deactivating the above catalyst with a specified compound. CONSTITUTION:Use is made of a polysiloxane compound of the formula (wherein R<1>-R<10> are each H or a 1-20C hydyrocarbon group, and m and n are each greater than 0), e.g.,methylhydrogensilicone oil. Namely, ethylene or an ethylene/ 3-18C alpha-olefin mixture is polymerized at an average temperature >=130 deg.C, and then the above polysiloxane is added in an amount of 50-1,000mg per mmol of the total of the transition metal compound and the organometallic compound in the catalyst to deactivate the catalyst.

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 the inactivation of a Ziegler-type catalyst used in the polymerization of ethylene and α-olefins.

Ziegler type 1 single-solvent copolymerized polyethylene and titanium-α-olefin copolymer is usually 0.8
It has a wide density range of 50 to 0.975710n3, such as films, blow molded products, fibers, extrusion molded products, etc.
It is used in large quantities for a wide variety of purposes.

Ziegler type catalysts are known as catalysts for polymerizing ethylene, vJ, and mixtures of ethylene and α-olefins. Ziegler-type catalysts include titanium and vanadium r.
Transition metals belonging to the ■-Sym group of the periodic table, represented by amberjack soup, and organometallic compounds such as organoaluminum compounds are included as main constituents.

Various processes are known for the production of ethylene and ethylene and α-olefins, but the
The solution polymerization method, which polymerizes at high temperatures below 0°C, and the high temperature/high pressure polymerization method, which does not use a solvent, can polymerize ethylene adiabatically. , B , fB Energy is safe for removing heat.
This is an energy-saving process that was a cause for concern because of its low energy consumption.

In recent years, highly active Ziegler-type catalysts have been developed, which eliminate the need to extract or neutralize the catalyst residue in the tun negative body with alcohol or caustic soda, and the acid content of the catalyst residue in the polymer is extremely small. Compared to conventional polymers, in which heat is used for qualitative catalyst removal, the catalyst removal process is similar to that of conventional polymers. Since it is in contact with a compound, it is impossible to use it directly for polymerization, and 1
It is necessary to separate these polar compounds in the iV manufacturing process. - When using a biocatalyst, it is necessary to not use polar compounds such as alcohols, to purify part or all of the polymerization solvent and unreacted monomers, or to use a simple purification method. It can be reused simply by processing it by passing it through molecular seeds, and it becomes possible to save a huge amount of energy such as steam required for distillation and purification.

However, if the catalyst removal step is omitted, the catalyst is not inactivated, so that polymerization after leaving the polymerization vessel, so-called post-polymerization, occurs. Post-polymerization is generally polymerization/l! The average temperature in the polymerization vessel is 1 (higher, so it is preferable, and low molecular acids (
This causes the formation of wax, grease, ethylene oligomers). Butene-1 hexene-1 etc. oligomers,
Ethylene homo-a coalescence/N, @ time, density) y low F causes.

Father, in the high-section high-pressure method, the polymerization conversion rate of ethylene is 10 to 3.
Since the coefficient is as low as 0, if the catalyst is not inactivated, a dense amount of unreacted hinomer will be present in the reaction mixture leaving the polymerization vessel.
There is a great danger that this will polymerize and cause a runaway reaction because the reaction is not controlled.

When a compound conventionally used to remove old catalysts, such as alcohol, is used as a deactivating agent to deactivate the catalyst, the alcohol is volatile and can dissolve the polymer together with unreacted monomers and solvent. The monomers and solvents are evaporated and contaminated, resulting in the need for purification of the monomers and solvents.

The present inventors have developed a deactivating agent that is not volatile by itself, does not generate volatile or reactive reactions after reacting with a catalyst, and is free from the risk of contaminating recovered monomers and solvents. As a result of continued efforts, we have arrived at the present invention. Of course, since the quencher remains in the polymer, it goes without saying that it will not adversely affect the properties of the polymer, such as its electrothermal stability.

That is, the present invention provides: In the presence F or absence-F of an inert hydrocarbon solvent,
Using a Cheekler-type catalyst containing a transfer metal compound and an organometallic compound, ethylene or ethylene and 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 resulting polymer mixture is added with a deactivator sufficient to inactivate the catalyst, and a general formula (wherein 1n and n represent an integer of 0 or less, Ill .

FL+! , B3.几4, 几5.几6, B), R
8, 几O2几10 are each hydrogen group or carbon number 1
~20 hydrocarbon groups. ) is added in the form of an inert hydrocarbon solution or suspension, or in a pure liquid or molten state, and mixed. deactivating the catalyst, separating the unreacted monomers or the unreacted monomers from the inert hydrocarbon solvent from the obtained polymer mixture, and the deactivating agent and the deactivating agent. The present invention relates to a method for producing an ethylene polymer, which comprises separating a polymer containing a reaction product of the catalyst.

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

Examples of transition metal compounds include titanium halides,
Transition metals of the side group such as Nonanadium, Nonanium oxynolide, etc.
Use the proboscis. Yes 4′ & metallized sweat → Of course, f.
Bamboo <y, °rluminium compounds such as alkyl aluminum, alkyl aluminum chloride, etc.
8 is an alkyl aluminum complex such as an alkyl aluminum complex, an alkyl aluminum complex, an alkyl aluminum complex, and an alkyl aluminum complex.

The Ziegler-type catalyst to be used in the present invention must be of a sufficiently high standard, requiring no catalyst removal, and must be inexpensive.
It must be one that rapidly reacts with the inactivating agent of the invention and inactivates it. An example of a preferable catalyst used in the present invention that meets these requirements is the bamboo-fired magnonium compound compound shown in JP-A No. 56-47409 and JP-A No. 111 (No. 56-59806). In combination with titanization or ζ-hexadation, there is a solid reaction product that can be used to react with a substance, and a catalyst consisting of an organoaluminum compound.

That is, in JP-A-56-47409, Vma, (A) (f
) General formula M, t~1g711', n-XI, X2.
(In the formula, M is AI.

Z II + I) + D c + J7 r, β is a number greater than or equal to 1, α1p1q, r, s are 0 or Q2L
is a number greater than O, p+Q + r 1- S =
mα→−2β, 0≦(rto)/(α”~β)≦1.0
If L, m is the valence of M, It', 11
Hydrocarbons having 1 to 2 carbon atoms, which may be the same or different, Q, X',
rb'+#, sa" group, 几', R'
, R8, 几9 represent a hydrocarbon group having 1 to 2 carbon atoms, "'+ 几5. 几6 represents a hydrogen atom, 1, carbon atom, 1 to 20 carbon atoms, 1 arsenic group. (11) formula "'(0""), ・X4-n C, +
E n10i, l: is a hydrocarbon group having carbon atoms a1 to 20, and X is halog/.

≦n≦3] was added to the organic magnesium component (1), and the titanium compound (11) was added at a molar ratio of 1.1 to 4.0-CIi. Disclosed is a catalyst comprising a solid reaction product (r3) and an organoaluminum compound (r3).

Moreover, in JP-A-56-59806, (A) (i) general formula M, tMgp几1. B2. XI
, X2. (In the formula, M is AI.

Zn, B, Be, Li, β is a number greater than or equal to 1, αl''1q, r, s are numbers greater than 0 or O, p+q+r+s=mα+2β, o <Cr+s
)/(α+β)<1.0, where m is the valence of M, and R+ and FL2 are carbon atoms e1. I to 20 hydrocarbon groups, Xl and X2 are the same or different groups, hydrogen atom, OR3,08il'L'
Indicates a group R'R', NR'R', SR',
B3, II7. R8 and R9 have 1 to 20 carbon atoms
R4, R5. FL6 is a hydrogen atom or a hydrocarbon base having 1 to 20 carbon atoms; (I) t) an organic magnesium component soluble in a hydrocarbon solvent; and (ii) at least 11 halogen atoms. The solid reaction product t, (lt
i) General formula % formula % VX c (ORlo) 4-c (in the formula, A solid catalyst obtained by reacting at least one compound selected from titanium and vanadium compounds represented by 9, where ~4, b is ■~3, and C is a number from 1 to 4; ) an organoaluminum compound, is disclosed.

Another example of a preferable catalyst used in the present invention is
JP-A-56-26905.28206, 32504゜4
59to, 47408.59805 and JP11g5
7-16005 includes a catalyst containing six molecules.

Examples thereof are: (1) General formula MdMgIL', l'L2. X'rX2.
D, (in the formula, M is a metal atom of Groups ■ to ■ of the periodic table,
αIPIQ+' is 0 or less than 0, S is greater than 0 and 1
Hereinafter, 1 is 0 or V or a number larger than 0, p+q+r++
+=mα+2.0〈(r+s)/(α11)≦1.0.
It has a one-row coefficient of s≦electron, and m is an atom of M 1+nit
R' r R" has 1 carbon atom, which may be the same or different
~20 hydrocarbon groups (XI represents a hydrogen atom or a negative group containing oxygen, nitrogen or sulfur atom, X2 represents a hydrogen atom, and D represents an electron-donating organic compound) From organomagnesium compounds and proboscis of IlfTm and (11) hydrogen chloride, organic halides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, lead, cadmium, and mercury halides. (iii) a titanium compound or a sodium compound (medium component CA) and an organometallic compound IC) It is a catalyst consisting of

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

Component CA) A solid catalyst obtained by reacting (4) and (5) in the presence of (3) shown below (1) General formula uttMgn'px', -nr (where M is a compound of the ■Group metal atoms, α+f'+q
l' is a number greater than or equal to 0, p-1-q=mα+2, O≦q/
(σ+1)×2, where m is the valence of M and ru′
is a hydrocarbon group having 1 to 201 carbon atoms or a mixture of two or more -H, X' is a hydrogen atom or oxygen,
An organomagnesium compound (2) Boron , silicon, germanium, tin, phosphorus, antimony, bismuth, chain halides I! /Here's C.'' If you'd rather shoot than depleted hydrogen, AfC1 or d, 24+,
A solid component (4) Organic metal compound (5) A mixture of (3) (+) and the anti-1,6 of (2) (5) A transition metal compound of any of (a) to (d) (Japanese) Titanium compound proboscis, 0+) □Nadium compound proboscis, (c) Titanium compound proboscis, (d) Titanium compound proboscis, zirconium compound proboscis, and others. , (1) General formula Ma M g7y R'pR',, X'
s
r4-s = mα+2β, 0≦(r+s)/(
α1β)≦t,.

, where m is the valence of M, tidO, or a number greater than 0, and 几1. R2 is a carbon atom that may be the same or different #! 1.1 to 20 hydrocarbon groups, Xl, X
l is the same or different group and represents a hydrogen atom or an implicit group containing oxygen, nitrogen or sulfur atom; dissolved organic magnesium compounds and (11) hydrogen chloride, organic halides, boron, aluminum, silicon, germanium, soot, lead, phosphorus, arsenic, antimony,
A reaction product of bismuth, salivary lead, cadmium, mercury halide or a mixture of two or more,
(iii) A catalyst consisting of a catalyst component [A] and an organometallic compound ([1] made by contacting a titanium compound, a proboscis, or/and a .zeta. nanoram compound).

The α-olefins used in the present invention are those having 3 to 18 carbon atoms, such as propylene, zothene-1, benzone-1, hexene-114-methylpentene-11, butene-1, and octene-1. N-11 Nonane-
11decene-1, etc., and can be used alone or as a mixture.

The polymerization method used in the present invention is carried out at a high temperature of 130°C or higher, typically at 130° to 300°C in the presence of an inert hydrocarbon solvent. At a polymerization temperature of 10 to 500 atm, the process was carried out to produce a mixture of ethylene and α-olefin. By supplying a Ziegler type catalyst instead of the catalyst, the polymerization temperature of ethylene or ethylene and α-olefin was 130' to 30nC, and the polymerization temperature was 50.
There is a high temperature polymerization method in which polymerization is carried out at a polymerization pressure of 0 to 3000 atm.

As an inert hydrocarbon solvent used in solution polymerization method,
Examples include butane, pentane, hexylane, isochlorohexane, heptano, octane, isooctane, nonane, decane, dodecane, and the like. These can be used as a clf or as a seven-piece proboscis.

, @ Concrete example of distributed legality and 1.2, O, T, R1
Canadian Patent No. 98 dated December 28, 1975 for 5lon
No. 0498;) The process of 戊 is here.

High-part, high-pressure K (H method) includes the autoclave method using an autoclave reactor, the tubular method using a tubular reactor, or various multistage polymerization methods in which autoclave and tubular reaction a* are combined for polymerization. An example of high temperature and high pressure market is BP 932,
231X+3Pf, 205,635, U8F 1,16
1,737 etc. are torn down.

After the end of polymerization, the reaction mixture ((
contains the polymer, unreacted monomers, some of which remain in the active state (Ziegler) (J4 catalyst, and when using the non-heptavalent hydrocarbon solvent, only the inert hydrocarbon solvent is used). After the IF stage is prevented and the catalyst is deactivated, a deactivating agent is mixed with the reaction mixture. The location 1 may be either before or after the vacuum pulp between the polymerization vessel and the polymer separator.As a mixing method, the flow of the two pipes may be combined in a ridge 21L and -C may be used. Any method may be used as long as the catalyst and the deactivator come into quick contact, such as a method of mixing in a mixer such as a static mixer or an in-line mixer.

The amount of deactivator added must be sufficient to ensure that the catalyst becomes inactive. Such inactivation of the catalyst is carried out by inactivating at least one of the +lt components of the catalyst, ie, the 4-transfer metal compound and the 11,4-metal compound. However, preferably V
It is preferable to use a sufficient quantity of deactivator to react with both catalyst components.

The IHI of the deactivator used for the wooden handle ψJ is transition gold 1.
- The amount of deactivating agent is in the range of 50 to -1000 per millimole of the total mole of 4 compounds' proboscis and 1 Hiba proboscis for sea bass. 50
mfl more than V'', deactivated; not enough, also 1000
In this case, the quencher remaining in the polymer or the reaction between the quencher and the catalyst exerts a negative influence on the performance of the polymer.

Akira Kio used the borine loxanide 8 to give various /recon oils and cX (i.e. methyl hydro) L
7 silicone oil, dimethyl 7 silicone oil, ethyl high lj I7,)ene/Ricoh/oil, Mebul ethyl silicone oil, methyl octyl silicone oil, methyl f full silicone oil, methyl octadecyl silicone oil, methyl phenyl high 10 diene 7 Silicone oil, methylphenylnoricone oil, diphenylsilicone oil, decamethyltetra/loxane, 1.1,1,3,5,7,7.7-octamethyltetra/logisan, octamethyltrinochloride, l
, 1,1,3,5,5.5-hezotamethylto-1-hasiloxane, 1,1,3,3,5.5-hexamethyltrifoxane, 1,1. :3.5.5-pentaphenyl-1
,,3,5-trinotyltrisoloxane,l:U,3
, 5-tetramethyl-1,1,5,5-tetraphenyltrisilogysan, hexamethylnonoxane, pentamethyldinoxane, 1,1,3.3-tetramethylnosiloxane, hexaethylno/loxane, 1 .3-,) Rhodityl-1,1,3,3-tetramethyldi/loxane', Hegisa n-provirdine loxane, 1,3-dimethyl-1,1,3,3-detraphenylnosiloxane, 1
．． 3- Nophenylu! , 1, 3,3-tetramethyldisiloxane, hexaphenylnonoxane, and the like. These rLs can be used alone or as a mixture. In addition, among these, the polymerization degree is high, the boiling point is high, and the thermal stability is excellent. Preferred are methyl octate/licon oil, methyl octyl silicone oil, menol octyl silicone oil, methyl octyl silicone oil, and methyl octyl silicone oil.

In particular, various high-10 diemborias having Si--H bonds are particularly suitable as they have high reactivity with catalysts.

The quenching agent 1lj1 can be applied to the reaction mixture either by diluting or suspending it in an inert hydrocarbon solvent, or in a pure liquid 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 has a polymer content of l/lI
In the I vessel, the volatile monomers or inert hydrocarbon solvent and the polymer are separated. Volatile substances are recovered in gaseous form from the polymer separator. In the polymer separator, the deactivator and the reaction product of the deactivator and the catalyst are not gasified and remain in the polymer. Got 4? The IJmer is added with an antioxidant and, if necessary, a catalyst neutralizer, and 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.

As a result, unreacted monomers in the polymer separator can be controlled, runaway polymerization reactions can be prevented, and low-molecular polymers (wax, grease, etc.) caused by parent polymerization
The generation of is suppressed. (2) Undesirable side reactions, such as the formation of butene-1 due to the two-way ratio of ethylene, are suppressed. (When butene-1 is produced, the density of the ethylene homopolymers decreases.) (3) The monomers and inert hydrocarbon solvent recovered from the reaction mixture are purified without a purification step.
．． Chirui can be recycled and used through an innovative purification process. (4) ,1′? The quencher remaining in the J-mer or the reaction product of the quencher and the catalyst does not adversely affect the properties of the polymer, and a polymer with good color and thermal stability can be obtained.

Mizumotori's ethylene is of course a regular stabilizer for the body,
Ultraviolet absorption, anti-banding, anti-blocking, lubricants, pigments, organic fillers, rubber and other polymers, and 69% addition to polyolefins.
Of course, you can add Jm for $p.

These additives include +3HT, Shell Ionox 330. Gutudrite 3114 manufactured by Gridlich, Irganox 10 manufactured by Chino Geigy
10,1076 Tinuvin 327, L8' manufactured by Sankyo Pharmaceutical Co., Ltd.
ITO1L8622, DMTJ'X Dr, TP,
Calcium stearate, hydrotalnite, basic magnesium carbonate, elca 1 amide, oleic acid amide, titanium white, russium carbonate, carzen black, talc, styrene-butadiene lano ζ-, ethylene-1 product, 8 tubes, high pressure Examples include processed polyethylene, ethylene-propylene rubber polyzorogylene, and the like.

Next, the present invention will be described in detail with reference to examples, but these examples do not control the present invention in any way.

(Synthesis of solid catalyst A) After removing oxygen and moisture inside the autoclave with dry nitrogen, 7 runs of trichlor, (), 11.6λ of hexane solution of 5 mol/ρ and 1.2ρ of hexane were charged, and the temperature was raised to 70°C. did. Next, A 16.15Mg (PBJ
, 75 (On-1'311) 0.7 (gold A/A# degree 0.9 +nol/Q2'z octane solution) o, 4s
i and hexa 70,35 I! , the total temperature was 70C for 1 hour.

Furthermore, T 1C140, hexa7 (1,6p, containing 7F)
was introduced and a 1 hour/11 cross 1 core test was conducted at 70°C. The produced f-soluble solid is designated as a monovalent medium A. Titanium in catalyst A (1
・-) When the acid content was measured, it was o, 5ljt, F-
).

In addition, "Q, 58 (g(n-Bt+),, 5
(On-+)u). , 7's ゛Battle] Kichi, I, according to Japanese Patent Application Laid-open No. 57-5709.

(Synthesis of solid catalyst B) In the same manner as A, A'Q, +66'g('-Bu)+,
i (On B11). , 7400 mmol, trichlorosilane 7400 mrnol, 3 mmol of titanium tetrachloride, and 12 m+nol of titanium tetrachloride. The total content of Nosu, Noum (V) and Titanium (T+) in Catalyst B was 2.0.

(Solid II! Assortment of lH medium C) Oxygen and moisture inside a flask with a culm diameter of 500+++/cm holding a 2-layer dropping funnel were removed by dry nitrogen substitution, and 160 cm of hexane was added to -Io Cooled to ℃. Next, AIMg('6 (n -04H1+)14.
5' (On-c+Ho). , an organomagnesium-aluminum compound having the composition of 4 and a heptane solution containing 1 to 40 mmol of magnesium 7-cum component.
80 ml and 1-cytoquine titanium trichloride)'
Hexane solution containing 60 +n Inot 80
Weigh out g/ into a drain funnel and keep it at -1o℃! Drop both ingredients into a mixing knife at the same time over an hour! -1 The hydrocarbon-insoluble solid produced by further aging at this temperature for 3 hours was isolated, washed with n-hexane, and dried.11.
．． Cheers at the solid-forming proboscis on 2F. The acid content of Ti was 21%. Note that AlMg, , 8(n O4Hg ) 1
44' (on 04HO). , 4 is Japanese Patent Application Publication No. 1983
-47409 was synthesized according to Example 1.

(Synthesis of solid catalyst) AIMg3 (02H5) 1.5 (na, horse) a (O
8iH・OH3・02+15) 4 with a composition of 1.5
11 Magnesium, Aluminum compound divided into 6 parts of organomagnesium, containing 40 + n no l, dissolved in heptane, 80 volumes and titanium tetrachloride 4Q + nmol
Weigh out 130 ml of hezotane solution I containing Hezotane into a round-neck funnel, and add 100 ml of hexane to a volume containing 160 me of hexane.

me nitrogen i! Add both components simultaneously over 1 hour to the flask with OC [f stirring], and then add this product IW.
Aged for 3 hours with 1 wick. The product was filtered and washed with hezothane to give a solid product. Next is the hard book 1. The composition Ti0 is added to the octane slurry 100- containing Ti-generated proboscis.
I35 (On 04Hg) (1,5 titanium compound 3
00 +n Inot (11-/Jlle, l 30
Solid catalyst CD of 12.2p after 3 hours of reaction at 'C
'l got it. The female containing T- weighed 19.8 lbs.
The organomagnesium aluminized piece FJ, JP-A+I ((5659806), was sweetened according to the actual example.

Examples 1 to 7, Comparative Examples 1 to 4 Sei 11 with toop! In the attached weight/meter, solid catalyst Aft, 07/Hr, concentration t), 1 m mo
l/fl of triethylminium rhinochlore/quinano solution, night total 200 fl/Hr (triethylaluminum 2
0 mmol/Hr), ethylene at 25 K9/
'+fr, 1 hg/+(r each continuously supplied L, +, t sweat r^AI'J: 200℃, pressure horn 80
The chassis moves at Kg/cm2. The polymerization conversion rate of ethylene is about 80%, and the amount of polyethylene produced is about 201%.
It was 1r/nr.

I'll deactivate it/Kurohegizan's 2 wI% bath is made into a slurry volume 1 night. anti-1,
Heat exchange - by mackerel) Tan 25
The mixture was heated to 1°C and introduced into the separator using a stainless steel needle valve.
6. Continuously recover gaseous unreacted ethylene and chloroxane from 6, cool to room temperature from the bottom of the separator.
child. The polymer slurry was separated into polymer and cyclohexane using a centrifuge, and then fed to a vent extruder and pelletized. The pellets obtained were crushed and dried under vacuum to completely remove the volatile matter, and then the basic properties of the polymer were measured.

The process was started again, and the IF was turned into an I.By the way, I collected the 1:2 from the container and the 4 centrifugal containers, and used the 7 ethylene and 7 talohexane again for polymerization without distilling them. Continuous use of 1j11 starts, , ('-7'l-
Please send it to the destination within 5 hours. Regarding the shortage of t2 due to the amount of ethyl/and/chlorhekiline added, 1. ．．
11 Russo/Yu's Necessary Eater Make r Nog (2/Hi.

11u Meme 1 call after the +ljl interview and 4 hours later, Zoro 2 of the troubled Catalyst A (
) 1 +5 remer producing acid (g)) per gram of judicial catalyst
．． 11 Su i style-/ko.

As a result, how much negative impact does ethylene, cyclohexane, and cyclohexane have on VC? r) /q
y-zosuka can be determined as 1'4].

The density of the polyethylene was measured at the scheduled time and after 4 hours of polymerization. When Noteno-1 is produced due to a side reaction, the density becomes low, so the degree of by-production of Guton-1 can be determined from the change in density jIF. 7jN quencher test binding first
Shown in the table.

Example 8 Solid catalyst A was placed in a polymerization vessel with a stirrer having a capacity of 1001 mm.
1. :(y/nr, cyclohexane solution of triethylaluminum with a concentration of 0.1 mmol/jL,
fL/Hr () Lie square aluminum 20 m +n
ol/Hr), ethylene at 20 Kg/Hr, and butene-1 at 10 Kq/Hr, respectively, and polymerization was carried out at a polymerization temperature of 200° C. and a pressure of 30 Kg/1yn2. The polymerization conversion rate of ethylene was about 85%, and the amount of ethylene/butene-1 covalent polymer produced was about I B l (+7/Hr). The polymerized reaction mixture and treatment of the proboscis were carried out in the same manner as in Example 1. The results obtained are shown in Table 2.

Example 9 Ethylene-
An octene-1-1 myopolymer was obtained. The obtained results are shown in the second
Shown in the table.

As is clear from the results in Table 1, when no quencher is used (comparison column 1), the amount of low polymerized polymers produced increases, the molecular weight distribution (MW/MN) becomes broader, and 5 hours after the start of polymerization. The density decreased with the later Zoro 2 Kuteibiigui.

Also, when methanol is used as a deactivator (Comparative Example 2)
When the polymerization is stable, a polymer with normal properties is obtained, but when the circulation of unreacted ethylene and solvent cyclohexane is started, the activity decreases rapidly, and after 4 hours of circulating use, the polymerization has completely stopped. Oops.

On the other hand, when the polysoloxane compound of the present invention was used as a quenching agent (Examples 1 to 7), a polymer with good color was obtained with a chassis of molecular weight distribution, and even after the unreacted ethylene and the solvent cyclohexane were recycled. , low-F of 14j and zero 2 activity was not observed. In addition, when the amount of the quencher is small (Comparative Example 3), the molecular weight distribution becomes wide, and when the amount of the quencher is too large, the color of the resin becomes poor.

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

Example 11 Ethylene-butene-1
The copolymer is long-lasting. The results obtained are shown in Table 2.

Example I2 By using a solid catalyst instead of the solid catalyst, t was polymerized in the same manner as in Example 9 to form ethylene-octene-
1 joint weight @ body is insulting. The results obtained are shown in Table 2.

Example 13 Stirring of internal volume 2a 11! Using a 1-knob autoclave,
I took a heavy dose of ethylene. Polymerization pressure 1200 Kq/
ryn2, anti-KiE, 1KIE At 220°C, ethylene 40Kg/Hr', solid catalyst (A) 0.15g/10r
, 3,0 mmol of triethylaluminum
/ Irr was supplied to the mulcher at a rate of 1 bundle. The yield of polyethylene was 3.8 ni/Hr. The quencher was liquid cedar mixed with mineral oil having an average boiling point of 150° C. and was added continuously after the reaction mixture left the polymerizer. The quenched reaction mixture was 250 K1
A medium pressure separator kept at 7 cm2 and a low pressure divider with a pressure of 10 to 9 are led to a separation system connected to 7 series.
Unreacted ethylene and polymer were separated. When stable at m level and no reversal! Table 2 shows the properties of the polyethylene that was cured after 4 hours of cyclic use of core ethitane.

Ratio: 1 + 15 Polyethylene was molded in the same manner as in Example 13 except that no deactivating agent was used. 1lfi of the obtained polyethylene
The raw materials are shown in Table 2.

Example inner diameter 5mm, length 40? Pressure 1000K17cm2, +M +l: 26oC using n-U-shaped reaction 5. Ethylene is converted into 161(ri/I)(butene-1
24Kq/Hr, solid catalyst [II3 o, rs, p/summer (', triethylaluminum 3, O m +nol/
Each was fed to the reactor at a feed rate of Hr. The production uncertainty of polyethylene was 3.5 q/H r. The steps after addition of the deactivator were performed in the same manner as in Example 13.

The results are shown in Table 2.

Note that the meanings of the terms used in the Examples are as in Section F.

(1) MI: Lengthen the melt index, A8TM
+) -1238, temperature 190℃, load 2.1
The measurement was 1- under condition F of 6Kv.

(2) Density It(:, JIS l(-(Measured according to i760).

(3) MW//MN: Waters GPO-1500
It was measured with

(4) Molecule in: Ratio of 5000 or less: Waters Co. (IPn-1500'C Nail 11i).

(5) Resin color: Measure the L value and blK of the Hunter method using a Kakki Machine Co., Ltd. Misaki color difference meter (7).

(Lisu/Kai [l Procedural amendment (spontaneous) October 1980 - Next day Commissioner of the Patent Office Wakasugi I1] Husband 1, Indication of case 1982 Patent Application No. 179076
No. 2 Name of the invention Process for producing ethylene polymer a Relationship with the case of the person making the amendment Patent applicant 1-2-6-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture Revised IJ-Specification ν (1. Name: Process for producing ethylene polymer 2, Claims (1) Ethylene is produced by using a coordination polymerization catalyst containing a transition metal compound and an organometallic adduct in the presence or absence of an inhospitable hydrocarbon solvent. Alternatively, a mixture of etitant α-olefins having 3 to 18 carbon atoms is prepared at an average polymerization temperature of 13
Polymerization was carried out under conditions of 0° C. or lower, and the obtained υ polymer mixture was added with a deactivator and 12 to form a compound of the general formula (where m and Un represent integers of 0 or more, 2, Itl
, n, 2. lir'+ tt4+ R5I IL'
l It'+ 几8r ) L9+ Rj' 辷t Each represents a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms. An ethylene polymer characterized by adding 1 ttr of a polysiloxane compound represented by ) to make the catalyst non-occupied, and separating unreacted monomers from the resulting polymer mixture. Production method (2) according to claim 1, characterized in that a polysiloxane compound containing at least one silicon-hydrogen bond (8i-I+ bond) in the molecule is used as the deactivator 7. Production method of ethylene-tlr combination (3) Ji of the agent is 50 to 111 per mmol of the total number of moles of the transition metal compound and the organometallic compound.
Detailed description of the invention The present invention provides polyethylene and ethylene-α-olefin co-producers i1i Concerning the 4# production method of the combination, % relates to the inactivation of the coordination polymerization catalyst used in the polymerization of ethylene and α-olefins.

Polymerization was carried out using a cape-141 polymerization catalyst. I5 IJ ethythlene and α-olefin copolymers usually have a wide density range of 0.850 to 975 g/-, such as films, blow molded products, fibers, extrusion molded products, etc. is used in large quantities for a wide variety of purposes.

Coordination polymerization catalysts are known as catalysts for polymerizing ethylene or a mixture of ethylene and α-molefin. Coordination gold catalysts include compounds of titanium and vanadium with a
? The transition gold m4 compound that flows into the r:
'1 is included as a relative component.

Ethylene and ethylene α-olefin (/') lR9
In addition to the straw method of polymerization and 15, is the polymerization temperature 130℃ or higher sieved? Solution 1 method of polymerizing with M and crystal temperature/high molecular weight ηi method 3 without using solvent (iJ, Since it requires energy to remove the heat of polymerization, it is an energy-saving method.

In 2011, a highly active coordination polymerization catalyst was developed, and even if the catalyst residue in the 71-coat polymer was removed by extraction with alcohol or caustic soda, the carrier residue in the polymer was extremely weak. The color and thermal stability of the polymer are similar to those of conventional offshore polymers that have been subjected to catalyst removal. When there is a catalyst removal process, the recovered polymerization solvent, unreacted monomers, and clay come into contact with polar compounds, which can cause damage to the vehicle chassis. If you use 1'1
It is necessary to separate these polar compounds in the purification process.

On the other hand, when an Il'+] oil-based catalyst is used, since a chemical compound such as alcohol is not used, there is no need to purify part or all of the polymerization solvent or unreacted monomer (1). ', &; t1, it is possible to reuse it by just processing it in about 1 step (by following the q-it molecular sieve), and it is necessary for making distilled water in-house. This makes it possible to save a huge amount of energy such as steam.

However, if the catalyst removal step is omitted, the contact ν,
is not inactivated, so that polymerization after leaving the 11 reactor, so-called 9j, occurs. In the case of extraction, the weighted eddy current generally sieves the moon from the average temperature in the combiner, so it is preferable to use low-molecular M (wax, grease, etc.).
This causes the formation of When producing oligomers such as butene-1 and chitin-1, and homogeneous ethylene, the density decreases.

In addition, in the high-temperature field pressure method, the conversion rate (of ethylene) is 10~
30%, the catalyst must be inactivated] 2. If not, there will be a large amount of unreacted monomer in the reaction mixture leaving the polymerization vessel, and this will sub-combine and the reaction will not be controlled. There is a huge risk of not causing a runaway anti-Lr1.

When a compound used as a quenching agent is used for the removal of conventional old catalysts such as alcohol, the alcohol is ), evaporates from the iLt combined solution together with unreacted upper ``J, ``+''+ and solvent 1, contaminates the monomers and solvent, and requires purification of the circumferential monomers and solvent.

The present inventors have developed a method that does not have volatile -C itself, does not produce extrusive reaction products that adversely affect the polymerization system even after reacting with a catalyst, and has no risk of contaminating recovered monomers or solvents. As a result of continued efforts to develop a deactivator, the present invention was achieved. Of course, since the quencher remains in the polymer, it is unlikely that it will have an adverse effect on the properties of the polymer, such as color thermal stability.

That is, the present invention provides coordination polymerization/llll comprising a transition metal compound and an organometallic compound in the presence or absence of an inert hydrocarbon solvent.
Using a ft medium, ethylene or a mixture of ethylene and an α-olefin having 3 to 18 carbon atoms is heated to an average polymerization Y grade of 1.
The polymerization is carried out at a temperature of 30°C or higher, and the resulting 7fj polymer mixture is added with the general formula (in the formula m and n) as a deactivator.
ld,' represents an integer greater than or equal to 0, R' +R2+I
IFI IN+ n5+ R6, R'+ R8+ Hu
t 1,10 are each a hydrogen group or a carbon number of 1 to 20
represents a hydrocarbon group. ). 11'IJ
Inactivating the catalyst by adding a siloxane compound in the form of a solution or suspension in an inert hydrocarbon, or in the pure liquid or molten state, from the resulting polymeric thermometal. If the unreacted monomers or unreacted monomers are removed from the inert hydrocarbon solvent, the solvent is separated from the deactivator and the unreacted monomer.
The present invention relates to a method for producing an ethylene polymer, characterized by obtaining a polymer containing a reaction product of the deactivator and the catalyst.

The coordination polymerization catalyst used in the present invention mainly contains transition metal compounds and organometallic compounds! It can be broken down as a component.

As the transition metal compound, use is made of transition metal halides of groups 1 to 2, such as titanium, vanadium halide, panadium mexihalide, and the like. As the organometallic compound, organoaluminum compounds such as alkylaluminium, alkylaluminum chloride, etc., or organic aluminium 11-magnesium complexes such as alkylaluminum-magnesium R form, alkylalkoxyaluminum-magnesium complex, etc. are used.

The coordination polymerization catalyst d1 used in the present invention must have sufficiently high activity that it does not require removal of the catalyst, and must rapidly react with the deactivator of the present invention to inactivate it. There must be. An example of a highly luxurious catalyst used in the present invention that meets these requirements is
09 and JP-A No. 56-59806, a solid Tsuma reaction 1f obtained by reacting a Jisugi, Shin magnesium compound and a titanium compound Qln with L nonanajiuno and compound 1\r-
= compound and a large number of catalysts made of inorganic aluminum compounds.

S2+-W:, 1%'l"l'Open III': 56-
47409 Te is (A) (1) General formula αMg/
JT,',rt2. x', x2. (In the formula, M is A
I.

zn+R, 口e+LI, β is a number greater than or equal to 1, σ, p
.

q+I・s lf O° is a number larger than 1.0, p+q + r + s = mα+2β, 0≦(
r+8)/(α+β)≦1.0, m lI
T, l: The valence of N+, 1t' + rt' is a white hydrocarbon group having 1 to 2 carbon atoms, whether it is the same or Nll, X' + X'' is the same or different group, and hydrogen atom.

onF 1(Is in; It51L" + N
% within I" + S I+, indicates the group 9, ■, 3.I
(7゜T-T R' i-1 represents a hydrocarbon group having 1 to 2 carbon atoms, n! ) and an organomagnesium component soluble in a hydrocarbon solvent represented by the formula (11)
-yl [In the formula, 1110 is a hydrocarbon group having 1 to 2 carbon atoms, X is a halogen, and 0≦n≦3] is added to the organomagnesium component of (1) (
The titanium compound of 11) is reacted at a molar ratio of 1.1 to 4.0, and the isomer reaction product produced by M) and (B) with T'S.
Catalysts made of aluminum compounds are disclosed.

Also, the general formula M(XM, / n, 1,1tz9x'
, x”, (where M tri A I +Zn + n
+ Lle * Li, and β is a number greater than or equal to 1, α.

p + q + r + S I'll', O or a number greater than 0, p + q + r + s
= mα+2β, 0≦(r+s)/(α+β)≦10
m Irj, the valence of M, R,′+
I(; 1171 A hydrocarbon group having 1 to 2 carbon atoms which may be the same or different, XI and X2 are the same group or d
Different groups, hydrogen atoms.

OR3, O8+ R; n, 5 tt' l NIL'
IL8r S R' represents a group, R3+1171R9
8, 9 represents a hydrocarbon group having 1 to 2 carbon atoms, and n! + n, s l R6 is a hydrocarbon group having a hydrogen atom and a carbon atom number of 1 to 2°);
The isomeric reaction product of ID with a titanium compound that puts on the tongue at least one halokenomiko is expressed as (lli) llft formula 'I' i X a (01LIO)4- a +V(
)X 6((,lB'')3-+3 + and V'X c
((')11.”)4-c (in the formula, X is halogen J, G
O is a hydrocarbon group having 1 to 2 carbon atoms, l is
l;) Rashi, a i, l 1-4, b is 1~: U, C
is selected from titanium and vanadium compounds represented by 1 to 4 (only 9 is 9);
13) A catalyst consisting of a Fusakaki aluminum compound is disclosed.

Another example of a suitable catalyst for use in the present invention is
! Hourly opening 1u'56-26905.28206.3250
4゜45910.47408.59805 and Unexamined Patent Publication TL
(457-16 (l 05 includes N1:1 catalyst).

Examples are: 1) 4αM to the general formula, 11.1, 1D21. x',
X2. l) l (4 in the formula is from group Ⅰ to m of the periodic table.
family gold m) Dr., a, p, q + r tri,
o size is above 0, S is greater than 0 and 1 or more 1, t is 0 or a number greater than 0, p + q + r 10s
2mα+2゜0<(r+s)/'(σ+1)≦1
．． 0, S≦1, m is the valence of M, 11. '
, 11.2 has 1 carbon atom, which may be the same or different
~20 hydrocarbon groups, Xl is a hydrogen atom or oxygen, 4
In the hydrocarbon solvent represented by 111 represents a child-isolated compound), Soluble bound magnesium compound and U (ll) gt
Hydrogen chloride, organic halides, boron, aluminum, silicon, gel manila l1, tin, lead, phosphorus, arsenic, anotymon, bismuth, 1 (1 lead, cadmilla A, zk trowel (D)
] - A mixture of one or more selected from halides I, (lii) a titanium compound/and a vanadium compound 1 is brought into contact with the reactant.
This is a catalyst consisting of a catalyst component [A] and a genus compound [B].

Another example is the queen component [A1 and organic: Imaka compound [I3
] It is a catalyst consisting of.

Ingredients [^] l-) The presence of J Rizu (3) (4) and (
React 5) to 1! ν solid catalyst (1) General formula Mα1lil gI+,'-'9・I),
(In the formula, M is a metal atom of Group Ⅰ to Group 3 of the Cylindrical Periodic Table, α・p
・q・rld.

With the above numbers, p+q=mα+2.0≦q/(α+1
) <All relations of 2>[j' L,, m is the valence of M, R'
is one or two hydrocarbon groups having 1 to 20 carbon atoms
a mixture of more than one species;
A mixture of 2 and 1 or more organic magnesium compounds represented by D (d, th' child-donating 4h compound 1) (2) halides of boron, silicon, germanium, tin, phosphorus, antimony, bismuth, and zinc捷p,
Id; , one type selected from 11 hydrogenated hydrogens or 12
Solid component (4) from the reaction of mixture (3) (1) and (2) above 41111
) Organometallic compound (5) - All transition class compounds of any of (a) to (d) + a) titanium compound, (b) vanadium compound,
(C) titanium compounds and vanadium compounds, (d) titanium compounds and zirconium compounds.
I (in the formula, M is a metal atom of Groups ■ to ■ of the periodic table, α
+p+q+r+8 is 0 or a number less than or equal to
s )/(a-i-β)-Sl, 0, m is the valence of M, ti(J: O!l: 7'?: is ()
is a larger number, n,', RF is a hydrocarbon group having 1 to 2 carbon atoms, which may be the same or different, XI, x
2I′i is the same or different group, 7 is an elementary atom or oxygen, g is a negative group that contains a yellow atom, and ■) is a harmful inorganic compound. Used organomagnesium compound and (
IIJ Hemorrhoid Hydrohydride Machine Halides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic,
A catalyst component obtained by contacting a reactant of antimony, bismuth, zinc, cadmium, and mercury halides with a titanium compound or/and a vanadium compound [ A'l
and organometallic compounds [! 3].

The α-melefin used in the present invention has 3 to 18 carbon atoms, and examples thereof include zoropyrene, butene-1, pentene-1, hexene-114-methylpentene-1, heptene-1, Octene-1, Nonene-11
A'sen-1 etc. can be used for φ without being used alone or as a mixture.

The IJi polymerization method used in the present invention has a polymerization temperature of 130°C.
It is carried out under the high temperature conditions listed in -1- below.
7 Teshi” 1, Inactive’I! 'In the presence of hydrocarbon clear ν, 1
30° ~; 400°C polymerization τM, 1q゛, jO ~ 500
Solution 111 method for 7-hour polymerization of a mixture of ethylene/ethylene and α-olefin at a polymerization pressure of atmospheric pressure, low density ty of conventional radical polymerization, 4? By supplying a coordination catalyst instead of a radical catalyst to a polyethylene plant, ethylene or a mixture of ethylene and α-,n-1/fins can be
There is a high 114 i% pressure polymerization method in which polymerization is carried out at a polymerization temperature of 30° to 300°C and a polymerization pressure of 200 to 30θO atm.

Examples of inert hydrocarbon solvents used in the welding process include butane, pentane, hexane, cyclohexane, heptane, octane, inoctane, nonane, decane, dodecane, and the like. These can be used alone or as a mixture.

Specific examples of solution type method include O, 'l', B15
There is a process described in 1975 tz)Izs Japanese Issun Canadian Special No. 980498 of tnn.

Takashi Takabuchi, JT: In the polymerization method and 1-2, there are the autoclave method using a mate crepe reactor, the tubular method using a tubular reactor, or the combination of an IT autoclave and a tubular reactor. Each step of polymerization includes a multi-stage polymerization method. -, l As an example of high temperature high pressure polymerization method +1:J, IIP 932,231, II'
1,205,635, t18F 1,161,737
etc. can be given.

After the polymerization was completed, the reaction mixture coming out of the H1 reaction vessel contained the polymer, unreacted monomers, a coordination polymerization catalyst partially in an active state, and an inert hydrocarbon solvent. When the inert hydrocarbon solution ν is contained. A deactivator is mixed with the reaction mixture to prevent postpolymerization and to deactivate the catalyst. The embankment t9r for mixing the deactivator and the reaction mixture may be a small diameter vacuum knob located between the polymerization vessel and the polymer separator. CJ as a way to mix, two l in a year! i('It is possible to combine the flows in the pipes, or to mix them in a mixer such as a study mixer or an in-line mixer, etc., so that the catalyst and the deactivator come into contact quickly. 1 Either method is fine.

The total amount of deactivator added must be sufficient to ensure deactivation of the catalyst. Ill'
l! The inactivation of the medium is carried out by inactivation of at least one of the structure 1 and components of the medium, namely translucent metal compounds and organic metal compounds. However, in the case of a quenching agent, it is necessary to use an amount sufficient to react with both catalyst components.

The amount of the quencher included in the present invention is in the range of 501 ng to 1 (100 fflr.
At this point, the deactivation is sufficient, and at 1,000 mm or more, the deactivating agent remaining in the polymer or the reaction product of the deactivating agent and the catalyst will have a negative impact on the performance of the polymer. .

The polysiloxane compounds used in the present invention can be used as various silicone oils, namely methylhydrogen silicone oil, dimethyl silicone oil, ethylhydrogen silicone oil, methylethyl silicone oil, methyloctyl silicone oil, methyldecyl 7 silicone oil, methyl Octadecyl silicone oil, methylphenyl hydrogen silicone oil, methylphenyl silicone oil 1. diphenyl silicone oil, decamethyltetrasiloxane, 1,
1,1,3,5,717.7-octamethyltitranoxane, octamethyltrisiloxane, 1,1°1.3
, 5,5.5-heptamethyltrisiloxane, 1°1.
3,3.5.5-hexamethyltrisiloxane, 111
．． 3,5,5-pintaphenyl-1,3,5-trimethyltrisiloxane, 1,3,3,5-tetramethyl-1
゜1.5.5-Tetraphenyltrisiloxane, hexamethyldisiloxane, pentamethyldisiloxane, 1.
1.3.3-Tetramethyldisiloxane, hexaethyldisiloxane, 1.3-dibutyl-1,l.

3.3-tetramethyldisiloxane, hexane-n-zolopyldisiloxane, 1.3-dimethyl-1,1,3,3-
Tetraphenyldisiloxane, 1,3-diphenyl-1
, 1,3,3-tetramethyldisiloxane, hexaethyldisiloxane, and the like. These can be used alone or as a mixture.

Among these, it has a higher degree of polymerization and a higher boiling point,
Preferably, methylhydrodiene silicone mail, ethylhydrodiene silicone mail, methylphenylhydrodiene silicone oil, dimethylsilicone oil, methylethyl silicone oil, methyloctyl silicone oil, methyldecyl silicone oil, and methyloctadecyl silicone oil have excellent thermal stability. .

In particular, various hydrogen polysiloxanes having a 5i-H bond are particularly suitable as they have high reactivity with catalysts.

The deactivator is dissolved or suspended in an inert hydrocarbon solvent,
Alternatively, it can be added to the reaction mixture in pure liquid or molten state. 1. When an inert hydrocarbon solvent is used, it is preferably the same as the polymerization solvent. If different, it must not cause any adverse effects on the recycling of the polymerization solvent.

The reaction mixture with the quencher 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 remain in the polymer without being gasified in the polymer separator. The obtained polymer is added with an antioxidant and, if necessary, a catalyst neutralizer, and finally pelletized using an extruder.

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

This prevents uncontrolled runaway polymerization of unreacted monomers in the polymer separator, and also suppresses the formation of low molecular weight polymers (wax, grease, etc.) due to post-polymerization. (2) Clever (-) side reactions, such as the formation of butene-1 due to ethylene conversion, are suppressed. (When butene-1 is produced, the density of the ethylene homopolymer decreases.) (3) The monomers and inert hydrocarbon solvent recovered from the reaction mixture can be recycled and used by passing them through various purification steps or a simple purification step. (4) Inactivation remaining in the polymer A polymer with excellent color and thermal stability can be obtained without adversely affecting the properties of the polymer due to the reaction product of the agent or deactivator and the catalyst.

Ethylene copolymer V: /I'i of the present invention, of course the usual stabilizers, ultraviolet absorption J1y agents, antistatic agents, anti-Zorocking agents, lubricants, pigments, free or organic fillers, Substances normally added to polyolefins, such as rubber and other small amounts of polymers, can be added.

This first addition (for example lhB lj, l, BHT1
Shell Ionox 33o1 Gridrich Gutdry) 3114, Chi/9 Geigy Irganox 1010, ]076, Tinuvin 327, Sankyo Pharmaceutical Co. 1, S 770, L S 622, DMTP, I) L
TP, calcium stearate, hydrotalcite, neutral magnesium carbonate, erucic acid amide, oleic acid amide, titanium white, calcium carbonate, card d
? black, talc, styrene-butadiene rubber,
Examples include ethylene-vinyl acetate copolymer, high-pressure polyethylene, ethylene-zolopyrene rubber, polyzolopyrene, and the like.

The present invention will now 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, a bexane solution of 7 runs of trichlor, 0.5 mol//1.61! and hexane 1.27? was charged and the temperature was raised to 70°C. Next, A 1045Mg (n f
lu k75(On-Uu)o, 7 (metal concentration Q, 9
mnl77? Octane solution) 0.45p and Hekiza 7
0.35e was introduced at 70° C. over a period of 111 h.

Further, hexa706/ml containing 140.7 g of T i O was introduced, and the reaction was carried out at 70° C. for 1 hour. The produced insoluble solid is designated as catalyst A. Titanium (Ti)-containing jt in catalyst A
'II: It was measured and found to be 0.5% by weight.

In addition, A lo, ls Mg(n-Bu 'h, n (
On-Bu ) o and t were manufactured according to Japanese Patent Application Laid-Open No. 57-5709.

(Synthesis of four bodies, H) In the same way as A, Alo, +sMg (n-Bu Takumi 75 (O
n + 3u) 0.7400 mmol, trichlorosilane 400 mmol, and nononadyl trichloride 8.8 m m
Synthesis was carried out using 12 mmol of titanium tetrachloride. Vanadium (V) and titanium ('r+) in catalyst B
The total content was 20%.

(Synthesis of solid catalyst 0) Oxygen and moisture inside a 500-capacity flask equipped with two M1 funnels were removed by dry 9-element substitution.1.
．． Add 160 rne of hexane and cool to -10°C. AlMg3.9 (n-c4Hs)+<,s in r'x
A heptane solution containing 41) mmol of H(On-04Hg)o, 4 as organomagnesium-aluminum compound of silk composition 80 tn
l, and n-butoxytitanium trichloride l' 60 n
80 td of hexane solution containing + mol was weighed into each dropping funnel, and both components were added simultaneously at -10°C under stirring.
The mixture was added dropwise over a period of time, and the mixture was further aged at this temperature for 3 hours. The resulting hydrocarbon-insoluble solid was washed with mono*[,,n-hexane and dried to yield a solid product in 11.2. The Ti content was 213m%. Furthermore, A'Mg
5. s (”-041-19)+<, 5((ln C4
14) 6.4 was threatened according to Example 1 of JP-A-56-47409.

(Synthesis of homogeneous catalyst 1) A1g3 (OzHs)+, s (no411++
)s ((+8 + H-0113+ C3zH5
)
40 aluminum compound as organomagnesium component
Heptane solution containing m+no19 80m/! and 80 ml of a heptane solution containing 40 mmol of titanium tetrachloride.
1 to each M) Weigh j&j-1160- of hexane into the lower funnel Wn: 500rd.

Both components were simultaneously added dropwise over 1 hour to a flask purged with nitrogen at 0° C. while stirring, and further aged at this temperature for 3 hours. Raw IJv! The snout was filtered [7] and washed with heptane to obtain the homologous product. Subsequently, this solid reaction product ``
The composition Ti (,3
13,5(On-04He)o,s titanium compound 30
Add 0 mmol and react at 130°C for 3 hours.
Obtained 2g of solid catalyst [D]. The content of 1゛i is 19.
I was in charge of 8. The above-mentioned magnesium aluminum compound was synthesized according to the example of JP-A-56-59806.

Examples 1 to 7.1-1 Comparative Examples J to 4 Each set of 100e was prepared (1-1 In a polymerization vessel equipped with a stirrer, solid catalyst A was added to 1.0g/fir Sm1 degree 0.1 m
A cyclohexane solution of triethylaluminum of mol / / was added at 200p/Hr (triethylaluminum 2
0 m+nnl/Ilr), ethylene ke251<q
/ )lr and hydrogen were continuously supplied at IKri/l-1r, respectively, and polymerization was carried out at a temperature of 200° C. and a pressure of 80 Kz/J. The 1p conversion rate of ethylene was about 80, and the produced phase of polyethylene was about 20 kg/)Ir.

The γ loss was made into a 2w+% solution or slurry solution of Schiff 111 hexane and was continuously enriched after the reaction mixture left the offshore vessel. The reaction mixture mixed with beef oil was heated to 250℃ using a heat exchanger, and then divided into portions using a stainless steel 2-Dolno ζ lubricant at a rate of 1,000 kq/J. Introduced into the vessel. Gaseous unreacted ethylene and cyclohexane were continuously collected from the top of the separator, and a slurry of polymer cyclohexane 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,
The mixture was transferred to a vented extruder and made into pellets. The pellets obtained were pulverized, vacuum dried to completely remove the pellets, and the basic marine properties of the polymer were measured.

In addition, when the 1-1 polymerization has started and the polymerization is safe, continuous circulation of the ethylene and cyclohexane recovered from the separator to be used in the 1-1 and 1-1 reactions without distillation purification is started. A saw that goes for 5 hours straight.

As for the insufficient f/i of recovered ethylene and cyclohexane, fresh ethylene and cyclohexane were used.

At the time of offshore stabilization after the start of polymerization and after 4 hours, the amount of polymer production (polymer production amount fg per 1 g of solid catalyst) on the solid catalyst was measured.

This makes it possible to determine how much of an adverse effect the quencher has on 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. Test results for seven quenchers are shown in Table 1.

As is clear from the results in Table 1, when no deactivator is used (Comparative Example 1), the amount of low polymer products increases, the molecular weight distribution (vw/MN) becomes broader, and after 4 hours of cyclic use. The grotactical efficiency and density of the material decreased.

Also, when methanol is used as a deactivator (Comparative Example 2),
When the Mf synthesis is stable, a polymer with normal properties is obtained, but when the circulation of unreacted ethylene and solvent cyclohexane is started, the activity rapidly decreases, and after 4 hours of 1ψ of circulation, a polymer with normal properties is obtained.
Polymerization has completely stopped.

On the other hand, when the polysiloxane compound of the present invention was used as a deactivator (Examples 1 to 7), a polymer with a sharp molecular weight distribution and good color was obtained, and after the recycling of unreacted ethylene and solvent cyclohexane, However, no decrease in density or productivity was observed. Also, if the amount of the quencher is small (Comparative Example 3), the molecular weight Xfj will be wide, and if the amount of the quencher is too much, the color of the resin will be poor.

Example 8 In a polymerization vessel with a stirrer having a capacity of 1001 V, 1.3 g/Hr of solid catalyst A was added at a concentration of 0.1 m+nol.
200 p/L (r(triethylaluminum 20
mmol/Hr), ethylene 29 Kq/Ilr
, butene-1 was continuously supplied at a rate of 1 Q Kq/Hr, and polymerization was carried out at a polymerization temperature of 200° C. and a pressure of 80 Kq/J. The polymerization conversion rate of ethylene is approximately 85%, and the amount of ethylene °butene-1-11:IC combination is approximately 18K.
g/l-1r. The combined reaction mixture was treated in the same manner as in Example 1. The crab results obtained are shown in Table 2.

$ Stream side 9 12 K/H of Mectene-1 instead of Butene-1
An ethylene-octene-1 co-car combination was obtained in the same manner as in Example 8 except that r was supplied. The obtained results are shown in the second
Shown in the table.

Example 10 Polyethylene was obtained by flying in the same manner as in Example J except that solid catalyst B was used instead of solid catalyst A. The results obtained are shown in Table 2.

Example 11 Ethylene-butene-1
Military combination λ・obtained. The results are shown in Table 2.

Example 12 [Polymerization was carried out in the same manner as in stain flow side 9, except that a homogeneous catalyst was used in place of the solid catalyst A, to obtain an ethylene-ocdene-J co-polymer. '7% leakage results are shown in Hx 2 table.

Example 13 Ethylene was produced using an autoclave with an internal volume of 2/2 and equipped with a stirrer. Polymerization pressure 1200 Kq/err?
.

At a reaction temperature of 220°C, ethylene 40 Icq/ITr
, (41-body catalyst (A) at 0.15 u/Ilx)
Ethylaluminum was fed to each reactor at a feed rate of 30 mmol/Ilr.

The amount of polyethylene produced was 3.8 Kp/Hr. The quencher was added continuously after the reaction mixture exited the MI combiner by pouring it into a mineral oil with an equal boiling point of 150°C. The inactivated reaction mixture was 250Kg/l
A medium pressure separator maintained at ri and a low pressure separator maintained at a pressure of 10 Ky/J were introduced into a separation system connected in series to separate unreacted ethylene and polymer. Table 2 shows the properties of the polyethylene obtained when the 111' reaction was stabilized and after 4 hours of circulating 1 ton of unreacted ethylene.

Comparative Example 5 Polyethylene was obtained in the same manner as in Example 13, except that no deactivating agent was used. IF of the obtained polyethylene! r
The properties are shown in Table 2.

Example 14 Using a tubular reactor with an inner diameter of 5 mm and a length of 40 m, the pressure was 100
01 (q/cJ) at a temperature of 260°C. Supply of ethylene at 15 Kq/TTr, butene at 124 Kg/Hr, solid catalyst [B] at 0, 15 R/Jlr, and triethylaluminum at 3.0 mmol/Hr. The amount of polyethylene produced was 3.5 Kg/Hr.
The culm was prepared in the same manner as in Example 13.

The results obtained are shown in Table 2.

Note that the meanings of the terms used in the examples are as follows below.

(1) Ml: represents melt intex, A8'l'M1) -12:38, temperature -1
Measurement was carried out under the conditions of 90°C and a load of 2.1 kg.

(2) Density: Is K-6760 and 1l11.

(3) MW/MN: Waters 0PO-15
0 (4) Molecule/Rhin-5000 ratio: Waters Inc. (IP (measured with 3-1500).

(5) Resin color: L value and b value were measured by the 1-4unter method using a color difference meter manufactured by Color Machine Co., Ltd.

Margin below

Claims (1)

[Claims] (1) In the presence or absence of an inert hydrocarbon solvent, ethylene or ethylene and a carbon number A mixture of 3 to 18 a-olefins is marketed at an average polymerization temperature of 130° C. or higher, and the polymer mixture is subjected to sufficient deactivation to render the catalyst inactive. agent, general formula (in the formula, 1jl and mouth represent an integer of 0 or less, Bl
, R2, R3, R4, Bll, Be, B?
, R8 and R9°Rlo each represent a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms. ) is added to an inert hydrocarbon in a solution or suspension state, or in a pure liquid or molten state, and the catalyst is rendered inactive by mixing. Separating unreacted monomers or unreacted monomers and an inert hydrocarbon solvent from the mixture, and separating the polymer containing the deactivating agent and the reaction product of the deactivating agent and the catalyst. (2) At least one silicon-hydrogen bond (S
Claim 1, which is characterized in that a boria xane compound containing (i-H bond) is used as a deactivator.
5(llp~1000q
(4) A method for producing an ethylene polymer according to claims 1 or 2, characterized in that the Ziegler type catalyst (A) (i) has the general formula -Mg, R'pR% X', X"
, (in the formula, M is AI. Zn, IJ, Be, Li, β is the number less than l, α
. p, q, r, sv 0! , or is a number greater than O,
p ''-q + r 10s == m α''-2β,
The relationship 0≦(′−toS,+β)≦1.0 is established, and m
is the valence of M, R1 and 几2 are hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different/2, X' −+
X' is different by the same size, hydrogen source, OR, 3, O
8il'L'R'几6, NB? B.B. 8 几91 group, It, 3. Rin? , R8, B1
1 represents a hydrocarbon group having 1 to 20 carbon atoms, R'
, R'. Il,' is a hydrogen atom or a carbon 7 having 1 to 20 carbon atoms
The hydrocarbon solvent represented by the formula Ti (OR'°
).・In the x*-nC formula, R" is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and 0≦n≦3] is added to the organomagnesium component of (1). The titanium compound of (11) was added to the ring 1 at a molar ratio of 1.1 to 4.0.
．． A method for producing an ethylene polymer according to Sections 1 to 3 of the scope of Patent No. 8, which is characterized by using a solid reaction product obtained by squeezing and (3) a catalyst comprising an organoaluminum compound. (5) As a Ziegler type catalyst (A) (i) General formula M , M g / R', R2,
X', X2. (In the formula, M is AI, Zn. B, Re, L+, β (number of 1 to 1, α1p
IQlr, s is O or a number greater than 0, p+q
+r + s = mα+2β, 0ku(r1S)/(α
+β)/:1.0, m is the valence of M, 几1
．． FL2 has 1 or more carbon atoms, which may be the same or different
20 hydrocarbon groups XI and X2 are the same or different groups, hydrogen atom, OR3,08iR'RIIR',
N exit, 7rt8. SR,” indicates a group, 几3.
几7, R8, ILQ represent a hydrocarbon solvent having 1 to 20 carbon atoms, R4, B5, RQ represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) 1. An organic magnesium component soluble in an aqueous solvent and (i+) a titanium compound containing at least 11 solid nitrogen atoms. S1 body skin L5. Generation (i e,
(iii) General formula TiXa(OR,”)4-, , V
OXb(OR”)3-b and VX'c(OR10)4
-o (in the formula, X is...a rogen atom, R10 is a carbon atom number of 1
-20 hydrocarbon groups, a is 1-4, b is 1-4
3.C is a number from 1 to 4)) By reacting with at least one compound selected from titanium and nonadium compounds represented by ('4),
3) A method for producing an ethylene polymer according to claims 1 to 3, characterized in that a catalyst consisting of an organoaluminium compound is used (6) As a Ziegler catalyst, (i) General formula M a M gR'p R'q X'y
X"@D or a number greater than 0, p +
q −1−r + s = mα+2.0 < (r+
s )/(α+1)≦1.0, S≦t, and m
is the valence of M, rLl, R2 is a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different; atom, D represents a child-donating organic compound) which is soluble in a hydrocarbon solvent, and (11) hydrogen chloride, an organic compound.
Logenides, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth,
1. to the reactant of one or a mixture of two or more selected from zinc, cadmium, and mercury compounds. (i
ii) Contact with titanium compound or/and nonadium compound! A method (7) for producing an ethylene polymer according to claims 1 to 3, characterized in that a catalyst consisting of a catalyst component (A) consisting of ~ and an organometallic compound CB] is used.As a Ziegler catalyst, The following ingredients [A]
and an organometallic compound [B] A method for producing an ethylene polymer according to Claims 1 to 3, characterized in that component [A] is used in the presence of (3) shown below ( 4) and (5) Solid catalyst (1) General formula M tt M- et al. ,
q and r are numbers greater than or equal to 0, and p + q = mα+
2.0≦q/(d+t)
:Valency of M, R' is one or more hydrocarbon groups having 1 to 20 carbon atoms, X' is a hydrogen atom or oxygen, nitrogen or sulfur atom. An organic magnesium compound compound represented by a negative group (I) or a mixture of two or more (D represents an electron-donating organic compound) (2) Boron, silicon, germanium, tin, phosphorus, antimony, bismuth , salivary lead halide still vi
One type selected from hydrogen chloride or 214! Mixture (3) of (1) and (2) solid component (
4) Organometallic compounds/proboscis (5) "Any of the transition metal compounds (a) to (d) in F. (a) titanium compound, proboscis, (b) vanadium compound, (C) titanium compound" and Nononadium compound,
(d) Titanium compound and zirconium compound (8) As a Ziegler catalyst, (i) General formula MaMg/R'pR2,X'rX2. I)
1 (In the formula, M is a metal atom of Groups ■ to Group ■ of the periodic table,
αI pl Q + '+8 is O still a number greater than or equal to 0,
β is a number greater than 0, 3, p+q0r+s−mα+2
β, 0≦(r10g)/(α+β)≦1.0, m is the valence of M, t is a number larger than 0, and the furnaces and 几2 are the same or different. 1 or more carbon atoms
20 hydrocarbon groups, An IjT-soluble organomagnesium compound in the indicated hydrocarbon solvent and (11) hydrogen chloride, organohalide, boron, aluminum, silicon, germanium, tin, lead, phosphorus, arsenic, antimony, bismuth, zinc, and hydrogen chloride. P
Catalyst component CAI and organic metal made by contacting (iii) a titanium compound or/and a pana-noum compound with the reaction proboscis of one or more mixed proboscises selected from halides of mium and mercury. A method for producing an ethylene polymer according to claims 1 to 3, characterized in that a catalyst consisting of compound [13] is used.