JPS5869215A - Continuous production of propylene/ethylene block copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer of a quality comparable to that obtained by batchwise polymerization by a continuous manner, by classifying a slurry from a propylene polymerization tank, then introducing the slurry into a propylene-ethylene copolymerization tank and, after adding a fresh aluminum halide compound, effecting the copolymerization of the reaction mixture. CONSTITUTION:To a propylene polymerization tank A are fed a catalyst 1 consisting of (i) a titanium-containing solid catalytic component and (ii) an Al compound of formulaI, wherein R1 is a 1-20C hydrocarbyl and 3>=m>1.5, and liquefied propylene 2, and the propylene is polymerized therein. The formed PP slurry is discharged via a pipe 3 and separated in a liquid cyclone B into a thickened PP slurry 5 and a supernatant liquid 4. The former is fed to the upper portion of a hydraulic settling classifier C and the latter is fed to the bottom of the classifier. In the classifier C, the thickened slurry is contacted coun tercurrently with the supernatant liquid, and the sedimented PP is transferred via a pipe 7 to a propylene-ethylene copolymerization tank D, where PP not sedimented is transferred via a pipe 6 to the tank A. The tan D is further fed with ethylene 8, propylene 9 and an Al halide compound 10 of formula II, wherein R<2> is R<1> and 1.5>=n>=0, and the mixture is copolymerized to obtain a block copolymer 11.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for continuously producing a propylene-ethylene block copolymer having excellent low-temperature impact resistance.

Crystalline polypropylene has the disadvantage of insufficient impact resistance at low temperatures.Currently, the best way to overcome this problem is to use a propylene-ethylene block copolymer as k. In order to produce this propylene-ethylene polymer with high productivity, a device consisting of a plurality of polymerization tanks connected in series is used to homopolymerize propylene in the first step, and then in the first step. A common method is to continuously carry out a combination of ethylene and propylene containing a relatively large amount of ethylene.

When using a multi-tank series continuous system like Jin, the logging reactor used is a so-called complete mixing type. Over a long period of time, the effluent extracted from the m contains catalyst particles themselves that do not contribute to the reaction, or small particles with insufficient polymer growth, which were extracted after a short bath. Various particles are included, including particles that have grown to a high molecular weight and/or coarse particle size due to stagnation. When the effluent in this state is fed to a propylene-ethylene copolymerization tank @Fi, the copolymer produced generally tends to have lower low-temperature impact resistance than that obtained by a batch method, and historically, the propylene polymerization tank The appearance of molded products becomes poor due to the formation of gel due to the particles grown over a long period of time due to the sheet-passed particles and copolymerization rights.

In order to solve these problems in continuous polymerization, glazing methods have been proposed.

For example, Japanese Patent Publication No. Shojj-21111 and Japanese Patent Publication No. 4I-18-11-11 Tata O@WCId have proposed a method using a large number of reaction vessels. Jin's method yields a block copolymer with physical properties close to those obtained by the batch method, but as the number of counts increases, construction costs increase, which is economically disadvantageous. As the number of tanks increases, product quality control becomes more complicated.

Tokukai Akira! J-1164117 discloses that during the first step of propylene-ethylene copolymerization, an electron-donating compound 4
A method of adding IIl11 has been proposed, but according to the results investigated by the present inventors, this method cannot be said to be sufficiently effective. A method for lowering the molecular weight during stepless propylene-ethylene copolymerization has been established. However, according to the results of studies conducted by the present inventors, this method resulted in a decrease in the impact resistance of the molded product.

Furthermore, Japanese Patent Publication No. 104333 discloses that the slurry in the first stage reaction tank is extracted from the wall of the reaction tank while stirring, and the slurry is extracted from the wall of the reaction tank while being stirred.

By counter-current washing with fresh media similar to the slurry media, a slurry with a substantially lower small particle content can be obtained and the liJ
A method of feeding a stage reactor is shown. [7 or [
7. However, the reactor suitably used in this method tends to form portexes and tends to cause particle concentration distribution within the tank, making it impractical. In other words, portex formation not only reduces the effective volume of the reactor, but also makes it difficult to control the liquid level, and if the particle concentration in the tank is distributed,
The effective residence time of the particles is reduced. There is also a possibility that stable operation cannot be achieved because the polymerization proceeds non-uniformly. Therefore, this method is difficult to apply in actual industrial production.

Furthermore, in JP-A-9I8JJ-//67/4, a slurry obtained by polymerizing propylene is continuously classified using a centrifuge and a liquid cyclone, and the entire slurry of coarse particles of 2θ to F7N is separated into ethylene- A method of supplying propylene copolymer to hinoki cypress has been proposed. However, according to the results studied by the present inventors, this method showed a tendency for the impact resistance of the molded product to decrease.

The various methods that have been proposed in the past, such as Jin, are still more satisfactory than the simple multi-tank series one-metal method, and compared to the batch method, each of which has some improvements. The present inventors have taken advantage of the advantages of continuous polymerization, and as an industrially advantageous method, in a method of continuous polymerization in serially connected polymerization tanks, we have developed a process between propylene polymerization tanks of shiI & 1 or between globylene polymerization tanks and globylene 1 polymerization. I previously proposed that a special classification system be installed between 11 stages of globylene and ethylene.
P/ ) This method improves the low temperature embrittlement and poor appearance observed as foreign gel, which are disadvantages of the continuous 1-method, and makes normal molded products different from those from one batch process. A product showing almost the same quality was obtained.

However, in the field of thin hats and injection molded products, which have become increasingly demanding in recent years, there are still aspects that are not sufficient. In molding in this field, strong orientation tends to occur during molding, and there are small gels such as #l that cannot be detected with the naked eye, causing a significant shadow 41t, which becomes a problem when used at low temperatures. Pull in the right angle direction! It was found that the low temperature brittleness against In stress was poor. Also, in the low-temperature falling ball test for a thin injection flat plate, the difference from the one-batch method is clearly visible.

As a result of further research to solve this problem to the Mth order, we discovered a surprising result by adopting a classification system and adding a new and unsatisfactory aluminum halide compound to the one-step copolymerization reaction. I discovered that it had a certain effect and made a single shot of fJ#VC'iA.

The present invention makes use of the advantages of continuous one-cup production, has four advantages in terms of equipment, allows for stable operation, and has the same excellent quality as a thin injection molded product in 1 batch. The object of the present invention is to provide a method for continuously producing a propylene-ethylene block copolymer that can be obtained by using a titanium-containing isocatalyst component and the general formula MzR104. -m (in the formula, R1 represents a hydrocarbon group with carbon number/~λθ, and 1m is J≧brittle) 1.2
Using a catalyst system mainly consisting of an organic al-1-um compound represented by In a continuous method for producing a propylene-ethylene block copolymer in which a combined slurry of propylene-ethylene is sent to a copolymer to perform stepwise propylene-ethylene copolymerization, the step K) between stage II/ and the first stage A classification system was set up for ff, fP) M-2m floor propylene-ethylene copolymerization using the general formula mR%, n(
In the formula, Hm represents a hydrocarbon bulk group of carbon number) to coO, and!
represents a halogen atom, and n represents the number of /, j≧n≧O) is added to the button. It depends on the manufacturing method.

The present invention will be explained in detail below.

In the present invention, the globylene-ethylene block copolymer is produced by a multi-step method, and the polymerization is carried out using a slurry containing an inert hydrocarbon such as hexane or heptane.
It can be applied to either polymerization or bulk polymerization in which only propylene is polymerized in a tube without using an inert hydrocarbon (slurry polymerization using propylene itself as a solvent).

In the process of the present invention, propylene is polymerized in the m/stage in the presence of a catalyst system consisting of a titanium-containing solid catalyst component and an organoaluminum compound.

As the titanium-containing monolithic catalyst component, a known carrier-supported catalyst component obtained by contacting a solid magnesium compound, titanium tetrahalide, and an electron-donating compound can also be used, but preferably titanium trichloride is the main component. That is.

A solid catalyst component whose main component is titanium trichloride.

For this purpose, titanium tetrachloride reduced with metallic aluminum, hydrogen or organoaluminum compounds, or ground titanium tetrachloride, and also those that have been subjected to contact treatment with an electron-donating compound or pulverized titanium tetrachloride are also used. Possible but %%
It is preferable that the aluminum content is 0. /i or less, preferably o
, i, more preferably O0θ or less.

And it contains a complexing agent. The content of the complexing agent is preferably 0.007 or more in molar ratio of the complexing agent to titanium trichloride in the solid titanium trichloride-based catalyst complex.
．． 07 or higher.

^ Physically, titanium trichloride, the atomic ratio of aluminum to titanium in titanium trichloride, is θ, l! The formula 'JR
"pxs-p (in the formula, R"a carbon number/-J Or) a hydrocarbon bulk group, Those containing a complexing agent in a molar ratio of 0.00/or more to titanium dichloride and titanium trichloride, such as those with the formula "OAm", ('JR"p"5-p
)s l)1 (In the formula, R"U is a hydrocarbon group with carbon number/~-〇, X is a halogen atom, and p ke O≦p≦
- is the number of %0 complexing agent (To), B is 0. /ji or less, and t is a number not less than 0.0θ/), but of course, TiO4 component, A
In addition to zR%,
, MgO4! The carrier may contain an inorganic solid, an olefin polymer powder such as polyethylene or polypropylene. Examples of the complexing agent 0 include ethers, thioethers, ketones, carboxylic acid esters, amines, carboxylic acid oxides, and polyxane groups, among which ethers and thioethers are preferred.

As the ether or thioether, the general formula R4-0-
R1 or R4-8-R1 (in the formula, R4, R1 is the number of carbon atoms
! The following hydrocarbon groups are shown. ).

MulRa,,xa-,toke,Mutat1,Mu1Ra
J, etc.

However, such a solid titanium trichloride catalyst complex.

0) Liquefied in the presence of an ether or thioether and precipitated from a liquid containing titanium 9 trichloride at a temperature of 110°C or lowerfp) Obtained by reducing titanium tetrachloride with an organic aluminum compound or metal aluminum Solid titanium trichloride%
It can be easily produced by methods such as treatment with a complexing agent and treatment with a halogen compound.

The above methods (a) and (b) are
J1 issue, same J1-/da j- issue, same! Same as J-J*/P4! ! -1003 issue, same tp-aio4to issue, same!
Goo No. 21314, JP-A-13-/, 27F4, same!
--Tada No. 77.

pjiJ! T! -114426, same jJ-JJjtd
Same issue! --In addition to the cloud blindness et al. Kn) and (B) methods described in publications such as @03mI, special public a8j4t-J
As arranged in the publication No. 717/41, h m1-form titanium trichloride obtained by reducing titanium tetrachloride with an organic aluminum compound has a [-molar ratio of 0.0% to the titanium trichloride. !
It is also possible to use a product prepared by adding an ether compound of ˜j and heating to ˜jθ˜/20″cK and then separating the solid.

The above titanium-containing solid catalyst component is used as is,
However, it is preferable to use it after pretreatment with a small amount of olefin in the presence of an organoaluminum compound. This pretreatment is effective in improving the properties of the polymer slurry, such as bulk density.

In step III/, the organic aluminium compound used as a cocatalyst, i.e., as a noodle component for the titanium-containing solid catalyst component, has the general formula ZR'mC4-m, where R' is the base prime number/~ Represents the verticalized water lily 1 of KoO, m is 3≧m>t,
(indicating the number of z).

When the titanium-containing solid catalyst II & component is a carrier-supported catalyst component containing a solid magnesium compound, MulR
: or a mixture of mR: and mR', 01 is preferably used. On the other hand, when the catalyst component is Ti013 as the main component, it is preferable to use A2B:Oj. Particularly preferred is a propyl group or a normal intermediate syl group;
If necessary, additives for improving stereoregularity may be added to 81N as a third catalyst component.For this purpose, various additives including M, O, P or 81 may be added. compounds and % swelling hydrogen compounds are used.

In the method of the present invention, one cup of propylene is.

/ It is carried out in a polymerization tank made of Japanese cypress or two or more pipes connected in series.

The polymerization of propylene in the method of the present invention means homopolymerization of propylene or copolymerization of propylene and a small olefin.

The polymerization time and temperature are set such that the amount of polypropylene is 4θ~27m(kX, preferably TO-F7 polymerization %) of the total amount of polymer produced.The polymerization temperature is usually UO~/
θθ°C, preferably selected from kezz-to°C. 16 Combined pressure is usually 7~jOkli/cd, preferably! ~4
It is tOkg/-.

The obtained polypropylene slurry is extracted from the 1st batch and fed to the classification system, where the original propylene polymerization 411 #/c is returned to the slurry containing fine particles and the subsequent propylene-ethylene slurry is 1 The slurry containing coarse particles is separated from the slurry supplied at the same time.

The classification system used in the method of the present invention may use a well-known classification system such as a hydrocyclone alone, but it is composed of a K, mai device and a precipitated PI# hydraulic classifier to ensure efficient classification. It is preferable to use a classification system.

A case in which a classification system consisting of a combination of a concentrator and a sedimentation liquid force classifier is used will be explained in detail.

The polypropylene obtained in the Jl/stage is extracted from the polymerization tank in an amount of slurry*tr~6on, preferably in a 10-10-layer lid, and fed to the fi, aJIii vessels. The contracted polypropylene tree is separated into the contracted polypropylene and the supernatant liquid. Is the 1i degree of concentrated polypropylene slurry J~? j heavy lid%, preferably 10
It is controlled to be 70% by weight. The particle concentration in the supernatant liquid is preferably as low as possible, but is usually 0.1% by weight.
% below, especially θ, 007 to 0. /Jyutan S・The ratio of the ratio of the polypropylene slurry to the upper fItf/IL depends on the properties of the polypropylene slurry, *the performance of the wrapping device, but the weight ratio is j O/ j O~fW// is preferred.

Examples of chains that can be used in the method of the present invention include hydrocyclones, centrifuges, V-transfers, etc., but hydrocyclones are easy to operate in terms of continuous operation, and one device is JSal! Moreover, it is inexpensive and requires a small equipment area, so it is preferable to install several pseudo compressors in series, resulting in 71111! If the supernatant liquid from the container is supplied to the No. 1 concentrator, the particle loss of the supernatant liquid from the Kite-2 concentrator can be further reduced and the classification effect of the sedimentation liquid force classifier can be increased. can.

The cyclone housing requires a special shape.1. However, it is preferable that the diameter of the slurry feed tube is such that the separated particle size is small.
It is preferable that the diameter is sθC or more, preferably ltJm/Bee or more, and that the inner cylinder of the cyclone' is thin enough to accommodate pressure loss.

Mobile polypropylene slurry from concentrator and J:fjt
The liquid is then fed into the upper and lower parts of the settling liquid force classifier and countercurrently contacted inside the Mfli for 1 minute. The polypropylene that has been hydraulically precipitated by the contact is recovered and taken out from the lower part of the classifier, and is fed to the next propylene-ethylene extraction. Polypropylene F that did not undergo hydraulic settling
i, the amount ratio with the slurry supplied to the ethylene copolymerization tank is preferably j Oj70-dide// in terms of weight ratio! 0/
jθ~? It is ♂/λ.

Preferably, it is tapered.

The residence time of the polypropylene slurry in the classifier is determined by the volume of the classifier and the amount of the hydraulically precipitated polypropylene slurry drawn out, but it is usually 7 minutes or more, preferably 3 minutes or more.

The volume of the classifier or the extraction lid is determined.

JlJ & floor propylene-ethylene copolymer cypress is continuously fed from 1/stage to polymer, medium % dripping mono! −
In addition to ethylene and propylene.

(Required) Additional hydrogen is supplied to the th9, as well as a specific aluminum compound, which is one of the features of the present invention.

Ethylene and propylene are combined into one composition with a high working shock resistance and a good storm resistance by changing the propylene/propylene + ethylene ratio in the gas phase.
- to obtain -27-90 mol%, preferably jo-rz
It is supplied to maintain the mol%.

Hydrogen has a copolymer melt index of io='~0.
It is controlled so that it remains lK. Therefore, when there is a large amount of hydrogen gas entrained in the effluent from the first stage, it is purged from the gas phase (if it is less than 2%, it is additionally supplied).

The aluminum halide compound newly supplied in the III-co-stage has the general formula MtR%,! , -n (wherein R8 represents a reverted hydrogen group having 7 to -0 carbon atoms, X represents a /10 gen atom, and %n represents the number of 8!≧n≧O), Specifically, ethyl alkaline dichloride (mu71t, 10jl, s), ethyl alkaline dichloride (muzitoz), or a mixture thereof are good. The amount added is usually 1 part of propylene in 1 stage
Use when 0.0/~0 for the organic Al 1=um compound represented by the aforementioned general formula MzR1oz, -m
．． The amount may be 50 moles, but if the amount is too small, the effect will be poor, and if it is 1, the copolymerization activity will decrease, making it impossible to obtain the desired monomer composition.

The polymerization temperature is usually Jj~71°C, preferably Jj~4°C.
! 1 polymerization pressure selected from °C is usually /-zOk & 7g, J
, preferably j-4tOJcg/-, the amount of pyrene-ethylene copolymer is 1 to 30% of the total amount of polymer produced.
Weight%. The content of ethylene is 7 to -0 weight X of the total amount of polymer produced, preferably 1 to 1! Weight % #1.

The pyrene-ethylene block copolymer obtained by the method of the present invention has high crystallinity and excellent impact strength at low temperatures.

Next, explanation will be given using one drawing. Algae/-711 is.

3 is a flow diagram of one embodiment of producing a tetrapyrene-ethylene block monomer according to the present invention. 'Hatake/The figure is a flow diagram when a Probile 2 polymerization tank and an ME classification system for boupyrene-ethylene copolymer cypress are installed. - Explain the specific Kw& for Figure 7.

A catalyst for propylene 1 synthesis is supplied to the polymer 21 polymerization pipe 11) and liquefied propylene is supplied from the propylene supply pipe 2, respectively, and polymerization of pyrene is carried out. The produced nine polypropylene slurry is extracted from the propylene polymerization tank, passes through a slurry extraction pipe (31), and is supplied to liquid cyclone B. In liquid cyclone B, it is separated into a concentrated polypropylene slurry and a supernatant liquid. The concentrated polypropylene slurry is extracted from the lower part of the liquid cyclen B, passes through a chain line polypropylene slurry extraction pipe (5), and is supplied to the upper part of the sedimentation liquid force classifier 0.

On the other hand, the supernatant liquid is extracted from the upper part of the liquid cyclone B, passes through the supernatant liquid extraction pipe (4), and is supplied to the lower part of the sedimentation liquid force classifier C. The condensed polypropylene slurry and the supernatant liquid were subjected to countercurrent shaking in the classification cylinder of the sedimentation liquid force classifier C.

The polypropylene that has been hydraulically precipitated by this contact is extracted from the lower part of the sedimentation liquid force classifier C, and is supplied to the propylene-ethylene copolymerization pipe through the sedimentation F4 liquid force classifier extraction pipe (7)'f-way. . On the other hand, the liquid that has settled and surfaced is extracted from the upper part of the sedimentation liquid classification (transfer) C and returned to the original propylene polymerization tank (8 tubes (6) 91) for the sedimentation liquid classifier. Propylene-ethylene copolymer mDKFi, hydro-sedimented polypropylene together with further ethylene and optionally additional propylene is fed into the ethylene supply pipe (8).

Fluohylene is supplied from 't;t (9), and copolymerization of propylene and ethylene is carried out. In the present invention, an aluminum halide compound is added to the propylene-ethylene copolymerization 111 through an aluminum halide compound supply pipe. The resulting propylene-ethylene block copolymer #'i1 is extracted from the combined discharge pipe av and converted into a product.

The figure is a flow diagram when one liquid cyclone is installed in series in the classification system.The supernatant liquid extracted from the liquid cyclone B1 is supplied to the liquid cyclone B. In the cyclone B2, a small amount of particles contained in the supernatant liquid of the first liquid cyclone B+IP is further separated, and a supernatant liquid that does not contain polypropylene particles is obtained. 4t
') Particles of the supernatant liquid supplied to the settling wave force classifier 0 ・If a liquid cyclone is provided, the particles of the supernatant liquid are supplied from the liquid cyclone B to the settling wave force classifier 0
Since F becomes close to θ, the classification effect of the settling liquid force classifier 0 increases. That is, propylene-ethylene copolymerization tank D
The fine particles of polypropylene supplied with K can be made into as much food as possible.

The J diagram is a flow diagram for the case where one cup of propylene is made into one anti-[6-t' line.

Mu, B, O, D and /, -2, J, in the jIJ diagram
Da-- is the same as @i-- figure.

Next, features of the present invention and comparative examples will be explained.

In addition, in these examples, each measurement value was determined by the following method: ■ Melt flow index (Mill) 187M
Extrusion 1 according to -D/JJIK at %2JO<0>C and load -/4jqi is shown in units of 9710 m1n.

■ Embrittlement temperature ffi (Tl)) The flow direction of the molten resin (MD
) and the direction perpendicular to the flow direction (TD) k.

■ Based on the dirt drop equilibration strength M8TE M-D/70fK, hold a 12m thick flat plate in the sample holder of 4I/inch at 10℃ at 0°C. The load at which the test plate 10X broke when dropped from a height of 10 was expressed as impact energy.

■Evaluation of mildew gel: In order to suppress the microscopic gel that cannot be visually identified as #'i, pi,
A film of rhinoceros JOμ was formed using a 100ulj die, and -! The area of 0- was cut off), enlarged and projected, and # was counted for all games. The correspondence between the constant number of gels and the symbols in II is as follows.

Example/2) Production of titanium-containing solid catalyst component: Autoclave with a capacity of 101 [n-hexane 2.0
2 and four pigeon titanium! , 0 mol, and further di-n
-07 mol of octyl ether are added. While stirring and maintaining az'cK, 0 mol of diethyl alkaline chloride was dissolved in n-hexane and gradually added dropwise over 20 minutes, resulting in a green color. Black-brown titanium trichloride in n-hexane I
11'Wk was obtained.Then, the temperature of the homogenized solution of titanium trichloride was raised over a period of about 4 tj minutes, and during the heating process, a purple precipitate of titanium trichloride was observed to form.

After stirring for 1F# at 3°C, the precipitate was separated from P and washed repeatedly with n-hexane to obtain a finely granular purple 1-body titanium trichloride catalyst anchor. An autoclave with a converted volume and weight of 01 Kn-hexane/J,jt was charged, and under stirring, 4 mol of diethylalkinium trichloride/4 mol and the above solid titanium trichloride-based catalyst complex were added to an autoclave with an amount of % TiO4 of -zzo.
Then, the internal temperature was set to tJO℃K111, and while stirring, the injection of propylene gas was started and the polymerized propylene was /co!・Blowing of propylene gas was continued at the same temperature until it reached 0fK1. Thereafter, the solid is separated and washed repeatedly with n-hexane to obtain polypropylene-containing titanium trichloride (titanium-containing solid powder).

g3) Preparation of globylene-ethylene block combination: Internal volume/, 4? and 0.4d reaction 11x+, in the middle of 6 anti-mi, 1 body cycle (the length of the cylinder relative to InliK is 1, the taper part is J) and a sinking force classifier (the length of the cylinder relative to the diameter is 7.j The taper part of the E part is 7.-)
KII was connected in series through a classification system consisting of a combination of A propylene-ethylene block copolymer was made continuously by KM using 7 liters of propylene as a single copolymer of globylene-ethylene. Liquefied propylene, hydrogen, and a catalyst were continuously supplied to perform so-called bulk polymerization.The catalyst was 1. Said (
This is due to the combination of the polypropylene-containing titanium trichloride obtained in step (g) and diethylaluminum chloride, and the molar ratio of diethylaluminum chloride to T104 K in the polypropylene-containing titanium trichloride is J. 1
The rational IiL is 20℃, the pressure is 11JJk41/-G, and the hydrogen line storm in the gas phase is! , J mole %, average residence time fi hours,
The liquid level was controlled to be kept constant at 1/y11.

The slurry chain degree of the polypropylene slurry extracted from the Pluville 2 polymerization tank was approximately 4tjl lid%. This slurry was supplied to the hydrocyclone by a pump at a moderate rate of approximately J-/HH, and from the top of the cyclone A supernatant liquid with a particle concentration of 0.00% by weight, with almost no solid particles present, was extracted from the lower part of the cyclone as a condensed slurry with a density of about 100% by weight. The supernatant liquid is /, Oyy/
*The reduced slurry was supplied to the upper part of the classifier at a flow rate of Od/H'kt, and the slurry extracted from the upper part of the classifier remained as it was. Slurry chain degree approximately 4t7% by weight, flow rate da, 71117/
III/reactor (propylene polymerization tank) KM in HR 1
The slurry extracted from the bottom of the classifier has a slurry concentration of about 100%! Reaction II with heavy lid %, flow rate O, J jd/HR
The px slurry (slurry containing rice grains) supplied to F (both 1 gold rights) and returned to the 90@i reaction reactor/slurry (slurry containing @ grains) supplied to the λ reaction reactor had a weight ratio of 9171. Ta.

Ethylene, oxidized propylene and hydrogen are supplied to the copolymerized cypress, and propylene 1llktttO#4 in the gas phase is supplied.
The amount of hydrogen per 1 mol N and the sum of ethylene and propylene was controlled to 3 mol %.

Furthermore, ethylaluminum 5-dichloride was continuously supplied so that the molar ratio to the diethylaluminium chloride supplied at 11/m was θ,0/m. Polymerization II
! I! ! During the residence, the random copolymer was combined.

Unreacted propylene was flash-removed from the monomer slurry thus obtained.

The mixture was then subjected to methanol steam treatment and drying to obtain a powdered polymer with a production volume of about 6 mm/HR.

BRte(-14
-di-t-butyl-p-cresol) 0-2111%
The mixture was then pelletized using a single screw extruder with an internal diameter of 41°. Then, a flat plate of /θθxiows and thickness of 2111 was obtained using a small injection molding machine. Melt flow index of the entire polymer #/iλ,! (The melt flow index of the joint part is o, o o i), and the embrittlement temperature is -Jj℃ in the flow direction and 177℃ in the perpendicular direction, and the dirt drop impact strength is 2j~ -It was a country. In addition, no foreign substance-like gel was observed in the visual inspection of the flat plate. Furthermore, when the microgel was evaluated, it was found to be 4tO pieces.

Example 1 The same apparatus as in Example 1 was used. Diethylaluminium monochrome in which ethylaluminum dichloride to be supplied to the amount of copolymerization was supplied to a tank of koji/3. Example 1 was carried out exactly as in Example 1, except that the residence time was set to 10 days in order to adjust to J weight %. The results are shown in Table 7.

Example J The same apparatus as in Example 1 was used. Ethylaluminum sesquichloride was used instead of ethylaluminum dichloride as an alkyl compound to be supplied to the co-merging process.
The molar ratio to diethylaluminum monochloride fed to the elm was 0.2/K, and the residence time was adjusted to /, /hour in order to adjust the total copolymerization amount to /3.11%. Same as Example/I except that
IK was carried out and the results shown in the table were obtained.

l! Example/Example/Kk decreases the amount of polypropylene tree withdrawn from the reactor by %, J, // HRK,
The hydrocyclone and the settling liquid force classifier were each replaced with those with positive capacities as in Example 1, and the residence time in the reactor was set to 2 hours.

Particle chain storm from the top of the housing cyclone about Q, 0/weight 1iX
The supernatant liquid is 0. At a flow rate of t d/HH, the slurry 1111 & approx.
, // HR, the supernatant liquid is supplied to the lower part of the settling liquid force classifier, and the chain line slurry is supplied to the upper part of the classifier. The slurry concentration is approximately J011%, the flow rate θ, 7
The slurry returned to JI&/Reactor 11 (propylene polymerization tank) K in d/HR and extracted from the bottom of the classifier is slurry 111 & about 30% by weight,
Flow rate 0. ! yd/BR in a subsequent Suwa reactor (copolymerization 4
11) K supplied. Rattan/Return to the reactor souffle (6
The slurry (slurry containing coarse grains) supplied to the slurry (slurry containing grains) was 1/4t by weight.The amount of copolymerization was as follows: The molar ratio to monochloride is 0. / 4 K, and the amount of copolymerization is 1 to 1 to 11 [, t/-tXK].
The humidity content was set to 0°C, and the procedure was carried out in exactly the same manner as in Example 9 except for 9.
/ @ # / One powder aggregate was obtained with a production amount of HR. The results showed the first IRK.

Reference Example A propylene-ethylene block comonomer was produced by one-minute polymerization using only 4117 reactor units. Edit/Dan Sui's single batch of propylene was carried out under the same conditions as in Example SI, but predetermined amounts of liquefied propylene, hydrogen, diethylalinium chloride, and trichloride were charged, the gas phase composition and temperature were adjusted, and trichloride was prepared. Polymerization was started by supplying titanium in a short time E7.

After the first stage reaction is completed, the temperature is lowered and 2 hydrogen is removed from the gas phase.
Part purge [7. Ethylene was added to carry out propylene-ethylene polymerization at the tm stage. The conditions for co-coating were as follows: except that ethylaluminum dichloride was not supplied, and in order to adjust the co-coupling volume to /JJ**%, the humidity content was set to θ°C, and the residence time was set to /, 2 hours. 7, ethylene was continuously supplied to keep the gas phase composition constant.

When a predetermined amount of polymerization is reached, about 1/l of methanol is added to stop the first reaction and the mixture is discharged to the post-treatment system.

Processes similar to Example/ and reIJ were carried out to obtain pelletized and injection flat plate molded products, and each &#I determination was carried out. The results are shown in the kite/table.

The same apparatus as in Example/Example/ was used. Propylene polymerization and minute N& were carried out under exactly the same conditions as in Example/, and slurry chain IIILμ! heavy h% polyglobulin tree O,J
9, both 1 and 1 were supplied to the duck at a flow rate of j tv//HR.
In contrast, no new supply of alkenium compound is carried out, and the copolymerization lid is /J with respect to the total polymer production ikK,
The polymerization temperature was set to θ°C and the residence time was set to 7. The test was carried out under exactly the same conditions as in Example except that the test time was one hour. The results are shown in Table #'ik&7.

ratio! 1IR Example - The same procedure as in Example 1 was carried out except that a classification system was not used and the holypropylene slurry from hinoki cypress was directly supplied to 1IK, and the results shown in Table 7 were obtained.

Do not use a classification system and do not supply new aluminum compounds to the joint wheels.

And the total amount of both is /3. ! Example 1 except that the humidity content was 4to℃ and the residence time was 81 hours to match the heavy electric XK.
The procedure was carried out in the same manner as in Example 1, and the results of the Tori 1 table were used. In both cases, U ethylaluminum dichloride was replaced by Kk - diethylaluminum chloride, the same as that supplied by Hinoki.

74 times the amount of rice fed to Iris-111 by mole was newly fed, and the moisture content was adjusted to 1°C so that the amount of copolymerization was /3.1*kura
The procedure was carried out in accordance with Example 1, except that the residence time was 7.2 hours, and the results shown in Table k1 were obtained.

A comparative example! Propylene was mixed and classified in exactly the same manner as in Example. In the 1-minute tank, the substitute for ethylaluminum dichloride was fed into a 1-m-hinoki pipe of ethylaluminum (K), and the molar ratio to diethylaluminum monochloride was O0θl. The process was carried out in exactly the same manner as in Example 1, except for the above, and the results shown in the koji table were obtained.

As is clear from these examples, 111 comparative examples, and reference examples, the classification system according to the present invention and the specific algorithm 1 to 1 gold right
It can be seen that the prepylene-ethylene block copolymer produced continuously by KM by adding a compound has extremely good low-temperature properties, and exhibits the same quality as that obtained by batch polymerization. . Also, comparative example! It can be seen that aluminum compounds other than those of the present invention have no effect at all.

1) IADO: ethylaluminum dichloride
) ICA30: ethylaluminum sesquichloride 3) Dli: diethylaluminum chloride 4) Tl: triethylaluminum da It is.

Mu: Propylene polymerization tank Mu+@'Propylene polymerization tank Mu,: Island copropylene 1 combination B: i [Body cyclone B,: IG/Liquid cyclone B,: U-housing cyclone C: Sedimentation rII# Liquid force classification culture D: Globylene-ethylene ax combination ttml; Catalyst supply pipe; Propylene supply pipe J% J/; Slurry discharge pipe; , evening": *Condensed polypropylene slurry extraction pipe 4: Sedimentation liquid force separator extraction pipe 2: Sedimentation liquid force classifier extraction pipe l: Ethylene supply pipe T: Propylene supply pipe 10 S Aluminum halide compound Supply pipe 7) = Polymer discharge pipe Patent issued by Mitsubishi Chemical Industries, Ltd. Representative Patent attorney Hase - 01 or 7)

Claims (1)

[Claims] (1) Titanium-functionalized solid catalyst component and general formula At~c4
−. (In the formula, R1 represents a vertical hydrogen group with a genus prime number/~J0,
Otori is J≧rn 〉/,! Using a catalyst system mainly consisting of an organic aluminum compound represented by 04k),
First, the first step of propylene polymerization is carried out in a propylene polymerization tank, and then the propylene slurry from the polymerization tank for 1 s/step is subjected to glupylene-ethylene copolymerization wK to perform the first step of propylene-ethylene copolymerization. - In the continuous production method of ethylene block copolymer, 0
) rattan 1 stage and a mlv, , x1-n (wherein R1 represents a leg prime number/~aOtD hydrocarbon bulk group, nFi8j to n
1. A method for continuously producing a brobylene-ethylene polymer p-p copolymer, which comprises newly adding a metal halide aluminide represented by ≧the number of O's. (2) The manufacturing method according to claim 1, wherein the classification system is a concentrator. (37) A method for manufacturing the method as described in Claim IIa, Paragraph 1, characterized in that the classification system is comprised of a condenser and a sinking force component. The manufacturing method according to claim 1A or -J, which is characterized by jin consisting of a part and 1
% mold according to claim 3. (6) IfIi mold is defined as IfIi mold when the ratio of the amount of slurry returned to the J147 stage from the classification system to the slurry supplied to the first stage is 30/10///// Manufacturing method described in section. (7) Claims characterized in that the use cap of the halogenated alkenium compound added in the jlJ stage is 0.0/~o3o mole times that of the organic alkinium compound used in the single stage. l! 1. The manufacturing method described in item 1. (8) The striped/staged propylene polymerization is carried out in one or more cypresses connected in series.