JPS6017403B2 - Preactivated α-olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst for Q-olefin polymerization, and more particularly to a catalyst for Q-olefin polymerization, particularly gas phase polymerization, and furthermore, as a variant of gas phase polymerization, slurry polymerization or bulk polymerization and gas phase polymerization. The present invention relates to a novel preactivated catalyst suitable for coarse phase polymerization.

Q-olefins are composed of transition metal compounds of groups N to W of the periodic table and organometallic compounds of metals of groups 1 to m of the periodic table, and include those modified by adding electron donors, etc., and are so-called Ziegler. It is well known that polymerization occurs using Natta catalysts. Among them, titanium trichloride is most widely used as a transition metal compound catalyst component to obtain highly fed crystalline polymers such as propylene and butene-1. Titanium trichloride can be divided into the following three types depending on its manufacturing method. ■
Titanium tetrachloride is activated by reducing it with hydrogen and then pulverizing it in a ball mill (referred to as titanium trichloride (HA)).

■ General formula TicI & KiA activated by ball milling after reducing titanium tetrachloride with metal aluminum
The compound represented by IC13 (so-called titanium trichloride (
AA).

■ Titanium tetrachloride is heat-treated after being reduced with an organic aluminum compound.

However, none of these titanium trichlorides are fully satisfactory, and various improvements have been considered and attempted.

As one method, titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound is treated with an electron donor and titanium tetrachloride to increase the catalytic activity and to prevent the formation of an amorphous polymer. A method has been proposed to reduce the number (for example, Samurai Seki Sho 47-134478). However, these methods have the disadvantage that the catalyst lacks thermal stability. In addition, a solid catalyst component is prepared by mixing and reacting two reaction solutions in which TIC14 and an organoaluminum compound are each mixed in advance with a certain amount of a complexing agent (an electron donor is also a type of complexing agent) and reacted. A method is also provided (Mochiseki Sho 53-9296).

This method also has the drawback of lacking thermal stability of the catalyst, similar to Tokkan Sho 47-34478. Furthermore, a method for producing a liquid material containing titanium trichloride by adding a homogeneous liquid material consisting of an organoaluminum compound and ether to TICi4, or by reversing the order of addition (JP-A-52-1
No. 15797) and a method of heating the liquid material to 150 qo or less to precipitate fine particulate titanium trichloride (Tokubatsu No. 5
No. 2-47594, etc.) have also been proposed, but these methods also have the disadvantage that the catalyst lacks thermal stability.

On the other hand, regarding the polymerization phase in a Q-olefin polymerization method using a Ziegler-Natta catalyst, slurry polymerization carried out in a solvent such as n-hexane (for example,
10596, etc.), bulk polymerization carried out in liquefied monomers such as liquefied propylene (e.g., Japanese Patent Publication Publication No. 10596,
14041, etc.), gas phase polymerization carried out in a gaseous monomer such as gaseous propylene (e.g.,
No. 812, No. 42-17487, etc.) are well known, and methods of carrying out gas phase polymerization after bulk polymerization are also known (for example, Samurai Ko No. 49-14862, Samurai Kai-Sho No. 51-1). 135987 etc.).

Among these, in the gas phase polymerization method, there is no recovery and reuse of the solvent used for polymerization, there is no recovery and reuse of liquefied monomers such as liquefied propylene, and the cost of recovering the solvent or monomer is small. There are advantages such as simplified production equipment for Q-olefin production. However, in the gas phase polymerization method, the monomer in the polymerization vessel exists in the gas phase, so the monomer concentration is relatively low compared to the slurry polymerization method and bulk polymerization method, so the reaction rate is low and the catalyst In order to increase the polymer yield per unit, it is necessary to increase the residence time, and for that purpose, it is necessary to increase the size of the reactor, and to increase the catalytic activity, it is necessary to use modified trialkylaluminium. However, it has the disadvantage of reducing the stereoregularity of the polymer. Furthermore, in the gas phase polymerization method, polymer particles tend to be irregular due to irregular catalyst particles. This tends to cause agglomeration of polymer particles and blockage of the polymer outlet of the polymerization vessel and the transportation line, making stable continuous operation difficult over a long period of time, and resulting in greater variation in quality. The present inventors previously proposed a polymerization method that does not have the above-mentioned drawbacks even in gas phase polymerization.
A solid product obtained by reacting a reaction product of an electron donor and an organoaluminium compound with titanium tetrachloride in the presence of an aromatic compound, or a solid product obtained by further reacting this solid product with an electron donor. We invented a method for producing polyQ-olefin using a catalyst in which a group product is roughly combined with an organoaluminum compound, but as a result of further research, we found that the reaction product of an organoaluminum compound and an electron donor was combined with titanium tetrachloride. In the presence of a catalyst obtained by combining a solid product obtained by reacting an electron donor and an electron acceptor with an organoaluminum compound,
Invented a method for polymerizing Q-olefin (Hakamagao Sho 55-
No. 12875 (hereinafter sometimes referred to as the earlier invention). According to this polymerization method, no polymer lumps are formed, and long-term stable operation can be achieved even in gas phase polymerization, especially when the catalyst is preactivated with Q-olefin, which is conventionally performed, and gas phase polymerization is performed. However, the polymer yield in gas phase polymerization was 5,000 to 6,000 polymers per polymer of the solid catalyst component, which was still not sufficient activity. For this reason, it is impossible to reduce the amount of catalyst used, and if the amount of alcohol, alkylene oxide, steam, etc. used for killing the catalyst after producing the Q-olefin polymer or for purifying the polymer is reduced too much, the polymer In some cases, the corrosive substances remaining inside were not sufficiently rendered harmless, causing the mold to rust during polymer molding or damaging the physical properties of the polymer. As a result of further improvement research, the present inventors discovered that when using a new catalyst prepared by adding and preactivating an unknown catalyst component to the catalyst used in the previous invention, gas phase polymerization is required. In addition, the polymer yield is sufficiently increased, the polymer can be easily purified, the stereoregularity of the polymer, especially polypropylene, can be controlled and produced, and the atactic polymer can be produced by controlling the stereoregularity of the polymer. The present invention was achieved by discovering that the production rate was low.

The purpose of the present invention is to provide a polymer with uniform particle size even in gas phase polymerization, high stability of the catalyst used, and high catalytic activity, so that the advantages of gas phase polymerization can be fully demonstrated. The object of the present invention is to provide a catalyst for the polymerization of preactivated Q-olefins, which allows the stereoregularity of the upper polymer to be easily controlled.

- Briefly stated, the present invention comprises an organoaluminum compound (A,) and an electron donor (ED).
The solid product (0) obtained by reacting the reaction product (RP, ) with titanium tetrachloride is further treated with an electron donor (
The solid product (m) obtained by reacting ED2) with an electron acceptor (EA) is treated with an organoaluminum compound (n),
When combining Q-olefin (Q-○) and the reaction product (RP2) of organic aluminum (n) and electron donor (ED3) (these three substances are called catalyst components), Q- This is a Q-olefin polymerization catalyst in which a part or all of the catalyst components are preactivated by polymerizing an olefin in the presence of at least a solid product (m) and an organoaluminum compound (A2).

In the present invention, the term ``polymerization treatment'' refers to polymerizing the olefin by bringing a small amount of Q-olefin into contact with the catalyst component under polymerizable conditions.In this polymerization treatment, the catalyst component is preactivated and the polymer is It becomes covered with.

The method for preparing the catalyst of the present invention will be explained below. solid product (
The production of m) is carried out as follows.

First, an organoaluminum compound (A,) and an electron donor (
ED,) to obtain a reaction product (RP,),
This (RP,) is reacted with titanium tetrachloride to obtain a solid product (b), and this is reacted with an electron donor (ED2) and an electron acceptor (ED2) to obtain a solid product (m). .

Organoaluminum compound (A,) and electron donor (ED,
) in the solvent (D) at -20qC to 200°C,
It is preferably carried out at -10qC to 100oo for 30 seconds to 5 hours.

There is no restriction on the order of addition of (A,), (ED,), and (D), and the ratio of amounts used is 0.1 to 8 mol, preferably 1 to 4 mol, of electron donor per 1 mol of organoaluminium, and solvent. 0.
5 to 5 mm, preferably 0.5 to 2 mm is suitable. Aliphatic hydrocarbons are preferred as solvents. The reaction product (RP, ) is thus obtained. The reaction product (RP, ) is in a liquid state (reaction product (R
P, ) can be used for the next reaction. The reaction between the reaction product (RP,) and titanium tetrachloride is carried out at 0 to 200 qC, preferably 10 to 90 qC for 5 minutes to
Do it for 8 hours.

Although it is preferred not to use a solvent, aliphatic or aromatic hydrocarbons can be used. (RP,), titanium tetrachloride, and the solvent may be mixed in any order, and it is preferable that the mixing of the entire amount be completed within 5 hours. The amount of each used in the reaction is 0 to 1 mole of titanium tetrachloride, and the solvent is
3,000 {, the reaction product (RP,) is the (RPI)
The ratio of the number of AI atoms in titanium tetrachloride to the number of Ti atoms in titanium tetrachloride (A
I/Ti) is 0.05 to 1, preferably 0.06 to 0.
It is 2. After the reaction is completed, the liquid part is separated and removed by separation or decantation, and the obtained solid product (b) is further refined with a solvent and used in the next step (while suspended in the solvent). Alternatively, the solvent may be separated and dried to obtain a solid product for use. The solid product (b) is then reacted with an electron donor (ED2) and an electron acceptor (EA). Although this reaction can be carried out without using a solvent, preferable results are obtained when an aliphatic hydrocarbon is used. The amount used is 10 to 1,000 g of (ED2) per 100 g of the solid product (b).
0 evening, preferably 50 evening to 200 evening, (EA) 10 evening to
1,000 nights, preferably 20 nights to 500 nights, solvent 0 to
3,000', preferably 100 to 1,000. These three or four substances are -1000 to 40CO
It is desirable to mix the sand for 60 minutes and react at 0 to 200°C, preferably 50 to 100°C, for 5 hours. Solid products (B), (ED2), (E
There is no restriction on the mixing order of A) and the solvent. (ED2) and (
EA) may be reacted with each other in advance before mixing with the solid product (0), in which case (ED2) and (
EA) is reacted at 10 to 100 pm C for 30 minutes to 2 hours, and then cooled to 40 q○ or less. After the reaction of solid products (B), (ED2) and (EA) is completed, the liquid portion is separated and removed by separation or decantation, and then
Further refinement with a solvent is repeated to obtain a solid product (m) which is a catalyst component for Q-olefin polymerization according to the present invention.
The obtained solid product (m) is dried and taken out as a solid product, or suspended in a solvent for the next use. The solid product (m) thus obtained is then combined with an organoaluminum compound (n) to constitute a catalyst, and is further combined with a Q-olefin (Q-○), an organoaluminum compound (A3), and an electron donor (ED3). The catalyst is preactivated by combining the reaction product (RP2) with (RP2), and by appropriately selecting the reaction product (RP2), a polymer with controlled stereoregularity can be obtained.

This preactivation will be detailed later. The organoaluminum compound used in the present invention has the general formula AIR Nagi n'X3-(n+n
') (In the formula, R and R' represent a hydrocarbon group or an alkoxy group such as an alkyl group, an aryl group, an alkaryl group, or a cycloalkyl group, and X represents a halogen such as fluorine, chlorine, bromine, or iodine, and n , n'' or any number in the range 0<n+n'<3), and specific examples include trimethylaluminum, triethylaluminum,
Tri-n-propyl aluminum, tri-n-phthyl aluminum, tri-butyl aluminum, tri-n-hexyl aluminum, tri-hexyl aluminum, tri-2-methylbentylaluminum, tri-n-octyl aluminum, tri-n- Trialkylaluminums such as decylaluminum, diethylaluminum monochloride, di-ni-f.

Dialkyl aluminum monohalides such as lopylaluminum monochloride, di-butyl aluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, diethylaluminum monoiodide, dialkylaluminium such as diethyl aluminum hydride hydrides,
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride and ethylaluminum sesquichloride, ethylaluminum dichloride, i-
Examples include monoalkylaluminum dihalides such as butylaluminum dichloride, and alkoxyalkylaluminums such as monoethoxyjethylaluminium and diethoxymonoethylaluminum can also be used. Two or more types of these organoaluminiums may be used in combination. Organoaluminum compound (A,) to obtain reaction product (RP,), combined with solid product (m) (A2), reaction product (RP2)
In order to obtain (A3), each of (A3) may be the same or different. Ether is used as the electron donor (ED, ) and (ED2) used in the production of the catalyst of the present invention. Also, those used as electron donors (ED3) are organic compounds having any one of oxygen, nitrogen, sulfur, and phosphorus atoms, such as ethers, alcohols, esters, aldehydes, fatty acids, ketones, These include nitriles, amines, amides, ureas or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, thioethers, thioalcohols, and the like. Electron donors (ED, ), (ED2) and (E
Specific examples of ethers as D3) include diethyl ether, di-n-propyl ether, di-butyl ether, diisoamyl ether, di-bentyl ether, di-hexyl ether, and di-hexyl ether. ,
Examples include ethers such as di-n-octyl ether, di-i-octyl ether, di-dodecyl ether, diphenyl ether, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran. In addition to the above-mentioned ethers, specific examples of the electron donor (ED3) include methanol, ethylphenol, pronofol, butanol, bentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol, and naphthol. Alcohols such as methyl methacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate,
2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl tolyl, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, naphthoic acid Esters such as butyl, 2-ethylhexyl naphthoate, and ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, fatty acids such as formic acid, acetic acid, propionic acid, oxalic acid, oxalic acid, succinic acid, acrylic acid, and maleic acid, and benzoic acid. Aromatic acids such as methyl ethyltone, methyl isobutyl ketone, ketones such as benzophenone, nitrile acids such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, 3(N,N-dimethylamino)ethanol, Amines such as pyridine, quinoline, Q-picoline, N,N,N',N'-tetramethylhexaethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide,
N,N,N',N',N''-bentamethyl-N'-8-
Dimethylaminomethylphosphate triamide, octamethylpyrophosphoramide, ureas such as N,N,N',N'-tetramethylurea, isocyanates such as phenylysocyanate and tolylisocyanate, azo compounds such as azobenzene, ethyl Phosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, phosphines such as triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphine, triethylphosphine phosphites such as tri-n-butylphosphite and triphenylphosphite; phosphinites such as ethyljetylphosphinite, ethylbutylphosphinite, and phenyldiphenylphosphinite;
Thioethers such as diethyl thioether, diphenyl thioether, methyl phenyl thioether, ethylene sulfide and propylene sulfide, and thio alcohols such as ethyl thio alcohol, n-propyl thio alcohol and thiophenol can also be mentioned. These electron donors can also be used in combination. an electron donor (ED,) to obtain a reaction product (RP,);
(ED2) for reacting the solid product (b) and (ED3) for obtaining the reaction product (RP2) may be the same or different. Examples of the electron acceptor (EA) used in the present invention include titanium tetrachloride and aluminum trichloride, and these can also be used in combination.

Most preferred is titanium tetrachloride. The following solvents are used.

Examples of aliphatic hydrocarbons include n-hebutane, n-octane, i-octane, etc. Carbon tetrachloride, chloroform,
Halogenated hydrocarbons such as dichloroethane, trichlorethylene, and tetrachlorethylene can also be used.
Aromatic compounds include aromatic hydrocarbons such as naphthalene and their derivatives such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, alkali substituted products such as 1-phenylnaphthalene, monochlorobenzene, orthodichlorobenzene, etc. halides, etc. are shown. The solid product (m) produced in this way has a diameter of 2 to 100 microns, preferably 10 to
It has spherical particles of 70 microns, and the particles have a narrow particle size distribution around the average value. Microscopic observation of the solid product (m) reveals the presence of a canal (camI). The specific surface area of the solid product (Wind) is in the range of 125-200/mm, which means that the solid product (D) with a specific surface area of 100-120/mm is combined with the electron donor (E).
By reacting D2) with an electron acceptor (EA), a higher specific surface area is obtained. solid product (
m), the interlattice distance d=4.
A strong, medium-wide diffraction line is seen near 85A. From the surface infrared measurement of the solid product (m), no absorption by hydroxyl groups near 3,450 cm-1 is observed.

As described below, the solid product (m) is thermally stable, and has the characteristic that the catalyst performance does not deteriorate even if it is stored at a high temperature of 30 qo to 50 pm. This high thermal stability
It is based on the structure of the solid product (m) described above, and this structure results from the manufacturing conditions carried out in the method for manufacturing the catalyst part according to the invention. Then the solid product (
m) is combined with an organoaluminum compound (A2) and a Q-olefin (Q-○), prepolymerized, and further combined with a reaction product (RP2) of an organoaluminum compound (n) and an electron donor (ED3). The method of preactivation will also be explained in detail.

Organoaluminum compound used for preactivation (F), (
A3), and used to generate the reaction product (RP,) (
A,) do not need to be the same, and may be different or the same.

The most preferred organoaluminum compounds (A,), (A2
) as dialkyl aluminum monohalide, (A3
) is trialkyl aluminum.

Q-olefin (Q-○) used for preactivation is ethylene, propylene, butene-1, hexene-1, heptene-1 and other linear monoolefins, 4-methyl-pentene-1,2-methyl-pentene. Branched monoolefins such as -1,3-methyl-butene-1, styrene, and the like.

These Q-olefins may be the same as or different from the Q-olefin to be polymerized, and two or more Q-olefins may be used.
- It is also possible to use a mixture of olefins. The electron donor (ED3) used for the preparation of the reaction product (RP2) can be the same as that described during the reaction to obtain the solid product (m), but It does not have to be the same as the one used to obtain it. Reaction product (RP2
) is usually carried out in the presence of a solvent such as n-hexane, n-hexane, n-heptane, etc., with 0.01 to 5 mol of the electron donor per 1 mol of the organoaluminum compound, and 1 mol each of the organoaluminum compound and the electron donor. 10 against the evening
It is obtained by reacting 1 to 30q0 to 10 and 0 for 1 to 3 hours using ~5,000 ml. Usually, an organic aluminum compound diluted with a solvent is reacted with an electron donor diluted with a solvent while being dropped. Pre-activation uses propane,
Butane, n-pentane, n-hexane, n-hebutane,
It can be carried out in a hydrocarbon solvent such as benzene or toluene, it can be carried out in a liquefied Q-olefin such as liquefied propylene or liquefied butene-1, or it can be carried out in gaseous ethylene or propylene, and it can also be carried out in the presence of hydrogen during preactivation. It's okay.

Preactivation is carried out by mixing the solid product (m) for 1 night and the organoaluminum compound (m) for 0.1 to 500 nights, preferably 0.5 m.
50 pm to 50 pm, reaction product (RP2) 0.05 pm to 10 pm in a state in which at least solid product (m) and organoaluminum compound (A2) among the catalyst components were combined, Q-olefin 0. This is done by polymerizing the catalysts combined as described above using 0.01 to 5,000 hours, preferably 0.05 to 3,000 hours.

Therefore, they may be combined after the polymerization treatment of (RP2). The polymerization treatment conditions are 0°C to 100°C, preferably 1
000 to 7000, and Q-olefin is 0.01 to 2,000 per solid product (m) per evening.
It is desirable to carry out the polymerization for 0 pm, preferably for 0.05 to 200 pm. 10 or less hydrogen may be present during the polymerization treatment. Further, in the preactivation, 50 or less catalysts may be used. At the time of preactivation, polymer particles previously obtained by slurry polymerization, bulk polymerization, or gas phase polymerization can also be made to coexist.

The polymer particles may be the same as or different from the Q-olefin polymer to be polymerized. The number of polymer particles that can be coexisted is 0 to 5,000 per 1 solid product (m).
It is in the range of 0 evening. Solvent or Q used during preactivation
- The olefin can be removed during the preactivation or after the completion of the preactivation by vacuum removal or separation, and the solid product related to the preactivation can be removed in an amount not exceeding 80% per night. Molten soot can also be added to suspend it in the solvent.

There are various methods of preactivation.

For example, '1) Combining the solid product (m) and the organoaluminum compound (A2), Q-olefin (Q-○)
A method of adding the reaction product (RP2) after polymerization treatment by adding (2'(Q-○))
Combine and (n), polymerize with (〇−○),
How to add (RP2), [3' solid product (dish) and (
After combining A2) and adding (RP2), (Q-○
) method of polymerization treatment.

'4) There is a method of further adding (RP2) after the glue. Regarding the above aspect '1}', more specifically (1)
-1) Combining solid products (m) and (n), (Q-
After polymerization treatment in gas phase or liquefied Q-olefin or solvent in
) and the solvent and add (RP2), (1-2)
, (1-1), unreacted (Q-○) or unreacted (
A method of adding (RP2) to Q-0) without removing the solvent, after adding (RP2) in (1-3) and (1-2), unreacted (Q-○) or unreacted ( Q-○) and the method of removing the solvent, (1-4) the method of (1-1) to (1-3) performed by adding Q-olefin polymer particles obtained in advance, (1-5) preactivation After that, solvent or unreacted (Q-○
) and the solvent to obtain the catalyst in the form of powder (1-1)
There are methods (1-4).

Similarly, regarding embodiment (2-1), combining (A2) and solid product (m) in the presence of dissolved propylene or liquefied Q-olefin or Q-olefin gas in a solvent,
- Method of adding (RP2) after polymerization treatment with olefin, (2-2) Method of (2-1) carried out in the presence of pre-obtained Q-olefin polymer particles, (2-3) Preactivation After that, unreacted (Q-○) and solvent are removed under reduced pressure to obtain the catalyst in the form of powder. In the method of m and {2-, the solid product (also), the component formed by reacting (A2) with (Q-○), and (RP2) are not mixed during the pre-activation described above, that is, during catalyst preparation. It can also be used by mixing it immediately before polymerization. Also, by the method of '1)~■, (Q-○
) and hydrogen can also be used. There is no essential difference in the catalyst of the present invention whether the catalyst is in the form of a slurry or in powder form. The preactivated catalyst of the present invention obtained as described above is used for producing a Q-olefin polymer.

Polymerization may be carried out by either slurry polymerization in which polymerization is carried out in a hydrocarbon solvent or bulk polymerization carried out in liquefied Q-olefin monomer, but since the catalyst of the present invention is highly active, Q-olefin It is particularly effective when used in gas phase polymerization, and when gas phase polymerization is performed after slurry polymerization as a modification of the gas phase polymerization, or when gas phase polymerization is performed after bulk polymerization. Favorable effects are also seen. Gas phase polymerization of Q-olefin is performed using n-hexane,
In addition to being carried out in the absence of a solvent such as n-heptane, Q-
It is also possible to carry out the process in a state in which the particles contain 0 to 500 hours of solvent per lk9 of olefin polymer particles.

The method for continuing the polymerization may be either continuous polymerization or batch polymerization. The type of equipment for the gas phase polymerization can be a fluidized bed type, a fluidized bed type equipped with a pressure blade, or a vertical or horizontal paddle light type. Examples of methods for performing gas phase polymerization after slurry polymerization or bulk polymerization of Q-olefin include:
In batch polymerization, after polymerizing Q-olefin in a solvent or liquefied Q-olefin monomer, the solvent or Q-olefin monomer is removed to a concentration of 500 ta or less per lk9 of polymer particles, and then the Q-olefin is vaporized. There is a method of polymerizing in phases.

Alternatively, the polymerization of the Q-olefin is continued without removing the solvent or the liquefied Q-olefin, and the solvent or the liquefied Q-olefin is absorbed by the polymer particles increased during the polymerization, and the polymer particles are absorbed into the gas phase without any operations. There are methods of transferring to polymerization, etc. Multistage polymerization reactions consisting of slurry polymerization or a combination of bulk polymerization and gas phase polymerization give favorable results, especially in continuous polymerization. In this method, in the first stage, slurry polymerization or bulk polymerization is carried out, and the slurry concentration is changed to polymer (k9) plus solvent or liquefied Q-
Continue the polymerization so that the olefin (k9) Basically, it is a method of performing gas phase polymerization of Q-olefin.

In this method, the catalyst is added during the first stage slurry polymerization or bulk polymerization, and in the subsequent gas phase polymerization, it is sufficient to use the catalyst from the previous stage as is. You may add new catalysts by eye.
The ratio of polymer produced in slurry polymerization or bulk polymerization and subsequent gas phase polymerization is preferably in the range of 0.1 to 100 (weight ratio) in gas phase polymerization to 1 in slurry or bulk polymerization. The stereoregularity of the polymer can be controlled by changing the molar ratio (hereinafter sometimes referred to as (RP2) molar ratio) of the electron donor (ED3), which is the raw material for the reaction product (RP2), and the organoaluminum (n). This can be done by The molar ratio can be effectively varied within the range of 0.01 to 5, with a lower molar ratio of 4.0% decreasing the stereoregularity and a higher molar ratio improving the stereoregularity. The polymerization conditions for Q-olefin are slurry polymerization, bulk polymerization, and gas phase polymerization, and the polymerization temperature is room temperature (20℃).
) ~ 200oo, polymerization pressure is normal pressure (okg no G) ~ 5
It is usually carried out for about 5 minutes to 1 hour at a G of 0k9/.

During polymerization, adding an appropriate amount of hydrogen to control the molecular weight is the same as in conventional polymerization methods. Q-olefins subjected to polymerization in the polymerization method using the catalyst of the present invention are linear monoolefins of ethylene, propylene, butene-1, hexene-1, octene-1, 4-methyl-bentene-1,2 These include branched monoolefins such as -methyl-bentene-1,3-methyl-butene-1, diolefins such as butadiene, isoprene, and chloroprene, and styrene.

In the polymerization method according to the present invention, these olefins are not only individually polymerized, but also copolymerized by combining them with other olefins, such as propylene and ethylene, butene-1 and ethylene, propylene and butene-1, etc. Polymerization can also be carried out, and in multi-stage polymerization, different Q-olefins may be used in the slurry monopolymerization or bulk polymerization in the first stage and the gas phase polymerization in the second stage. The main effect of polymerizing Q-olefin using the catalyst of the present invention is that even in gas phase polymerization with a relatively low monomer concentration, a highly silky crystalline polymer with good powder shape can be produced with high polymer yield. It is possible to freely control the stereoregularity of the resulting polymer within a certain range.

The effects of the present invention (hereinafter referred to as the effects of the present invention) will be explained in more detail.

The first effect of the present invention is that the activity of the catalyst obtained is very high, and high polymer yields can be obtained in slurry monopolymerization and bulk polymerization, but the monomer concentration is relatively low. Even in the phase polymerization method, the polymer yield per evening of the solid product (m), which is the catalyst component of the present invention, is 7,000 to 12,000 m.
It is possible to reach even 0.00 yen (polymer).

The second effect of the present invention is that since the polymer can be obtained in high yield, the amount of alcohol, alkylene oxide, steam, etc. used for killing the catalyst and purifying the polymer after producing the Q-olefin polymer is Even if I further reduce the amount, there is no coloring of the polymer.

-ness index (YI) of 0 to 2.0. This effect also eliminates the generation of corrosive gases that have an adverse effect on the physical properties of the polymer and cause molds to rust during polymer molding.For example,
Even when the polymer was heated to 200°C, no acidic gas was generated that would discolor Congo Red test paper. The third effect of the present invention is that the production rate of amorphous polymers is reduced during the production of Q-olefin polymers, and this effect is particularly large when producing copolymers in which two or more types of Q-olefins are polymerized. . For example, Pu. In the production of pyrene polymer, n-hexane (2 and 0
) Isotactic polypropylene as an insoluble material reaches 98 to 99.8% in isotactic and solenoid index, and atactic polymer as an n-hexane soluble material has an atactic index of only 0.2 to 2%. Therefore, even if the atactic polymer is not removed from the polymer produced using the catalyst of the present invention, there is no disadvantage in that the physical properties of the polymer, such as stiffness and thermal stability, are reduced. Therefore, the step of removing the atactic polymer can be omitted, and the polymer manufacturing process can be simplified. The fourth effect of the present invention is that the stereoregularity of the polymer can be controlled without increasing the amount of atactic polymer soluble in n-hexane. Regarding polypropylene, 995 arc-1 and 974 skin-1 were determined by measuring its stereoregularity using infrared absorption method.
The absorbance ratio (hereinafter expressed as IR-7) is 0.88 to 0.90 for homopolymer and 0.83 for copolymer.
It can be freely controlled within the range of ~0.95 without increasing the amount of atactic polymer. Previously, when the stereoregularity of a homopolymer was lowered or the stereoregularity of a homopolymer was changed to a copolymer in order to improve physical properties such as rigidity, impact, and heat-sealing temperature of polymer molded products, the amount of atactic polymers increased. According to the present invention, it has become possible to omit the step of removing the atactic polymer and to freely control the stereoregularity according to the purpose of the polymer. The fifth effect of the present invention is that the physical properties of the polymer, especially the stiffness, are expressed by the bending modulus of 0.90×1.4×1 pik9/
It means that it can be freely controlled within the limits of the earth.

Therefore, it has become possible to easily supply polymers suitable for use in various fields. The sixth effect of the present invention is that polymer particles with a good shape can be obtained, and compared to conventional examples, the average particle size of the particles is small, and 90 to 99% of the particles are between 32 and 60 mesh. contains polymers. The particles are nearly spherical, with fewer coarse particles and fine particles, and a narrow particle size distribution. In addition, the bulk specific gravity of the polymer (
BD) is in the range of 0.45 to 0.52, so the volume of the storage tank per weight of polymer can be small, making the polymer production plant more compact, and preventing line blockage problems caused by agglomeration of polymer particles. Transportation troubles caused by fine powder particles have been eliminated, and stable long-term operation has become possible even with the gas phase polymerization method. The seventh effect of the present invention is that the catalyst itself has high storage stability and thermal stability.

This effect has already been seen in the above-mentioned previous invention, but it is also maintained in the present invention. For example, the solid product (m) which is the catalyst component is 30
Even when the catalyst of the present invention was produced after being left at a high temperature of about qo for about 4 months, the catalyst no longer caused a significant decrease in polymerization activity. Therefore, unlike known catalyst components, there is no need for special storage equipment such as cooling and storing the solid product (m) to about 0°C, and it is possible to combine the solid product (m) with organic aluminum. Therefore, even if the solid product concentration is kept at a high concentration of 1.0% or more and at a temperature of 30q○ or more for about one week until the start of polymerization, powdering due to the solvent tank is difficult to occur, and the shape of the polymer particles is maintained. No deterioration occurred, and no decrease in polymerization activity was observed. This effect is significantly improved by preactivation with the Q-olefin according to the present invention. As a result, even when the catalyst of the present invention is used after being stored as a powder, there is little decrease in polymerization activity, and the particle shape of the Q-olefin polymer obtained using this catalyst is also good. Its strengths have come to be demonstrated. Example
1 {1} Preparation of solid product (m) n-hexane 60 [, diethylaluminum monoc.

0.05 mol of DEAC and 0.12 mol of diisoalumiether were mixed at 25oo for 1 minute, and reacted for 5 minutes at the same temperature to form the reaction product liquid (RP,) (diisoamyl ether). /DEAC molar ratio of 2.4) was obtained. Put 0.4 mol of titanium tetrachloride into a reactor purged with nitrogen, and add 350 mol of titanium tetrachloride.
0, and the entire amount of the reaction product liquid (RP.) was added dropwise to this over 30 minutes, and then kept at the same temperature for 30 minutes, and 75q
The temperature was raised to 0 and reacted for another 1 hour, cooled to room temperature, the top lighting solution was removed, 400 g of n-hexane was added, and the top lighting solution was removed by decantation. This operation was repeated 4 times to obtain a solid product. (
0) I got it on the 19th. The total amount of this (0) is n-hexane 3
00, 16 parts of diisoamyl ether and 35 parts of titanium tetrachloride were added at 20°C over about 1 minute at room temperature, and the mixture was reacted at 65°C for 1 hour. After the reaction is complete, cool to room temperature (20°C), remove the supernatant liquid by decantation, add 400 ml of n-hexane, leave to stand still for 10 minutes, and remove the supernatant liquid. After repeating the operation five times, it was dried under reduced pressure to obtain a solid product (m). '2)
After purging the stainless steel reactor with inclined blades with nitrogen gas, prepare the preactivation solvent with a volume of 2 and n-hexane.
0 of [, diethylaluminum monochloride 420 of 9
After adding 30 m of the solid product (m) obtained in the above {1} at room temperature, 150 m of hydrogen was added, and the propylene partial pressure was 5 k9.
/ Carp G for 5 minutes (propylene 80.0 t reaction per 19 solid product (mountain)), and after removing unreacted propylene, hydrogen and n-hexane under reduced pressure, 20.0 g of n-hexane was added to the material to be removed. 9 of triethylaluminum 85 and 9 of hexamethylphosphoric acid triamide 110 are combined into 35q○
Then, the reaction products reacted for 30 minutes were added and mixed at room temperature to obtain a preactivated catalyst.

[3' Propylene polymer] Hydrogen 1
A gas phase polymerization reaction was carried out for 2 hours at a propylene partial pressure of 22 k9/g and a polymerization temperature of 70 oo.

After the reaction is complete, add methanol for 30 minutes to kill the reaction for 70 minutes.
After heating for 10 minutes, the polymer was cooled to room temperature (20° C.) and the resulting polymer was dried to obtain a polymer No. 3039. Polymer yield per evening of solid product (m) is 10
, 100 evenings, and the isotactic index (2
n-hexane insoluble content (%) at 0oo is 99.0
The polymer BD was 0.48, and the polymer particles were aligned and there were no lumps. No coloring of the polymer was observed and the yellowness index (YI) was 0.8. Also,
In order to find out the degree of corrosiveness of the polymer depending on the heating stability after killing the catalyst, the polymer was heated to a certain temperature and the difficulty of acid gas generation was tested by checking whether there was a Congo red color change (JISK-6723). However, there was no discoloration. Comparative Example 1 In the preactivation of Example 1, after combining diethylaluminum monochloride and the solid product (m), hydrogen was only added to react propylene, and triethylaluminum and hexamethylphosphoric acid were combined. Catalyst preparation and gas phase polymerization of propylene were carried out in the same manner as in Example 1, except that the reaction product with triamide was not added.

Polymerization activity was low. Comparative Example 2 In the preactivation of Example 1, after adding diethylaluminum monochloride and the solid product (m), the reaction product of triethylaluminum and hexamethylphosphoric triamide was added without reacting propylene. When Example 1 was repeated except for adding , polymer lumps were formed in the polymerization of [3} and the polymer yield did not increase.

Comparative Example 3 Example 1 was repeated, except that in the preactivation of Example 1, triethylaluminum and hexamethylphosphoric triamide were not reacted but were added separately.This catalyst had low polymerization activity. , the isotactic index of the obtained polymer was also low.

Comparative Example 4 In the production reaction of the reaction product (RP,) of Example 1,
Example 1 was repeated except that the diethylaluminum monochloride was not used.

Comparative Example 5 0.12 mol (19
Solid product (RP2) is not used in the production reaction.
Example 1 was repeated, except that the diisoamyl ether 16 used in the reaction with was added later in the evening.

Comparative Example 6 Example 1 was repeated except that diisoamyl ether was not reacted in the reaction for producing the solid product (m) of Example 1.

Comparative Example 7 In place of the solid product (0) of Example 1, 0.05 mol of diethyl aluminum monochloride was replaced with 0.4 mol of titanium tetrachloride.
Example 1 was repeated, except that a solution of 0.12 moles of diisoamyl ether and 0.12 moles of diisoamyl ether was used.

Comparative Example 8 Example 1 was repeated except that solid product (0) of Example 1 was used instead of solid product (m).

Comparative Example 9 Example 1 was repeated except that titanium tetrachloride was not used in the reaction with the solid product (b) in the reaction for producing the solid product (m) of Example 1.

Example 2 80 mol of di-n-heptane, 0.10 mol of di-n-butylaluminum monochloride, 0.30 mol of di-n-butyl ether
The moles were mixed at 30 qo for 3 minutes, and the two powders were reacted to obtain a reaction product liquid (RP,).

The total amount of this reaction product liquid (RP,) was added dropwise over 6 minutes to a solution containing 50% of toluene and 0.64 mol of titanium tetrachloride maintained at 4yo, then heated to 85°C and further 2
Allowed time to react. Then, cool to room temperature, remove the supernatant, and
The operation of adding 300 units of hebutane and removing the top liquid by decantation was repeated twice to obtain 49 units of solid product (0). The entire amount of (0) was suspended in 300 g of n-heptane, 20 g of di-n-butyl ether and 150 g of titanium tetrachloride were added at room temperature for about 2 minutes, reacted at 9,000 g for 2 hours, and after cooling, After decantation, washing with n-hebutane and drying, a solid product (m) was obtained. after that,
Preactivation of the catalyst and polymerization of propylene were carried out in the same manner as '2) and '3' of Example 1. Comparative Example 10 Polymerization was carried out in the same manner as in Example 2 except that a preactivation solvent without the addition of the reaction product (RP2) was obtained.

Comparative Example 11 Example 2 was repeated except that solid product (0) of Example 2 was used instead of solid product (m).

Example 3 In the production reaction of solid product (0), titanium tetrachloride was
Example 1 was repeated, except that the reaction product solution (RP,) was added dropwise at 1〆○ for 45 minutes while the temperature was kept at 0, and then the temperature was kept at 350 for 60 minutes.

The solid product (m) obtained in this example was brown in color. Comparative Example 12 Polymerization was carried out in the same manner as in Example 3 except that a preactivated catalyst without the addition of the reaction product (RP2) was obtained.

Example 4 Example 1 was repeated except that in the production reaction of the solid product (b) of Example 1, the temperature raised after dropping the reaction product liquid (RP,) onto titanium tetrachloride was changed from 75q0 to 65q0. .

The solid product (m) obtained in this example was brown in color. Comparative Example 13 Polymerization was carried out in the same manner as in Example 4 except that a preactivated catalyst without the addition of the reaction product (RP2) was obtained.

Example 5 0.057 mol of diethylaluminum monochloride and 0.15 mol of diisoamyl ether in n-hexane 40
The reaction solution was added dropwise at 18 qo over 5 minutes and reacted at 35 qo for 30 minutes.
500 for 180 minutes).

The reaction mixture was further held at 35 qo for 60 min, then 76 qo
The temperature was raised to 0 and heated for 60 minutes, cooled to room temperature (2000), removed the supernatant liquid, added 400 m of n-hexane, and removed by decantation, which was repeated twice to obtain a solid product (
0) Obtained on the 24th. This entire amount was suspended in 100 g of n-hexane, 12 g of diisoamyl ether was added, and 35 g of diisoamyl ether was added.
The reaction mixture was allowed to react at ℃ for 1 hour, and 12 portions of diisoamyl ether and 72 portions of titanium tetrachloride were added at 3500℃ for 2 minutes, and the temperature was raised to 65℃. After reacting for 1 hour, it was cooled to room temperature (20:00). , decantation, n-hexane washing and drying,
A solid product (m) was obtained. Thereafter, the same equipment as in Example 1 was used to prepare a preactivated catalyst and polymerize propylene. Comparative Example 14 Polymerization was carried out in the same manner as in Example 5, except that a preactivated catalyst without the addition of the reaction product (RP2) was obtained.

Example 6 Example 5 was repeated except that 0.06 mol of diisopropylene aluminum monochloride and 0.14 mol of di-n-octyl ether were reacted in the reaction to form the reaction product (RP, ).

Comparative Example 15 Polymerization was carried out in the same manner as in Example 6 except that a preactivated solvent without the addition of the reaction product (RP2) was obtained.

Example 7 Example 5 was repeated except that in the production reaction of the solid product (0) of Example 5, the amount of titanium tetrachloride used to react with the reaction product (RP,) was 0.12 mol. Ta.

Comparative Example 16 Polymerization was carried out in the same manner as in Example 7 except that a preactivated catalyst without the addition of the reaction product (RP2) was obtained.

Example 8 Solid product (b) 24 obtained in the same manner as in Example 5
Suspend the mixture in 200 g of toluene and add 1 g of titanium tetrachloride.
0 qo, add 26 qo of di-n-butyl ether,
After 18 hours of reaction, the reaction mixture was cooled to room temperature (20 qo), followed by decantation, washing with n-hexane, and drying to obtain a solid product (m), and prepare a preactivated catalyst in the same manner as in Example 1. Polymerization of bu-o-pyrene was carried out.

Comparative Example 17 Polymerization was carried out in the same manner as in Example 8 except that a preactivated catalyst without the addition of the reaction product (RP2) was obtained.

Example 9 A reaction solution (RP,) obtained by reacting 0.03 mol of triisoptylaluminium and 0.07 mol of di-n dodecyl ether for 30 minutes in 100 units of n-hexane at 20 oo was mixed with titanium tetrachloride. After dropping it into 0.15 mol at 20 oo over 120 minutes, keeping it for 30 minutes at 30 o'clock, raising the temperature to 5,000 ℃ and reacting for 60 minutes, then decanting the supernatant solution and washing with n-hexane. After drying, a solid product (2) was obtained.

This total amount was suspended in 50 m of n-hebutane, 21 m of di-n-butyl ether and 40 m of titanium tetrachloride were added, and 50 m of n-hebutane was added.
After reacting at o0 for 140 minutes, the reaction mixture was cooled, and the supernatant liquid was decanted, washed with n-hexane, and dried to obtain a solid product (m). Thereafter, in the same manner as in Example 1, a preactivated catalyst was prepared and propylene was polymerized. Comparative Example 18 In the preactivation of Example 9, the reaction product (
RP2) Polymerization was carried out in the same manner except that a preactivated catalyst without additives was obtained.

The results of Examples 1 to 9 and Comparative Examples 1 to 18 are shown in Table 1.

In the table, one fixed catalyst component r is the solid product (m)
It is also a general term for the solid product (m) and the solid product (b)) used in the polymerization in combination with organoaluminium etc. in the comparative example.

The same applies in the table below. Notes to Table 1) 1) Melt flow rate, (ASTM D-12
38 (L)) 2) Yellowne index (JI
According to SK-7103) 3) According to JIS K-6723.

Example 10 4 parts of n-pentane, 160 parts of diethylaluminum monochloride, 32 parts of the solid product (m) obtained in Example 1, and 5 parts of polypropylene powder were added and mixed, and then n-bentane was added under reduced pressure. The propylene was removed and reacted in the gas phase at a propylene partial pressure of 0.8 k9/dg at 3000 °C for 20 minutes while fluidizing with propylene gas (
solid product (m) propylene 1.8 reactions per evening),
Unreacted propylene was purged.

Next, a reaction product (RP2) obtained by reacting triethylaluminum 30 9 and ethyl benzoate 41 c in n-pentane 10 at 20 ° C. for 10 minutes was added to the above reaction mixture to obtain a preactivated catalyst. , Gas phase polymerization of propylene was carried out in the same manner as '3' of Example 1. Comparative Example 19 Reaction product (RP2) in preactivation of Example 10
Polymerization was carried out in the same manner except that a preactivated catalyst with no additives was obtained.

Example 11 In 30 g of propylene, 9 of 120 di-n-butylaluminum monochloride and 9 of 25 of the solid product (mountain) obtained in Example 2 were added at 20 q○, and heated at 9.8 k9/g for 10 minutes. After reaction (120 units of propylene reacted per unit of solid product), the reacted propylene was purged.

Then triisobutylaluminium 54 9 and ethyl benzoate 30 9 were dissolved in 18' n-hexane at 30 qC.
The reaction product (RP2) reacted three times in Step 3 was added to the above reaction mixture to obtain a preactivated catalyst, and the reaction product (RP2) of Example 1 was
} The gas phase polymerization of propylene was carried out in the same manner. Comparative Example 20 Reaction product (RP2) in preactivation of Example 11
Polymerization was carried out in the same manner except that a preactivated catalyst with no additives was obtained.

Example 12 Z of n-bentane 20 is 9 of diethylaluminium monochloride 280, solid product obtained in Example 2 (m) 2
9 of 5 was added, and at 15:00, the propylene partial pressure was increased to 5k9/G over 5 minutes (heating rate: lk9/G/min), and the propylene was reacted (solid product (m)
(3.2 ta reaction of propylene per night), unreacted propylene was purged.

Next, 9 of triethylaluminum 23 and methyl p-toluate 1&o are reacted in n-pentane 20 at 150° for 3 minutes, and the reaction product (RP2) is added to the reaction mixture to obtain a preactivated catalyst. Example 1 (31
Gas phase polymerization of propylene was carried out in the same manner as described above. Comparative example
21 Reaction product (RP2) in preactivation of Example 12
Polymerization was carried out in the same manner except that a preactivated catalyst with no additives was obtained.

Examples 13 to 15 In the catalyst preactivation of Example 12, instead of using the reaction product of triethylaluminum and p-methyl tolylate, the following reaction product (RP2) was used for each example.
Example 12 was repeated except that .

Example 13: Reaction product of triisobutylaluminum 8.4 part 9 and N,N,N',N'-tetramethylhexalenediamine 90 part 9 Example 14: Diethyl aluminum monochloride 24 part 9 and the reaction product of triethylaluminum 40 and ethyl p-anisate 36-9,
Example 15: Ethylaluminum dichloride 25-9
and triethylaluminum 75 9 and N, N, N', N
-Reaction product of tetramethylurea 28 with 9.

Example 16 Example 12 was repeated except that 9 of 34 diphenyl ether was used in place of methyl p-toluate in the preparation of the reaction product (RP2).

Example 17 9 of diethylaluminum monochloride 210 over 10 of n-hexane, 28 m of the solid product obtained in Example 1 (m)
g and 20% of n-hexane, 11% of triethylaluminum, 15% of ethyl benzoate and 3% of it at 2800.
It was added to the reaction product (RP2) that had been reacted for 0 minutes.

Then, while fluidizing the catalyst obtained by removing n-hexane under reduced pressure with propylene, the propylene partial pressure was 2k9/Funa G,
A preactivated catalyst was obtained by reacting in the gas phase at 30 oo for 10 minutes. Thereafter, gas phase polymerization of propylene was carried out in the same manner as in the case of the lake in Example 1. Comparative Example 22 Reaction product (RP2) in preactivation of Example 17
Polymerization was carried out in the same manner except that no was added.

Example 18 In n-hexane 100%, propylene partial pressure 2k9/
Carp G, 50 oo of propylene was dissolved, 9 of diethyl aluminum monochloride 180, 9 of 20 of the solid product (m) obtained in Example 1, and 10 of n-hexane [
The reaction product (RP
2) was added.

Then, after maintaining the propylene partial pressure for 7 minutes so that 20 parts of propylene were reacted per 1 part of the solid product (m), unreacted propylene was purged and n-hexane was removed under reduced pressure. Then, in the same manner as in {3} of Example 1, gas phase polymerization of propylene was carried out. Comparative Example 23 Reaction product (RP2) in preactivation of Example 18
Polymerization was carried out in the same manner except that a preactivated catalyst with no additives was obtained.

Example 19 In the preparation of the preactivated catalyst of Example 1, ethylene was added in place of propylene at lk9/g, 10 minutes, 35qo
(solid product (m) ethylene per night).
Example 1 was repeated with the exception of 4-ta reaction).

Example 20 In the preparation of the preactivated catalyst of Example 1, butene-1 was added in place of propylene at 0.5 k9/g for 10 minutes at 3
Example 1 was repeated, except that the reaction was carried out at 5° C. (0.3 night of butene-1 reaction per night of solid product (m)).

Example 21 Example 1 was repeated except that diisopropylene aluminum monochloride Soho 9 was used in place of diethyl aluminum monochloride in step (1) of Example 1.

The results of Examples 10 to 21 and Comparative Examples 19 to 23 are shown in Table 2.

Table 2 Example Pine After obtaining a preactivated catalyst in the same manner as Example 12,
Add 300 ml of hydrogen and 600 ml of propylene, and add 70 ml of hydrogen.
Bulk polymerization was carried out for 2 hours at a propylene partial pressure of 31k9/equal G at 00.

After the reaction was completed, unreacted propylene was purged and post-treatment was performed in the same manner as in Example 1 to obtain a polymer. Example 23 After obtaining a preactivated catalyst in the same manner as in Example 12,
300 tons of hydrogen and 200 tons of propylene were charged, and bulk polymerization was carried out at 60 qo for 3 minutes at a propylene partial pressure of 26 k9/lump G to polymerize 35 tons.

Next, the slurry containing unreacted propylene was flashed into a fluidized bed with a diameter of 2 mm and a volume of 20 mm, equipped with a cylindrical blade, and propylene was circulated at a flow rate of 5 k/sec at a reaction temperature of 70 oo and a propylene partial pressure of 21 kg/sec. Gas phase polymerization reaction was carried out for 2 hours while fluidizing the polymer. After that, Example 1
A polymer was obtained by post-treatment in the same manner as above. Example 24 Bulk polymerization was carried out in the same manner as in Example 23 at 26k9/average G, 60
After running for 30 minutes at 00C, the reacted liquefied propylene was transferred to another feed tank connected to the reactor, and the reactor was heated to 72C.
While feeding propylene from the feed tank to the reactor so that the temperature rose to 0 and the polymerization pressure became 26k9/Sakaki G,
Gas phase polymerization was carried out for 2 hours.

Thereafter, the polymer was post-treated in the same manner as in Example 1 to obtain a polymer.
Example 25 Bulk polymerization was carried out in the same manner as in Example 23 at 26k9/ground G,
After 3 minutes at 6,000 ℃, the polymerization temperature was raised to 7,000 ℃, and the polymerization pressure became 31 kg/G.

As the polymerization continued, the pressure decreased every four ships until 26k9/light G, and the bulk polymerization was continuously shifted to gas phase polymerization. Gas phase polymerization was further carried out for 6 seconds while feeding propylene to maintain a G of 26 kg/g, and the polymer was then post-treated in the same manner as in Example 1 to obtain a polymer. Example 26n
- 1,000 g of hexane, 206 g of diethyl aluminum monochloride, 1 m of the solid product obtained in Example 2
Add 8 o, propylene partial pressure 1.2k9/g, 20
℃ in one proportion of propylene (solid product (m)
After purging the unreacted propylene, 9 of 23 of triethylaluminum and 9 of 24 of methyl p-tolylate were dissolved in 20 of n-hexane.
A reaction product (RP2) reacted at 20 qC for 30 minutes was added to obtain a preactivated catalyst.

Add 150% hydrogen to this, and propylene partial pressure 13k
9/After performing slurry polymerization at 70qo for 3 hours,
The n-hexane was removed by steam stripping to obtain a polymer. Comparative Example 24 Reaction product (RP2) in preactivation of Example 26
Polymerization was carried out in the same manner except that a preactivated catalyst without any additives was obtained.

Example 27 In Example 26, instead of using 1,000 g of n-hexane, 80 g of n-hexane was used and 200 g of hydrogen was added, and the slurry was made between 6 powders at 7030 G and 7030 g with a propylene partial pressure of 10 k9/. Monopolymerization was carried out, 60 times multipolymerization was carried out (3,300 propylene polymerized per night of solid product (m)), and the reaction product (RP
2) was added to obtain a preactivated catalyst.

Using this slurry polymerization containing the solvent and unreacted propylene, it was placed in a fluidized bed equipped with a fly wing and subjected to gas phase polymerization of propylene in the same manner as in Example 23. Example 28 200 parts of n-hexane, 1.8 parts of dimethylaluminum monochloride, and 0.3 parts of the solid product (m) obtained in Example 2 were placed in a fluidized bed equipped with a blade, and the propylene content was Pressure 1.5
After reacting propylene for 1 hour at k9/G, 25 qo (1.1 ta of propylene reacted per 1 m of solid product), 0.45 q of triethylaluminum was reacted in 80 ml of n-hexane. and methyl p-toluate 0.36 to 20
A preactivated catalyst was obtained by adding the reaction product (RP2) that had been reacted at 00 for 5 hours.

Next, 3,000 ml of hydrogen was added to the liquid bed, and 70 ml of hydrogen was added.
When the reaction was carried out at a propylene partial pressure of 21k9/g and propylene was circulated at a rate of 5 skins/sec, slurry polymerization occurred at first, but after 1 hour (a solid product (
The polymer particles began to fluidize, and gas phase polymerization was continued for an additional hour. After polymerization, post-treatment was carried out in the same manner as in Example 1 to obtain a polymer. Comparative Example 25 Reaction product (RP2) in preactivation of Example 28
Polymerization was carried out in the same manner except that a preactivated catalyst without additives was obtained.

Example 29 The solid product (blood) obtained in the same manner as in Example 1 was
After storing the mixture for 4 months, propylene was polymerized in the same manner as in Example 1 [2} and {31].

Example 30 A preactivated catalyst obtained in the same manner as in Example 12 was left standing at 30° C. for one week, and then propylene was subjected to gas phase polymerization in the same manner as in Example 12.

Comparative Example 26 In preactivating the catalyst of Example 12, n-pentane was mixed with diethylaluminum mo/chloride, solid product (m
) was added, a catalyst was prepared in the same manner as in Example 12 except that propylene was not reacted, and after being left at 30 oo for one week, propylene was polymerized in the same manner as in Example 12. Ta.

Not only the polymerization activity decreased significantly, but also the polymer BD decreased.
In addition, polymer lumps were also formed. The results of Examples 22 to 30 and Comparative Examples 24 to 26 are shown in Table 3.

Table 3 Example 31 Using the preactivated catalyst obtained in Example 1, hydrogen 12
Ethylene polymerization was carried out in accordance with Example 1 at a G of kg/g, an ethylene partial pressure of 12k9/G, and a mass of 8.

Example 32 In Example 27, after the first stage slurry polymerization was carried out using propylene, the second stage gas phase polymerization was carried out at a hydrogen partial pressure of 8 k9/g and an ethylene partial pressure of 12 kg/cm.
oo, Example 27 except that the ethylene polymerization was carried out for 2 hours.
Block copolymerization of propylene and ethylene was carried out in the same manner as described above. Example 33 In Example 23, a polymer (propylene-ethylene copolymer ) was obtained.

Example 34 In Example 33, a polymer was prepared in the same manner as in Example 33, except that 30 days of butene-1 was used instead of 20 days of ethylene.

. A pyrene-buteso 1 copolymer) was obtained. Example 35 In Example 1 (■), a preactivated catalyst obtained in the same manner as in Example 1 (m) and [2} was used except that 9 of triethyl aluminum 320 was used instead of diethyl aluminum monochloride. Then, ethylene polymerization was carried out in the same manner as in Example 31.

Example 36 9 of diethylaluminum monochloride 941 on n-hexane 500, solid product obtained in Example 1 (m) 4
Triethylaluminum 95-9 (0.83 mmol) and methyl p-tlu'ilate 37-9 (0.25 mmol) were added to 280 mmol of 95-95 (0.25 mmol) in 80-9 and 300 mmol of n-hexane.
The reaction product (RP2) obtained by reacting at 0 for 1 hour (
RP2) Add 9 with a molar ratio of 0.30) 132, propylene partial pressure 2k9/c liquid G, react with propylene for 1 powder at 3500 (solid product (m) 17 reactions per night), Unreacted propylene was purged and preactivated]
I got a catalyst.

Next, 3,900 screams of hydrogen were fired. Pyrene partial pressure 22k9
Polymerization of propylene and ethylene was carried out between 12 and 6,000 g/min at 6,000 liters while maintaining the G of 1/2 and adding ethylene at a rate of 1.6 min/min. The ethylene content in the polymer is 3.
It was 4%. Comparative Example 27 In the preactivation of Example 36, the reaction product (RP2
) Polymerization was carried out in the same machine except that a preactivated catalyst without additives was obtained.

Comparative Examples 28-30 In the preparation of the preactivated catalyst of Example 36, 9 of triethylaluminum 95 (0.83 mmol) (Comparative Example 28) and p-tolyl were used instead of the reaction product (RP2). Methyl acid 37-9 (0.25 mmol) (Comparative example 2
9), and Example 36 was repeated, except that 9 of triethylaluminum 95 and 9 of methyl p-toluate 37 were added momentarily and simultaneously without reacting (Comparative Example 30).

In both cases, atactic polymer increased. Comparative Example 31 Example 36 was repeated except that the propylene was not reacted in the preparation of the preactivated catalyst.

In this propylene-ethylene copolymerization, polymer lumps were formed during the polymerization, and the polymer yield could not be increased.
Example 37 Example 36 was repeated except that ethylene was fed at a rate of 2.3 min/min.

The ethylene content in the polymer was 5.1%. Table 4 shows the results of Examples 31 to 37 and Comparative Examples 27 to 31.

Table 4 Example 38 n-octane 45 [in which triethylaluminum 0.
07 mol and 0.15 mol of di-n-propyl ether
The reaction product (RP,) which was mixed at 0.000 °C for 2 hours and reacted between three powders at the same temperature was added dropwise into 0.6 mol of titanium tetrachloride at 3 °C over 4 hours.

The reaction mixture was then held at 35q0 for 1 hour and further heated at 78
qo and react for 2 hours, cool to room temperature (20q0), remove the upper lighting solution, add 400% of n-hexane, and remove the upper lighting solution by decantation. Repeat this operation 5 times.
After confirming that titanium tetrachloride is no longer detected in the decanted liquid, it is separated and dried to form a solid product (0)2.
I got 3 nights. To 300 pieces of n-hebutane, 47 parts of di-n-benzyl ether and 5 parts of anhydrous aluminum trichloride were added and reacted at 80°C for 2 hours to remove the anhydrous aluminum trichloride, and the mixture was cooled to 3,000 ml of n-hebutane.

Add the above solid product (b) 23 to this reaction product,
After reacting at 8,000 ℃ for 2 hours, cool to room temperature, remove the upper lighting solution by decantation, add 300ml of n-hexane, and remove the upper lighting solution by decantation.
After repeating the process several times, the mixture was separated and dried to obtain a solid product (m). Thereafter, preactivation of the catalyst and polymerization of propylene were carried out in the same manner as in Example 1, '3'. Example 39
In Example 1, instead of reacting the solid product (0) with diisoamyl ether and titanium tetrachloride, diisoamyl ether paper, silicon tetrachloride, and A solid product (b) 19 was added to a mixture of 17 titanium tetrachloride and 17 titanium tetrachloride at room temperature (20 °C) over about 1 minute.
After addition of water, the mixture was allowed to react at 75q0 for 2 hours.

After the reaction was completed, the mixture was washed with n-hexane and dried to obtain a solid product (m). Thereafter, preactivation of the catalyst and polymerization of propylene were carried out in the same manner as in Example 1 (1), '3}. Comparative Example 31 In the preparation of the solid product (m) of Example 1, after reacting titanium tetrachloride with the reaction product liquid (RP,), n-hexane was added to 300 ml without removing the supernatant liquid. Example 1 was repeated, except that the suspension of solid product (b) was used in place of the suspension of solid product (b) in the subsequent reaction between diisoamyl ether and titanium tetrachloride. .

Comparative Example 32 In the preparation of solid product (m) of Example 1, solid product (0) was replaced by the following solid product.

That is, 60 M of n-hexane was added to a solution consisting of 0.4 mol of titanium tetrachloride and 0.12 mol of diisoamyl ether.
and 0.05 mol of diethylaluminum monochloride
After adding for 30 minutes at zero temperature, keep at the same temperature for 30 minutes,
The temperature was raised to 75°C and the reaction was continued for an additional hour. The reaction mixture was cooled to room temperature and washed with n-hexane to obtain a solid product No. 19. Example 1 was repeated except that this was used in place of solid product (b). The above example spots -
Table 5 shows the results of Comparative Examples 31-32.

Example 40 n-hexane 80 was added to a stainless steel reactor with slanted blades.
0', diethylaluminum monochloride 2,880
9, 540 m of the solid product obtained in Example 1 was added to 20
After adding at 00, propylene partial pressure 1.5k9/G, 2
000 for 7 minutes (solid product (
m) 14 ta of propylene per night reaction).

After purging unreacted propylene, the reaction mixture was mixed with 181 o of triethylaluminum in 200 o'hexane.
The reaction product (R
P2) 9 of 419 was added and mixed at room temperature to obtain a preactivated catalyst. Subsequently, 7,200 g of hydrogen was charged into the reactor holding the catalyst, and the propylene partial pressure was increased to 22 k9.
/ Carp G, a gas phase polymerization reaction was carried out at a polymerization temperature of 70 qo for 2 hours. After the reaction, add 48 methanol and heat at 70°C for 1 hour.
After performing a time-kill reaction, it was cooled to room temperature (20 qo),
A polymer was obtained by drying. This polymer was pressed at 20,000 for 3 minutes at 10 k9/g, the resulting film was cooled with water, annealed at 135 qo for 120 minutes, and then Lu
Method of on-paddy [J. P. Luongo, J. Appl.
Polymer Sic. , 3, 302 (1960
)], and the flexural modulus was measured according to JISK-7203.

In addition, other measured values were obtained in the same manner as in Example 1. Example 4
1-44 Example 40 was repeated except that the amount of methyl p-toluate used in the preparation of the reaction product (RP2) was as follows for each example.

Example 41: 477 of 9 (3.18 mmol) ((RP
2) molar ratio 2.0, (RP2) amount 658 p) Example 4
2:119 of 9 (0.79 mmol) ((RP2) molar ratio 0.5 (RP2) amount 300 of 9) Example 43:60
9 (0.4 mmol) ((RP2) molar ratio 0.25 (
RP2) Amount 241 female) Example 44:36 o (0.24
mmol) ((RP2) molar ratio 0.15 (RP2) amount 2
17-9) Comparative Example 33 Example 40 was repeated except that no reaction product (RP2) was added in the catalyst preparation.

Comparative Example 34 Example 40 was repeated except that 9 of triethylaluminum 181 (mmol of 1.5 stage catalyst) was used in place of the reaction product (RP2) in the catalyst preparation.

Atactic polymers increased. Comparative Examples 35-39 Example 40 was repeated except that the following amounts of methyl p-toluate were used in place of the reaction product (RP2) in the catalyst preparation.

Comparative Example 35: 477 of 9 (3.18 mmol) Comparative Example 3
6:238 (1.59) Comparative example 37:119
〃(0.79〃) Comparative example 38:60〃(0.4
〃) Comparative example 39:36〃(0.24 〃)IR
-7, flexural modulus remained unchanged.

The results of the above Examples 40 to 4 and Comparative Examples 33 to 39 are
Shown in the table.

Table 6 Example 45 Specific surface area, surface infrared measurement, X-ray diffraction and AI (metal), Ti of the solid products (m) obtained in Examples 1, 2, 5, and 8
(metal), CI, and diisoamyl ether were analyzed and observed using an optical microscope.

The results are shown in Table 7 and the infrared diagram M. Shown in 1. '1) Measurement of specific surface area Micromeritics
) The specific surface area was measured using the automatic specific surface area measuring device 220 using nitrogen gas at the liquid nitrogen temperature using the one point BET method.

(2) Surface infrared measurement The diffuse reflection spectrum of a sample sandwiched between KRS-5 plates was measured using a Fourier transform infrared spectrophotometer (JIR-400) manufactured by JEOL Ltd.

'3} X-ray diffraction Using a goniometer (PMG-S2) manufactured by Rigaku Denki Co., Ltd., CuKa radiation (input = 1
．． 54A), using nickel for the filter, 40KV2
X-ray diffraction was performed on melon hA.

{4) Composition analysis After decomposing the weighed sample with water, AI and T were determined by Fujiko absorption method.
i was separated.

The electron donor was extracted with n-hexane and then measured using a gas chromatograph, and the content was calculated from a calibration curve. '51
Observation using an optical microscope A sample sandwiched between glass plates was observed using an optical microscope (manufactured by Olympus Optical Co., Ltd.).

Comparative Example 40 For comparison, Tsubaki Sekisho 47-34478 (USP-4, 21
A catalyst collar body manufactured according to Example 1 of 0.7 paper) was measured.

The results are shown in Table 7 and infrared diagram M. Shown in 2. The method for manufacturing the catalyst rust body used in Comparative Example 40 is as follows.

A. Production of reduced solids Hexane 600M and TIC 14150 I were fitted with a two-plate vane lantern rotating at 16 pm under an inert atmosphere.
into the reactor.

Cool the hexane-TIC14 solution (250/1 diluent) to 1°C. Dry hexane 450' and Al
A solution consisting of Et2CI173 (375 min/1 diluent) was added within 4 hours, during which time the temperature in the reactor was kept at 1°C.
Kazu Niho). After adding the hexane-NELCI solution, the reaction mixture consisting of a suspension of fine particles was incubated for about 18 minutes at 1°C under a sandbox.
The reaction soot was then kept under a light for an additional hour at 65 qo.

The liquid phase is then separated from the solid by passing through and the brown solid product is purified five times with 500 g of dry hexane.

The solids are resuspended after each wash. Finally, the solid product is freed from absorbed hexane by flushing with nitrogen. 285 ml of the dried product was collected, which will hereinafter be referred to as reduced solid.
It contains approximately 200 ta of TIC13 in type 8 crystalline form. B Treatment of reduced solid with mirroring agent Obtained reduced solid 2
Suspend 85 ml of diluent (hexane) in 1720 ml of diluent (hexane),
To this is added diisoamyl ether (EDIA) 256'. This is EDIAO.per TIC13/mole.
This corresponds to 95 moles and 6 moles of EDIAI per diluent. This suspension was heated at 35° C. for 1 hour. The resulting treated solid was then separated from the liquid phase and washed five times with 25 qo of hexane 500. This treated solid was
Optionally can be dried with dry nitrogen. C TIC1 of treated solid
Reacting the solid with 4 as a 40% by volume solution of TIC14 in hexane 8
Suspend in 50'.

This suspension was kept under the control for 2 hours at 65 pm. The liquid phase was then removed and the solid product obtained, so-called solid catalyst complex, was washed four times with 500 g of hexane at 25°C,
Finally, wash once with 500ml of hexane at 65°C. The solid catalyst body is separated from the hexane and dried with pure dry nitrogen. In this way, 256 pieces of dry solid catalyst body are collected. Table 7 Strength s>m>w>ww Comparative Example 41 Propylene polymerization was carried out in the same machine as in Example 1, using the catalyst body obtained in Comparative Example 40 instead of the solid product (m). Ta.

The polymer yield per night of catalyst rust was 4,700 times. Example 40 Comparative Example 42 The solid product (m) obtained in Example 1 or the catalyst body obtained in Comparative Example 40 was heated at 55 qo in an inert gas atmosphere, respectively.
After heating for one day, the mixture was cooled, and propylene was polymerized in the same manner as in Example 1.

The results are shown in Table 8. As is clear from the table, the solid product (dish) obtained in Example 1 had excellent thermal stability, and the decrease in polymer yield was less than 5% compared to Example 1 ( Example 46). On the other hand, when the catalyst complex obtained in Comparative Example 40 was used, the polymer yield decreased by 75%. Table 8

[Brief explanation of drawings]

Infrared Figure 1 is the surface infrared diagram (measured in Example 45) of the solid products (m) obtained in Examples 1, 2, 5, and 8, and Infrared Figure 2 is the surface infrared diagram of the solid products (m) obtained in Examples 1, 2, 5, and 8. FIG. 2 is a surface infrared diagram of the catalyst complex obtained in . Fin diagram Figure 2

Claims (1)

[Scope of Claims] 1. A solid product (II) obtained by reacting a reaction product (RP_1) of an organoaluminum compound (A_1) and ether with titanium tetrachloride, and further containing ether and titanium tetrachloride or titanium tetrachloride. The solid product (III) obtained by reacting aluminum chloride (EA) with an organoaluminum compound (A
_2) and prepolymerized in combination with α-olefin,
Furthermore, an organoaluminum compound (A_3) and an electron donor (
A preactivated α-olefin polymerization catalyst comprising a reaction product (RP_2) with ED_3). 2. The catalyst according to claim 1, which uses a reaction product (RP_1) obtained by reacting an organoaluminum compound (A_1) and an ether in a solvent at -20°C to 200°C for 30 seconds to 5 hours. 3. The reaction product (RP_1) and titanium tetrachloride are combined into the (R
The ratio of the number of Al atoms in P_1) to the number of Ti atoms in the titanium tetrachloride (Al/Ti) is 0.05 to 10, 0°C to 200
Solid product (II) obtained by reacting at °C for 5 minutes to 8 hours
The catalyst according to claim 1, which is formed using: 4 Solid product (II), ether and titanium tetrachloride or aluminum trichloride (EA), based on said (II), 10 to 1000% by weight of ether and 10 to 1000% by weight of titanium tetrachloride or aluminum trichloride (EA). % -1
Mix for 30 seconds to 60 minutes at 0°C to 40°C, and mix at 40°C to 20°C.
A solid product obtained by reacting at 0°C for 30 seconds to 5 hours (
III). The catalyst according to claim 1. 5 Ether and titanium tetrachloride or aluminum trichloride (
A reaction mixture obtained by reacting EA) at 10°C to 100°C for 30 minutes to 2 hours and cooling to 40°C or lower is mixed with solid product (II) and reacted to produce a solid product (III
). 6 Solid product (III), organoaluminum compound (A
_2) and the reaction product (RP_2) of an organoaluminum compound (A^3) and an electron donor (ED_3) are supplied to a catalyst containing α-olefin and heated at 0 to 100°C for 1
The catalyst according to claim 1, which is preactivated by polymerizing 0.01 g to 2,000 g per 1 g of solid product (III) in the catalyst in minutes to 20 hours. 7 Solid product (III), organoaluminum compound (A
_2) By supplying α-olefin to the catalyst combined with
The solid product (I
II) 0.01 to 200g per 1g of polymerization, and then the reaction product (RP_2) of the organoaluminum compound (A_3) and the electron donor (ED_3) is combined with the catalyst after the polymerization. catalyst. 8 Per 1 g of solid product (III), 0.1 to 500 g of organoaluminum compound (A_2) and reaction product (R
P_2) The catalyst according to claims 6 and 7, comprising a combination of 0.05 g to 10 g.