JP2006316158A - Polymerization apparatus for manufacturing polyolefin and manufacturing method of polyolefin using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerization apparatus for manufacturing a polyolefin that permits operations under a wide-ranging conditions without restrictions imposed on conventionally known polymerization processes in a polymerization reaction system comprising a multistage polymerization reaction using a solid catalyst component or the like containing a transition metal component. <P>SOLUTION: The polymerization apparatus for carrying out an olefin polymerization reaction using the solid catalyst containing the transition metal component is constituted of a raw material-feeding system (1) capable of arbitrarily changing the composition of respective raw materials used for the polymerization reaction, a polymerization reactor system (2) for polymerizing the raw materials fed from the raw material-feeding system and a purging system (3) for the raw materials from the polymerization reactor system, where the solid catalyst component is batchwise introduced into the polymerization reactor while the raw materials other than the solid catalyst component are continuously introduced into and derived from the polymerization reactor and the polymerization reactor is equipped with a filter so that the solid catalyst component and a formed polymer cannot be derived from the polymerization system during the polymerization reaction. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymerization apparatus for producing polyolefin using a solid catalyst containing a transition metal catalyst component and a method for producing polyolefin using the same, and more specifically, using a solid catalyst containing a transition metal catalyst component, The present invention relates to a polymerization apparatus for producing polyolefin capable of providing a wide range of polymerization conditions with one polymerization reactor and a method for producing polyolefin using the same.

A method of polymerizing olefins such as ethylene and propylene using a solid catalyst containing a transition metal component is widely known. These olefins are polymerized in a slurry polymerization method in which polymerization is performed in an inert hydrocarbon solvent, in a bulk polymerization method in which polymerization is performed in a liquefied monomer such as liquefied propylene, or in the absence of a liquid phase. There is a gas phase polymerization method in which polymerization is performed in a phase.
In addition, as a classification according to the polymerization mode, a continuous polymerization method in which a solid catalyst component, a monomer component, an organoaluminum component, etc. are continuously charged into a reaction system, and polymer particles that are polymerized are continuously taken out. A batch polymerization method in which a set of components are put together and reacted in a reactor, and after the polymerization is completed, the batch polymerization method is taken out of the system, and the catalyst components are fed into a batch type while the raw materials are reacted in parallel with the progress of the polymerization reaction. There is a semi-batch polymerization method to supply to the vessel.
These techniques have already been described in detail in various documents and the like (for example, see Non-Patent Document 1), and a method for producing a propylene copolymer by a semi-batch polymerization method is described in Examples (for example, (See Patent Document 1).
In the polymerization of such olefins, in order to control the processing characteristics as a resin and various physical properties of the product, copolymerization using a plurality of monomer components and adjustment of molecular weight using hydrogen as a chain transfer agent are performed. It has been broken. In addition, so-called multistage polymerization in which the concentration of these reactive components, the polymerization temperature, and the pressure are changed stepwise is also widely performed. These techniques make it possible to adjust the molecular weight distribution and the resin composition distribution that cannot be obtained under a single polymerization condition, which is one of the reasons why olefinic resins are used in a wide variety of processing methods and applications.

  By the way, if such multi-stage polymerization is to be applied to the continuous polymerization method, a process is required in which reactors corresponding to the number of polymerization stages are connected in series. Further, in this case, since the raw material or the like charged into the former reactor flows into the latter reactor, for example, when performing polymerization with a lowered ethylene or hydrogen concentration on the latter stage, a large amount of purge is performed during that time. It is necessary to install a process for diluting the concentration of the component by supplying a large amount of monomer or separating and removing a specific component. Because of these circumstances, there are restrictions on the range of operating conditions for the existing polymerization process, and when a corresponding process is newly installed, economic problems including its construction cost and operation cost will be reduced. It needs to be solved.

  On the other hand, when performing multi-stage polymerization by semi-batch polymerization method or batch polymerization method, polymerization is possible with a single reactor, but from the viewpoint of economy or operation, basically charged raw materials and catalyst components are used. Is not taken out in the middle of the reaction, and it is substantially difficult to adjust to reduce the concentration except for consumption by the reaction. In the case of the batch polymerization method, when there is a substance consumed or produced in the reaction, it is generally difficult to operate the component concentration at a constant level. For example, when copolymerization of ethylene and propylene is carried out by a batch polymerization method, the monomer composition changes sequentially from the beginning as the polymerization conversion increases due to the copolymerizability of both monomers. If this is performed by semi-batch polymerization and the reaction conditions are to be controlled to be constant, it is necessary to accurately add the monomer components consumed in the polymerization. Another example is the problem of molecular weight control when using a catalyst system that generates hydrogen during polymerization. Since hydrogen functions as a chain transfer agent, it is extremely difficult to obtain a polymer having a desired molecular weight by performing batch polymerization or semibatch polymerization in these systems.

As described above, the conventionally used polymerization process is not necessarily suitable for arbitrary multistage polymerization. By the way, as is widely known, recent advances in so-called metallocene catalysts enable the polymerization of olefin polymers having a sharp molecular weight distribution and composition distribution compared to conventional Ziegler catalysts, and their practical application is progressing. . In order to preferably control processability and various product properties using such a catalyst system, optimization of polymerization conditions including multi-stage polymerization is an important issue. For this reason, a polymerization process capable of operating under a wide range of conditions without the limitations of the conventionally known process has been desired.
The Chemical Society of Japan "Polymerization process technology 1994" JP-A-5-117342

  In view of the above problems, the object of the present invention is to provide a wide range of conditions in which a conventionally known polymerization process is removed in a polymerization reaction system including a multistage polymerization reaction using a solid catalyst component including a transition metal component. Another object of the present invention is to provide a polymerization apparatus for producing a polyolefin capable of being operated at a low temperature and a method for producing a polyolefin using the same.

  As a result of intensive studies to solve such problems, the present inventors have conducted olefin polymerization using a solid catalyst component containing a transition metal component in an olefin polymerization reactor, and only the solid catalyst component and the produced polymer. It is found that a polymerization apparatus for polyolefin production that can be operated under a wide range of conditions is obtained by removing the restrictions on the polymerization process by making the introduction and derivation of other raw materials free. did.

  That is, according to the first invention of the present invention, a polymerization apparatus for performing an olefin polymerization reaction using a solid catalyst containing a transition metal component, wherein the composition of each raw material used in the polymerization reaction is arbitrarily changed. It consists of a possible raw material supply system (1), a polymerization reactor system (2) for polymerizing the raw material supplied from the raw material supply system, and a raw material purge system (3) from the polymerization reactor system. A solid catalyst component for polymerization is introduced into the reactor batchwise, and raw materials other than the solid catalyst component are continuously introduced and derived, and the solid catalyst component and the polymer produced during the polymerization reaction are derived from within the polymerization system. It is equipped with a filter so that it becomes impossible, and the raw material composition of the polymerization reactor system can be arbitrarily controlled after the introduction of the catalyst, or it can be changed over time to obtain a polymer having a different composition over time. Is possible Polyolefin production for the polymerization apparatus is provided, wherein the door.

  According to the second invention of the present invention, in the first invention, the polymerization reactor system is a tank reactor having a jacket for controlling the reaction temperature and a stirring mechanism. A polymerization apparatus for producing polyolefin is provided.

  According to the third invention of the present invention, in the first invention, the polymerization reactor system is a solid-gas fluidized bed reactor in which the introduced raw material is substantially a gas, or the introduced raw material is substantially A polymerization apparatus for producing polyolefin is provided, which is a solid-liquid fluidized bed reactor that is liquid in nature.

  According to the fourth aspect of the present invention, in any one of the first to third aspects, the filter in the polymerization reactor system is at least one filter having an opening size of 2500 mesh or more. A polymerization apparatus for producing a polyolefin is provided.

  Moreover, according to 5th invention of this invention, the manufacturing method of polyolefin characterized by superposing | polymerizing an olefin using the polymerization apparatus for polyolefin manufacture of any one of 1st-4th invention is provided.

  According to the polymerization apparatus for polyolefin production of the present invention, the raw material composition in the polymerization reaction can be arbitrarily controlled, and in a case where polymerization is performed with different raw material compositions over time, including so-called multi-stage polymerization, etc., high accuracy and wide range of conditions Polyolefins can be produced under

  Hereinafter, a solid catalyst component containing a transition metal component used in the present invention, a feedstock used for polymerization, a polymerization system for polyolefin production, an apparatus, and a polyolefin production method using the same will be described in detail.

1. Solid catalyst component In the present invention, the solid catalyst component containing a transition metal component for olefin polymerization includes magnesium, titanium, halogen and an electron donating component, a Ziegler catalyst mainly composed of titanium trichloride, and an appropriate one. A metallocene catalyst using a support can be mentioned. These solid catalyst components are generally controlled to have a particle size in the range of 1 to 3000 microns, preferably 5 to 1000 microns.

Specific examples of the solid catalyst component containing a transition metal component include (i) a so-called Solvay-type titanium trichloride obtained by controlling the particle size of the catalyst component itself (components described in JP-A-47-34478, etc.) ), (Ii) Magnesium-supported solid catalyst components obtained by controlling the particle size by dissolution and precipitation and further containing a titanium compound (for example, Japanese Patent Laid-Open Nos. 58-157808 and 58- Components described in Japanese Patent No. 83006, Japanese Patent Laid-Open No. 58-5310, Japanese Patent Laid-Open No. 61-218606), (iii) Inorganic oxidation of silica, silica alumina, clay mineral, magnesium oxide and the like with controlled particle size Titanium compounds such as organic compounds and granular organic compounds typified by polymer particles with controlled particle size, such as polyolefin, polystyrene, and polyvinyl chloride. A so-called carrier-supported catalyst component carrying a catalyst component such as a zirconium compound, a chromium compound, a metallocene compound, an organometallic complex of Groups 8 to 10 of the periodic table, or an organoaluminum compound (for example, JP-A-5-295022) Among these, a metallocene catalyst component is preferable.
Further, as these solid catalyst components, prepolymerized solid catalyst components preliminarily polymerized with a small amount of monomers can be suitably used.

2. Raw materials other than the solid catalyst component The raw materials other than the solid catalyst component used in the polymerization apparatus of the present invention are used as components that inactivate the olefin component, the co-catalyst or the catalyst poison water and active compounds constituting the polymer. Various additives for the purpose of organometallic compounds, molecular weight control agents, stereoregularity improvement, particle property control, control of soluble components, control of molecular weight distribution, and the like are used.

  Examples of the raw material olefin component include ethylene, propylene, 1-butene, 1-hexene, 4-methylpentene-1, and 1-octene. In the present invention, the olefin component can be used alone or copolymerized. In the case of copolymerization, it includes that a small amount of a diene compound such as 1,5-hexadiene, 1,7-octadiene, methyl-1,7-octadiene, etc. is copolymerized.

  Examples of the organometallic compound used as a component that inactivates moisture or an active compound serving as a promoter or catalyst poison include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Examples of organoaluminum compounds include (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethyl. Alkyl aluminum halides such as aluminum sesquichloride and ethylaluminum dichloride, (c) Alkyaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, (d) Alkyaluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum phenoxide and methylaluminum diphenoxide , ( ) Methylalumoxane, tetra butyl alumoxane, the alumoxane, such as methyl butyl alumoxane, (f) methyl boronic acid dibutyl, and combined organic aluminum compounds such as lithium aluminum tetraethyl is. Examples of the organic magnesium compound include butylethylmagnesium, dibutylmagnesium, butylmagnesium chloride and the like. Examples of the organic zinc compound include diethyl zinc, a reaction product of diethyl zinc and water, a reaction product of diethyl zinc and phenol, and the like.

  As a molecular weight control agent, a molecular weight control method using hydrogen, which is widely employed in olefin polymerization, a compound having a Si—H bond, an organic metal compound, for example, a chain transfer agent such as organic zinc or organic tin, may also be used. Can do.

  Various additives for the purpose of improving stereoregularity, controlling particle properties, controlling soluble components, controlling molecular weight distribution, etc. include organosilicon compounds, esters, thioesters, amines, ketones, nitriles, and phosphines. Examples include electron donating compounds such as ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes, organic acids, azo compounds, and alcohols.

  Examples of the organosilicon compound include diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, and phenyltrimethoxysilane. Methoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, methyl tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, isopropyl tert-butyldimethoxysilane, methyl-tert-butyldiethoxysilane, Methyl sec-butyldimethoxysilane, (α, α-dimethylbenzyl) triethoxysilane, (2-cyclohexylpropyl-2) triethoxysilane, diisobutyldimeth Xysilane, (α, α-dimethylbenzyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane, tert-butyltriethoxysilane, (2-methylbutyl-2 ) Triethoxysilane, isobutyl sec-butyldimethoxysilane, disec-butyldimethoxysilane, isobutylcyclopentyldimethoxysilane, ethyl tert-butyldimethoxysilane, propyltert-butyldimethoxysilane, diisopropyldimethoxysilane, isopropyl (cyclopentylmethyl) dimethoxysilane, Tert-butylcyclopentyldimethoxysilane, tert-butylcyclohexyldimethoxysilane, isobutylcyclohexyldimethoxysilane, methyl-p-to Examples include rildimethoxysilane, methyl o-tolyldimethoxysilane, di (p-tolyl) dimethoxysilane, di (o-tolyl) dimethoxysilane, dibenzyldimethoxysilane, and bis (cyclohexylmethyl) dimethoxysilane.

  Examples of the electron donating compound include ethyl formate, methyl acetate, ethyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, croton Ethyl acetate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, butyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, toluic acid Monoesters such as amyl and ethyl benzoate, diesters such as diethyl succinate, dibutyl succinate, diethyl tartrate and dibutyl tartrate, and aromatic dicarboxylic acid esters include monoethyl phthalate and monobutyl phthalate Can monoethyl terephthalate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, be mentioned methyl isobutyl phthalate, and the like. Further, esters such as γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, organic acids such as benzoic acid and p-oxybenzoic acid, succinic anhydride, benzoic anhydride, p-toluic anhydride, etc. An acid anhydride can also be mentioned as an electron-donating compound. Further, methyl ether, ethyl ether, isopropyl ether, n-butyl ether, isopropyl methyl ether, t-butyl ethyl ether, t-butyl-n-butyl ether, t-amyl methyl ether, t-amyl ethyl ether, amyl ether, tetrahydrofuran, Ethers such as anisole, diphenyl ether, ethylene glycol butyl ether, 2,2-dimethyl, 1,3-propanediol dimethyl ether, 2-isobutyl-2-methyl-1,3-propanediol dimethyl ether, di-t-butyl-1,3 -Diethers such as dipropanediol dimethyl ether are exemplified as additives for improving stereoregularity.

  Also, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, tolualdehyde, benzalded, naphthylaldehyde, acetyl chloride, butyryl chloride, isobutyryl Chloride, 2-methylpropionyl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethylhexanoyl chloride, cyclohexanedicarbonyl dichloride, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthalo Acid halides such as yl chloride and benzene-1,2,4-tricarbonyl trichloride; Acid amides, acid amides such as benzoic acid amide, toluic acid amide, tributylamine, N, N′-dimethylpiperazine, tribenzylamine, aniline, pyridine, pyrroline, amines such as tetramethylethylenediamine, acetonitrile, benzonitrile, Nitriles such as tolunitrile, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and t-butyl alcohol, and phenols such as phenol and pentamethylphenol are mainly particles. It is advantageously used as an additive for the purpose of controlling properties, controlling soluble components, controlling molecular weight distribution, and the like.

3. Polymerization apparatus The polymerization apparatus for polyolefin production of the present invention comprises a raw material supply system (1) capable of arbitrarily changing the composition of each raw material used in the polymerization reaction, and a polymerization reactor for polymerizing the raw material supplied from the raw material supply system. It comprises a system (2) and a raw material purge system (3) from the polymerization reactor system.
The configuration of the polymerization apparatus will be described with reference to the drawings. FIG. 1 is a schematic diagram illustrating the concept of the basic configuration of the polymerization apparatus of the present invention. In FIG. 1, (1) shows a raw material supply system, (2) shows a polymerization reactor system, and (3) shows a raw material purge system.
The raw material supply system (1) is a raw material such as a monomer, a co-catalyst, a hydrocarbon solvent, a polymerization additive component represented by a donor, and hydrogen as a molecular weight regulator (shown as raw materials A to D in FIG. 1). It is a supply system, and is continuously supplied to the polymerization reaction system (2). A control valve for arbitrarily controlling the flow rate and a flow meter for detecting the flow rate may be installed in each raw material supply line. Further, when the supply fluid is a liquid, it can be supplied by a positive displacement pump such as a plunger pump as long as the influence of flow rate pulsation on the reaction system can be ignored. These raw material supply lines can be controlled so as to have a predetermined temperature and pressure in advance by providing a heat exchanger and a pressure regulating valve corresponding to the control of the polymerization reaction conditions.

The polymerization reaction system (2) includes a heat exchanger and a pressure adjustment mechanism for controlling to predetermined polymerization conditions, and includes one polymerization reactor in the system. Examples of the reactor include a vertical reaction tank and a fluidized bed, and each may be provided with a jacket for adjusting the reaction temperature. The reaction temperature can also be adjusted by controlling the temperature of the fluid part flowing from the raw material supply system into the reactor. As a structure of the reactor, it is also effective to provide a stirring mechanism for the purpose of homogenizing the reaction and promoting heat removal. Any stirring blade can be used in this case, and it may be freely selected depending on the catalyst used and the form of the polymer particles produced by the polymerization.
Among these, a tank reactor having a jacket for controlling the reaction temperature and a stirring mechanism, a solid-gas fluidized bed reactor in which the introduced raw material is substantially a gas, or the introduced raw material is substantially A solid-liquid fluidized bed reactor that is liquid is preferred.

  The solid catalyst component is supplied batchwise to the polymerization reaction system or all before the start of the polymerization. For this purpose, a catalyst cylinder is provided to be led directly to the reactor part of the reaction system. There is no limitation on the method of supplying the solid catalyst component, but a predetermined amount of catalyst can be obtained by pressurizing a catalyst cylinder preloaded with catalyst with an inert gas such as nitrogen to exceed the reactor pressure and instantaneously opening the valve. A press-fitting method can be applied. In addition, depending on the purpose, additional introduction into the batch system is not prevented during the polymerization.

  The polymerization reaction in the polymerization reaction system (2) is started from the time when the catalyst is added, but when performing gas phase polymerization from the first stage, an appropriate dispersion medium is used to promote the dispersion of the catalyst. It is desirable. The dispersion medium is not particularly limited as long as it is inert and has excellent catalyst dispersibility. For example, sufficiently dried sodium chloride, fluorine resin beads, ceramic beads, and the like are preferably used.

  The raw material is continuously supplied to the reactor system, but a mechanism for preventing the charged solid catalyst component or the generated polymer particles from being discharged from the reactor system is provided. As this mechanism, filters having a sufficiently small opening size to substantially prevent the permeation of the solid catalyst particles are used. The specific filter opening size can be selected according to the particle size of the solid catalyst component used. To prevent unnecessary catalyst leakage, the integrated distribution of the solid catalyst component on the sieve It is desirable to select such that the value is equal to or smaller than the particle size corresponding to 95 wt%.

The material of the filter is not limited as long as it has mechanical and chemical resistance, but a screen mesh made of stainless steel is preferably used. The filter structure and attachment method are not limited as long as the solid catalyst component or the generated polymer particles do not easily block the filter surface. Since the solid catalyst component used for the olefin polymerization is generally about 1 to 3000 microns, a mesh size filter having an opening that prevents the smallest particles from passing therethrough is used. Specifically, in consideration of gas permeability, it is preferable to use a filter of 2500 mesh or more, and in the case of a catalyst with many fine particles, at least one fine filter of 5000 mesh or more is preferably used.
In addition, such a fine mesh size filter is difficult to permeate gas, so for example, a shape that increases the filter surface area as much as possible to reduce the linear velocity of fluid passage on the filter surface, such as a conical shape, is adopted. Or a method of preventing clogging by causing a flow on the filter surface with a stirring blade.
Furthermore, in general, reducing the mesh size will reduce the strength of a single unit. Therefore, a sintered metal filter in which screens of different mesh sizes are laminated in layers and heat-pressed is used. More preferably, it is used.
The raw material led to the reactor system is partially consumed in the reactor by the reaction, and the raw material excluding the consumed part is guided to the outside of the reactor through a mechanism for preventing the solid particles from being led out, and the raw material purge system ( 3).

An example of a specific apparatus of the polymerization reactor system will be described with reference to FIGS.
FIG. 2 shows an example in which a filter is attached to a tank reactor equipped with a stirrer. In FIG. 2, the solid catalyst component 2 is supplied to the tank reactor 3 with a stirrer, and the other raw material components are supplied from 1 to the tank reactor 3, and the polymer particles and solid catalyst components produced in the reactor 3 are supplied. Is prevented from flowing out by the filter 4, and unreacted raw materials and the like are recovered by the line 5.
FIG. 3 shows an example of a fluidized bed reactor in which a filter is provided at the gas or liquid outlet. In FIG. 3, the solid catalyst component 2 is supplied to the fluidized bed reactor 3, the other raw material components are supplied from the lower part of the fluidized bed reactor 3 through 1, and the polymer particles generated in the fluidized bed reactor 3 and The solid catalyst component is prevented from flowing out by the filter 4, unreacted raw materials and the like are recovered by the line 5, and further recycled to the raw material supply system using a circulating gas compressor or a circulating pump 6.

  In any case, application to bulk polymerization with liquefied propylene, slurry polymerization using an inert hydrocarbon solvent, or gas phase polymerization is possible. In particular, in the fluidized bed process, the heat of polymerization generated by the polymerization can be removed by an external heat exchanger installed in the raw material circulation system, so the heat removal efficiency when the scale increases is the jacket of the reactor body. This is advantageous compared to the case of using only.

  In the raw material purge system (3), post-processing is performed to return the raw material flowing out from the reaction system to the disposal or recycling system. For example, the organic aluminum component contained in the raw material system is inactivated, the hydrocarbon solvent that is a heavy component is separated from hydrogen or monomers that are light-boiling components, and the process is sent to an appropriate processing system. . From an economical point of view, it is desirable that the raw material in the purge system is returned to the purification system and recycled.

4). Polymerization Process In the olefin polymerization process using the polymerization apparatus of the present invention, slurry polymerization using an inert solvent typified by hexane and heptane, bulk polymerization in which polymerization is performed in a monomer component in a liquefied state, and substantially In particular, gas phase polymerization in which polymerization is performed in a vaporized monomer environment where no liquid is present can be applied. However, in any case, reaction conditions capable of maintaining the form of solid particles are employed for the produced polymer.

  In this polymerization process, a more characteristic reaction mode can be achieved when the raw material consumed in the polymerization reaction is relatively small compared to the flow rate of the raw material supply system containing the organoaluminum component and additive component. . That is, when the raw material consumption in the reaction system is small relative to the supply amount, the reaction composition given to the solid catalyst component is approximately equal to the composition of the raw material supply system, so the reaction composition changes with the reaction time. In order to perform the polymerization reaction, it is possible to control the composition in the raw material supply system. Further, in the form of changing the reaction composition over time, when it is desired to control the composition with better response, the actual volume of the polymerization reaction system can be operated to be sufficiently smaller than the volume flow rate of the raw material supply system. desirable. This corresponds to operating the raw material with a short average residence time.

The characteristics of the polymerization reaction in the present invention will be described more specifically with reference to FIG. 4 schematically showing the change with time of the concentration of one component X in the feedstock in the raw material system and the reactor system. In FIG. 4, (a) schematically shows the change with time of the concentration of a certain component X in the raw material system. The concentration of the raw material X introduced into the polymerization reaction system is constant.
In FIG. 4, (b) to (d) show the results of a model calculation of how the concentration of component X in the polymerization reactor responds in each case where the average residence time of the raw material is different. It is a thing.
FIG. 4 (b) shows that if the average residence time of the raw material is sufficiently short (average residence time = 0.05H), the concentration of the component X in the reactor follows the concentration in the raw material system well in a short time. become.
FIG. 4 (c) shows that if the average residence time of the raw material is slightly longer (average residence time = 0.1H), the follow-up of the concentration of the component X in the reactor to the concentration in the raw material system is slightly delayed.
FIG. 4 (d) shows that when the average residence time of the raw material becomes longer (average residence time = 0.3H), the concentration of the component X in the reactor gradually increases even if the concentration of the component X in the raw material system is changed abruptly. Will change.

  Therefore, if these characteristics are taken into consideration in advance, it is possible to arbitrarily control the polymerization reaction conditions over time, and it is possible to implement multi-stage polymerization and gradient composition polymerization in which the reaction composition changes with time.

  These raw material supply amounts can be controlled by combining a suitable flow meter and a control valve, or in the case of liquid, a method of feeding a constant flow rate with a positive displacement pump such as a plunger pump. For these controls, the actual flow rate measurement value is guided to the computer, and sequence control is performed so that the flow rate pattern is set in advance, or the result of calculation using the measurement value is applied to other control systems, etc. Is possible. In particular, if the flowmeter has characteristics that require correction according to the temperature and pressure of the fluid, it is possible to perform such calculation in real time by a computer and perform more accurate operation.

  The polymerization reaction performed using the polymerization apparatus of the present invention is substantially batch-wise. Therefore, in order to stop the polymerization reaction, the feed of the raw material is stopped, the raw material is purged, and the system is cooled. Or a method of batch feeding a polymerization terminator such as carbon monoxide or carbon dioxide into the system.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In addition, the physical-property measuring method in the Example and the preparation method of a catalyst are as follows.

1. Physical Property Measurement Method (1) Particle Size Measurement of Ion Exchange Layered Silicate Particles Measurement was performed using a laser diffraction / scattering particle size distribution measuring device (“LA-920” manufactured by Horiba, Ltd.). For the measurement of the ion-exchangeable layered silicate in the slurry before granulation, water was used as a dispersion medium, and the particle size distribution and average particle size (median diameter) were calculated with a refractive index of 1.32 and a shape factor of 1.0. The ion exchange layered silicate after granulation was measured in the same manner using ethanol as a dispersion medium.
(2) MFR measurement The melt index value measured according to JIS-K-6758 is shown.
(3) Polymer BD
It shows the bulk density of the polymer according to ASTM D1895-69.
(4) Measurement of powder particle size It measured using the particle size distribution measuring device camsizer by Lecce Technology.
(5) GPC measurement The weight average molecular weight Mw and the number average molecular weight Mn were determined by the following methods. Using a Waters GPC150C type apparatus and three Showa Denko AD80M / S columns, using orthodichlorobenzene as a solvent, the measurement was performed at 140 ° C.

2. Preparation of catalyst (1) Granulation of catalyst carrier fine particles (first stage granulation step)
Distilled water (2850 ml) and commercially available montmorillonite (Mizusawa Chemical Benclay SL) (150 g) were gradually added to a 4.5 liter metal container, stirred for several hours, and then homogenized using polytron for 10 minutes. . When the average particle size was measured, it was 0.63 microns for the montmorillonite water slurry. This slurry was subjected to spray granulation using a spray granulator (LT-8) manufactured by Okawara Chemical Corporation. The physical properties and operating conditions of the slurry are as follows.
Slurry properties: pH = 9.6, slurry viscosity = 3500 CP; operating conditions: atomizer rotation speed 30000 rpm, feed rate = 0.7 L / h, inlet temperature = 200 ° C., outlet temperature = 140 ° C., cyclone differential pressure = 80 mmH ₂ O
As a result, 90 g of granulated fine particles were recovered. The average particle size was 10.1 microns. The shape was spherical.
(2) Acid treatment To a glass flask equipped with a 1.0 liter stirring blade, 510 ml of distilled water and 150 g of concentrated sulfuric acid (96%) were slowly added, and 80 g of the granulated fine particles were dispersed. And heat treatment at 90 ° C. for 2 hours. After cooling, the slurry was filtered under reduced pressure to recover the cake. Distilled water was added to the cake in an amount of 0.5 to 0.6 liter, and the slurry was reslurried and then filtered. This washing operation was repeated 4 times.
The collected cake was dried at 110 ° C. overnight. The weight after drying was 67.5 g.
(3) Re-granulation The acid-treated fine particles 50 g thus obtained were gradually added to 150 ml of distilled water and stirred. This slurry was subjected to spray granulation using a spray granulator (LT-8) manufactured by Okawara Chemical Corporation. The physical properties and operating conditions of the slurry are as follows.
Slurry properties: pH = 5.7, slurry viscosity = 150 CP; operating conditions: atomizer rotation speed 10000 rpm, liquid supply amount = 0.7 L / h, inlet temperature = 130 ° C., outlet temperature = 110 ° C., cyclone differential pressure = 80 mmH ₂ O
As a result, 45 g of granulated particles were recovered. The average particle size was 69.3 microns.
(4) Preparation of catalyst The following operations were carried out under inert gas using deoxygenated and dehydrated solvent and monomer. The granulated product of the ion exchange layered silicate was dried at 200 ° C. under reduced pressure for 2 hours.
10 g of the granulated particles obtained above were introduced into a glass reactor equipped with a stirring blade having an internal volume of 1 liter, normal heptane and further a heptane solution of triisobutylaluminum (25 mmol) were added, and the mixture was stirred at room temperature. After 1 hour, the slurry was thoroughly washed with heptane to prepare a slurry of 100 ml.
Next, 43 ml of mixed toluene was added to 0.30 mmol of (r) -dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl]} hafnium dichloride in advance for 1 hour or more. After stirring, a mixed solution in which 1.5 mmol of triisobutylaluminum (heptane solution, 2.13 ml) was allowed to react at room temperature for 1 hour was added to the granulated particle slurry and stirred for 1 hour.
(5) Preliminary polymerization Subsequently, 105 ml of mixed heptane was introduced into a stirring autoclave having an internal volume of 1.0 liter sufficiently substituted with nitrogen and maintained at 40 ° C. The previously prepared granulated particle / complex slurry was introduced there. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 2 hours, the propylene feed was stopped and maintained for another 2 hours. The prepolymerized catalyst slurry was recovered with a siphon, and about 100 ml of the supernatant was removed and dried at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained. The prepolymerized catalyst had a 50 wt% average particle size of 120 microns, and a particle size corresponding to a cumulative distribution value on the sieve of 95 wt% was 81 microns.

Example 1
(1) Apparatus The polymerization apparatus used was the apparatus shown in FIG.
(I) A line was connected to the raw material supply system so that liquefied propylene, hydrogen, and organoaluminum could be supplied. The liquefied propylene was refined so as to be suitable for the polymerization reaction, and then the pressure was increased using a reciprocating diaphragm pump, and the liquefied propylene was circulated using a thermal mass flow meter and a flow control valve. Hydrogen was pressurized with a diaphragm compressor and supplied using a thermal mass flow meter and a flow control valve. The organoaluminum was supplied using a plunger pump equipped with an inverter control solution diluted in heptane. The supply flow rate was quantified by a calibration curve prepared by measuring the actual flow rate from the pump stroke and the inverter frequency in advance. These raw materials were gathered in one line and heated to a required temperature with a double-pipe heat exchanger.
(Ii) For the polymerization reactor, a jacketed vertical tank with an internal volume of 30 L, in which a stirring blade was installed, was used. A conical filter was installed in the upper part of the reactor, and the nozzle was led so that the line from the raw material supply system was on the lower side of the reactor. As the filter, a sintered metal filter manufactured by Manabe Kogyo Co., Ltd., in which screens made of stainless steel SUS316 were laminated in seven layers, was used. The mesh configuration was 2600-1400-200-100-60-40-40 (mesh), and the reactor chamber side in contact with the solid catalyst component was configured to be 2600 mesh. The reference value of the 2600 mesh transmitted particle sphere by the manufacturer was 4.9 microns. The solid catalyst was weighed into a pot with powder or heptane slurry, set to a pressure higher than that in the reactor with high-pressure nitrogen gas, and then pressed into the reactor by opening the lower valve.
(Iii) The fluid mainly composed of liquefied propylene introduced into the polymerization reactor system was led to the raw material purge system through a filter. In the raw material purge system, it was gasified by a heater through a buffer tank subjected to liquid level control, and then returned to the recovery system.

(2) Polymerization reaction In the raw material supply system, liquefied propylene was circulated at 150 kg / hr, hydrogen at 0.4 NL / hr, and triisobutylaluminum / n-heptane solution (concentration 59 g / L) at 600 ml / hr. . The hot water temperature of the reactor jacket was adjusted so that the internal temperature would be 70 ° C. When the flow state was stabilized, the prepolymerized catalyst prepared previously was slurried in normal heptane, and 150 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected using high-pressure nitrogen to initiate polymerization. The temperature inside the tank was maintained at 70 ° C., and after 30 minutes, the hydrogen flow rate was changed to 19.2 NL / hr, and the polymerization was continued for 30 minutes while maintaining the polymerization temperature at 70 ° C. During this time, the raw materials from the raw material supply system and the polymerization reaction system were sampled over time, and the hydrogen concentration in the monomer was analyzed by gas chromatography. Thereafter, 0.25 NL of a mixed gas of carbon monoxide / nitrogen (carbon monoxide concentration 5%) was added to stop the reaction. The polymer obtained by purging the residual monomer was dried. As a result, 2230 g of a polymer was obtained. The catalyst efficiency was 14900 g-PP / g-catalyst. The polymer BD was 0.41 (g / cc), the MFR was 21 (dg / min), and the molecular weight distribution was Mw / Mn = 3.2. Moreover, the hydrogen concentration in the raw material sampled from the raw material supply system and the polymerization reaction system is shown in FIG.
As is clear from FIG. 6, the hydrogen concentration in the reaction system followed the hydrogen concentration in the raw material system in a short time.

(Example 2)
In Example 1, the polymerization was carried out under the same conditions except that the amount of catalyst was changed to 300 mg and the change in the amount of hydrogen flow was changed 45 minutes after the start of polymerization. As a result, 2980 g of a polymer was obtained. The catalyst efficiency was 9930 g-PP / g-catalyst. The polymer BD was 0.43 (g / cc), the MFR was 7.5 (dg / min), and the molecular weight distribution was Mw / Mn = 3.6.

(Example 3)
In Example 1, polymerization was carried out for 1 hour under the same conditions except that the amount of catalyst was changed to 1 g and the flow rate of hydrogen during polymerization was fixed at 0.1 NL / hr. During the polymerization, the raw materials from the raw material supply system and the polymerization reaction system were sampled over time, and the hydrogen concentration in the monomer was analyzed by gas chromatography. After completion of the polymerization, 2330 g of polymer was obtained. The catalyst efficiency was 2330 g-PP / g-catalyst. The polymer BD was 0.41 (g / cc), the MFR was 0.25 (dg / min), and the molecular weight distribution was Mw / Mn = 2.7. The hydrogen concentration in the raw material sampled from the polymerization reactor was constant at about 1 ppm.

(Comparative Example 1)
In Example 1, polymerization was carried out with the filter in the reactor removed. At the stage where 5 minutes had passed after the start of polymerization, the line from the reactor to the raw material purge system was blocked, and the reaction could not be continued. When the reactor and the raw material purge system were opened, it was confirmed that a large amount of catalyst was scattered and an amorphous polymer was produced.

(Comparative Example 2)
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution was added, and the internal temperature was maintained at 30 ° C. Next, 5.7 g of the prepolymerized catalyst was injected with nitrogen to initiate polymerization, and the temperature was raised to 70 ° C. over 34 minutes. From this point, the polymerization temperature was maintained at 70 ° C., and after 1 hour, 100 ml of ethanol was added to stop the reaction. During this time, the gas in the gas phase portion in the reactor was sampled over time, and the hydrogen concentration in the monomer was analyzed by gas chromatography. After unreacted monomer purge, 15.9 kg of polymer was obtained. The catalyst efficiency was 2800 g-PP / g-catalyst. The polymer BD was 0.41 (g / cc), the MFR was 0.27 (dg / min), and the molecular weight distribution was Mw / Mn = 4.0. The hydrogen concentration in the raw material sampled from the polymerization reactor is also shown in FIG. As the polymerization proceeds, the hydrogen concentration in the reactor increases, suggesting that hydrogen is being generated during the polymerization. This is a tendency generally seen when a metallocene catalyst is used.

  The polymerization apparatus for polyolefin production of the present invention can arbitrarily control the raw material composition in the polymerization reaction, and is highly accurate and under a wide range of conditions in the case of performing polymerization with different raw material compositions over time including so-called multistage polymerization. Since it can be obtained, the polymerization process can be easily analyzed, and the industrial value is extremely high.

It is the figure which showed schematic structure of the superposition | polymerization apparatus. It is the figure which showed one specific implementation aspect in a polymerization reaction system. It is the figure which showed the other concrete embodiment in the polymerization reaction system. It is the figure which showed typically the time-dependent change of the density | concentration of the component X in a reactor. It is a figure which shows the outline | summary of the superposition | polymerization apparatus used in the Example. It is a figure which shows the time-dependent change of the hydrogen concentration in Example 1. FIG. 6 is a diagram showing a change with time in hydrogen concentration in Comparative Example 2.

Explanation of symbols

1 Raw material supply system 2 Solid catalyst component 3 Reactor 4 Filter 5 Outflow raw material 6 Circulating compressor or pump

Claims (5)

  A polymerization apparatus for carrying out an olefin polymerization reaction using a solid catalyst containing a transition metal component, from a raw material supply system (1) that can arbitrarily change the composition of each raw material used in the polymerization reaction, from the raw material supply system It comprises a polymerization reactor system (2) for polymerizing the supplied raw material, and a raw material purge system (3) from the polymerization reactor system, in which a solid catalyst component for polymerization is batch-wise. Introduced into the system, raw materials other than the solid catalyst component are continuously introduced and derived, and a filter is provided so that the solid catalyst component and the produced polymer cannot be derived from the polymerization system during the polymerization reaction. A polymerization apparatus for producing polyolefins, wherein the raw material composition of the polymerization reactor system can be arbitrarily controlled later, or polymers having different compositions with time can be obtained by changing with time.   The polymerization apparatus for polyolefin production according to claim 1, wherein the polymerization reactor system is a tank reactor equipped with a jacket for controlling the reaction temperature and a stirring mechanism.   The polymerization reactor system is a solid-gas fluidized bed reactor in which the introduced raw material is substantially a gas, or a solid-liquid fluidized bed reactor in which the introduced raw material is substantially liquid. Item 2. A polymerization apparatus for polyolefin production according to Item 1.   The polymerization apparatus for polyolefin production according to any one of claims 1 to 3, wherein the filter in the polymerization reactor system is at least one filter having an opening size of 2500 mesh or more.   A method for producing a polyolefin, comprising polymerizing an olefin using the polymerization apparatus for producing a polyolefin according to any one of claims 1 to 4.

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