JPH029047B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a gas phase polymerization process for directly converting gaseous alpha-olefins into polymers. More specifically, the present invention relates to a method for continuously producing high-quality polymers (including copolymers) using a fluidized bed reactor. Crystalline α-olefin polymers have been industrially produced since the invention of stereoregular polymerization catalysts for α-olefins by Ziegler and Natsuta et al. Among the industrial manufacturing methods proposed to date,
The most important method is the so-called solvent polymerization method, in which a catalyst is dispersed in a liquid inert solvent and α-olefin is polymerized while stirring.
However, in such solvent polymerization methods, after the completion of polymerization, the catalyst is deactivated and the catalyst residue is extracted, and then the polymer particles are separated from the inert solvent and further dried to obtain a product polymer. On the other hand, separated inert solvents are usually used industrially as
This requires a very complex and energy-intensive process since the low molecular weight, amorphous polymer dissolved in an inert solvent and the catalyst residue must be separated, purified and reused. With the aim of improving such methods, many proposals have already been made regarding gas phase polymerization methods in which polymerization is carried out in a gaseous α-olefin in the absence of a substantially liquid inert solvent. However, these polymerization methods in the gas phase have many problems that must be overcome compared to solvent polymerization methods. First, when polymer particles are stirred and polymerized in a gas phase, it is extremely difficult to achieve uniform mixing compared to solvent polymerization, which tends to cause localized areas of high temperature. Furthermore, even when a catalyst is added to the polymerization system, it is difficult for the solid catalyst component to be quickly dispersed, so that a large amount of polymerization reaction occurs locally, which tends to generate high-temperature areas. Furthermore, heat transfer through the walls of the reactor is significantly poorer than in the solvent polymerization method, so it is extremely difficult to remove the polymerization heat from the walls of the reactor, which is normally carried out in the solvent polymerization method. In order to overcome these problems, solid catalyst components and/or polymer particles and/or dispersions containing solid catalyst components are fluidized by an upward flow of α-olefin gas to form a bed in which α- The olefin is polymerized and the unreacted α-
A polymerization method using a so-called fluidized bed reactor has been proposed in which the heat of the polymerization reaction is removed by guiding the olefin gas through a circulation system with an external heat exchanger, cooling it, and feeding it into a fluidized bed again. ing. The monomer to be polymerized in the present invention has 2 or more carbon atoms.
8 α-olefins, preferably α-olefins having 2 to 6 carbon atoms, more preferably ethylene, propylene, butene-1, 4-methylpentene-1
It is. In the present invention, it is possible to perform homopolymerization, random polymerization, or block copolymerization of these monomers by changing the type and/or composition of the monomers in two or more steps. . Particularly in the case of block copolymerization, the method of the present invention is particularly preferably applied since it is possible to produce polymers of extremely high quality compared to ordinary continuous polymerization methods. In addition, a preferred embodiment of block copolymerization is as follows:
Ethylene or/and butene, either alone or copolymerized with propylene as a result.
A first step of polymerizing or copolymerizing so that α-olefin of 1 or C 5 to 8 is 6 mol% or less, and a first step of polymerizing or copolymerizing so that the resulting copolymerized propylene is 90 mol% or less. The above process also consists of a second step of copolymerization. Each step can also be carried out by changing the composition of the monomers supplied stepwise or continuously. The catalyst used in the present invention is a so-called Ziegler-Natsuta catalyst, that is, a catalyst consisting of a transition metal compound of Groups 1 to 1 of the periodic table and an organic compound of a typical metal of group 1 of the periodic table. It is preferable that the catalyst component contained is solid. Preferable transition metal compounds are compounds containing at least titanium and halogen, among which compounds with the general formula Ti(OR) _o X _no (R is a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen) , m represents a number from 2 to 4, and n represents a number from 0 to m-1). Specific examples of such compounds include:
_{TiCl4 , TiCl3} , _TiCl2 , Ti( _OC2H5 ) _Cl3 , Ti
_{( OC6H5} ) _Cl3 , etc. The transition metal compound can be used as the main component itself or as a catalyst component supported on a suitable carrier. Among titanium halogen compounds, TiCl ₃ is one of the most preferred transition metal compounds in the present invention, but it is known to take α, β, γ, and δ crystal forms, and TiCl 3 is one of the most preferred transition metal compounds in the present invention. For stereoregular polymerization of α-olefins, α, γ and δ forms of TiCl ₃ having a layered crystal form are preferred. TiCl ₃ is generally obtained as a TiCl ₃ composition by reducing TiCl ₄ with hydrogen, metallic aluminum, metallic titanium, an organoaluminum compound, an organomagnesium compound, or the like. preferable
TiCl ₃ composition is produced by reducing TiCl ₄ with metal aluminum, further reducing so-called TiCl ₃ AA and TiCl ₄ activated by mechanical grinding etc. with an organoaluminum compound, and then using a complexing agent and a halogen compound. It is activated by In the present invention, the latter is particularly preferred. When the TiCl ₃ composition was polymerized for 4 hours at 65°C in combination with diethylaluminium chloride in the presence of hydrogen in liquefied propylene,
Particularly preferred are those capable of producing 6000 g or more of polypropylene per gram of TiCl ₃ composition. Such a TiCl ₃ composition is disclosed in Japanese Patent Application Laid-Open No. 47-34478.
No. 76196, Japanese Patent Application Laid-Open No. 1983-76196,
Publication No. 33289, Japanese Unexamined Patent Application Publication No. 11985-1985, Patent Application No. 1983
It can be manufactured by the method disclosed in, for example, Japanese Patent No.-21252. When a transition metal compound is used as a catalyst component supported on a suitable carrier, examples of the carrier include various solid polymers, especially α-olefin polymers, various solid organic compounds, especially solid hydrocarbons, and various solid inorganic compounds. In particular, oxides, hydroxides, carbonates, halides, etc. can be used. Preferred carriers are magnesium compounds, ie, magnesium halides, oxides, hydroxides, hydroxyhalides, and the like. Magnesium compounds can also be used as complexes with other solid substances mentioned above. A commercially available magnesium compound can be used as it is, but it can be mechanically pulverized, dissolved in a solvent and then precipitated, or treated with an electron-donating compound or active hydrogen compound, or treated with a Grignard reagent, etc. Preferably, it is a magnesium compound obtained by decomposing an organomagnesium compound. In many cases, it is preferable to use these operations in combination to obtain a preferable magnesium compound, and these operations may be carried out in advance when producing the carrier, or may be carried out when producing the catalyst component. Particularly preferred magnesium compounds are halogenated magnesium compounds, and particularly preferred transition metal compounds are the aforementioned halogenated titanium compounds. Such a supported catalyst component consisting of titanium, magnesium, and halogen is one of the most preferred catalyst components in the present invention, and is disclosed in Japanese Patent Publication No. 47-41676, USP 3642746, Japanese Patent Application Laid-Open No. 49-86482, and Japanese Patent Application Laid-Open No. 1987-86482. 92885, JP 52-74684, JP 53-39991, JP 54-2988,
JP-A-54-3183, JP-A-54-17988,
It can be produced by the methods disclosed in JP-A-54-112982, JP-A-54-112983, and Japanese Patent Application JP-A-54-107471. In order to perform stereoregular polymerization of α-olefin having 3 or more carbon atoms, it is preferable to use a supported catalyst component consisting of titanium, magnesium, and halogen containing an electron-donating compound. Preferred organic compounds of typical metals of Groups ~ of the Periodic Table are organic compounds of aluminum, particularly those with the general formula ReAlX _3-e (R is 1 to 1 carbon atoms).
Preferred are organoaluminum compounds represented by 20 hydrocarbon groups, X represents hydrogen or halogen, and e is a number from 1 to 3. Specific examples of such compounds include triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diethylaluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, and ethylaluminum dichloride. The most preferred compound is
triethylaluminum, diethylaluminium chloride and mixtures thereof. The amount of the catalyst component added is not particularly limited, but the molar ratio of organoaluminum compound/TiCl ₃ is 1 to 1.
100 is preferred, and a range of 3 to 50 is particularly preferred. The catalyst used in the present invention consists of the transition metal compound and the organometallic compound, but an electron-donating compound can be further used in combination to improve activity and/or stereoregularity. Such electron-donating compounds include ethyl acetate, ε-caprolactone, methyl methacrylate,
Ester or acid anhydride such as ethyl benzoate, ethyl p-anisate, methyl p-toluate, phthalic anhydride, ether compound such as di-n-butyl ether, diphenyl ether, diglyme, tri-n-butyl phosphite , triphenyl phosphite, hexamethylene phosphoric triamide, and other organic phosphorus compounds. In addition, ketones, amines, amides, thioethers, etc. can also be used. Preferred electron-donating compounds are esters and phosphites, especially titanium, magnesium,
Aromatic monocarboxylic acid esters are preferred for supported catalyst components consisting of halogens. The electron-donating compound is usually used in an amount of 1 mol or less per 1 mol of the transition metal compound or organometallic compound. Next, a preferred embodiment of the reactor is shown in FIG. The reactor has a cylindrical reaction zone 1 and a classification zone 3 with a length-to-inner diameter ratio in the range of 1 to 6, or even an upper part of the reaction zone 1 with a diameter of 1 to 6.
It has a speed reduction zone 11 with twice the diameter. If the ratio of the length of the reaction zone 1 to the inner diameter is less than 1, gas will blow through the fluidized bed, making it difficult to mix the particles uniformly, which is not preferable. If it is larger than 6, slugging occurs and stable flow cannot be maintained, which is not preferable. In the present invention, it is essential to use a fluidized bed reactor having a classification zone 3 having a classification effect. The classification zone 3 is located below the reaction zone 1 and has the function of selectively collecting polymer particles having a predetermined particle size or more. , an area having a gas distribution device 5 and having a cross-sectional area of 1/1.5 to 1/5 of the cross-sectional area of the reaction zone 1;
Or (b) the gas distribution device 5 is located below the reaction zone 1, and the cross-sectional area of the reaction zone is 1/1.5 to 1/
A single hole plate or a perforated plate with a hole area of 1 to 5
This is an area where 10 sheets have been installed. Note that in the perforated plate, the pore area refers to the total value. Although the shape of the hole is not particularly limited, it is generally circular. Although the single-hole plate or the perforated plate may be attached directly under the reaction zone, it is preferable to provide a region below the reaction zone with a cross-sectional area smaller than the cross-sectional area of the reaction zone, and to attach the plate thereto to increase the classification effect. In addition, in a fluidized bed reactor equipped with a stirrer, it is also possible to attach it to a stirring shaft. The deceleration zone 11 has the function of reducing the rising gas flow velocity and returning particles accompanying the gas to the bed, but if the deceleration zone 11 is made more than twice the diameter of the reaction zone, the effect will be small despite its large size, which is not preferable. Furthermore, the reactor may be equipped with a stirrer in order to obtain a uniform fluidized bed. Although a stirrer is not essential in the polymerization method of the present invention, it is used to quickly and uniformly disperse the supplied solid catalyst in order to prevent abnormal flow phenomena such as slugging and channeling, and to prevent the polymer from adhering to the bottom of the reactor. It may be installed to prevent The stirring blade is preferably a multi-stage paddle blade, but is not particularly limited, and a stirring speed of 5 m/sec or less at the tip of the stirring blade is sufficient. Further, the reactor may be equipped with an insert 7 above the reaction zone to prevent polymer particles or solid catalyst particles from scattering into the circulation system along with unreacted gas. The insert 7 is installed at a position above the upper end A of the fluidized bed, and suppresses scattering of polymer particles or solid catalyst particles entrained in the unreacted rising gas flow by colliding with the insert 7. . One interpolant is 1/of the cross-sectional area of the reaction zone.
It has a horizontal projected area of 1.5 or less, and is most effective in suppressing scattering when installed on the reactor wall or agitator in combination so that the horizontal projected area is 90% or more of the cross-sectional area of the reaction zone. The gas distribution device introduces into the reactor the monomer-based gas that is used for polymerization and creates an ascending gas flow for fluidized bed formation. The gas distribution device may be just one installed in the classification zone, or one or more gas distribution devices can be installed in the reaction zone if necessary to achieve more uniform flow in the reaction zone. The gas distribution device has a structure that maintains a stable flow state during the polymerization reaction, with no clogging of the gas nozzles, no abnormal flow phenomena such as channeling, and no localized high-temperature areas. It is preferable that there be. For this purpose, bubble cap type perforated plates, pipe spargers, etc. may be used. Particularly preferred are bubble cap type plates and pipe spargers with holes below the horizontal. As described above, the catalyst used in the present invention consists of at least two components: a solid catalyst component and an organometallic compound catalyst component. It is preferable to supply these catalyst components separately, since clogging of the supply nozzle is minimized. Although the feeding position of the catalyst component is not particularly limited, it is preferable to feed the solid catalyst component into the bed because this reduces scattering of the solid catalyst component from the reaction zone.
Regarding the order of addition, it is preferable to supply the solid catalyst component and, after sufficient dispersion, supply the organometallic compound or further the electron-donating compound, since melt agglomeration of the polymer particles does not occur. The solid catalyst component to be supplied is prepared in advance at a rate of 1 part by weight.
It may also be a mixture with an α-olefin polymer obtained by polymerizing 100 parts by weight or less of α-olefin. Polymerization proceeds under conditions in which the polymer particles are uniformly fluidized in an ascending flow of gas consisting primarily of monomers supplied from a gas distribution device. The rising flow rate of the gas is preferably in the range of about 1.5 to 10 times the minimum gas flow rate (Gmf) necessary for fluidizing the layer formed by the polymer particles in the reaction zone 3.
A range of 6 to 6 times is most preferred in order to form a stable fluidized bed. Furthermore, it is essential that the polymerization proceed under conditions in which the gas does not liquefy in the reactor and the polymer particles do not melt into agglomerates. Particularly preferred polymerization conditions are a temperature range of 40 to 100°C and a pressure range of 1 to 50 kg/cm ² (G). Also,
It is preferable to add a molecular weight regulator such as hydrogen for the purpose of adjusting the melt fluidity of the resulting polymer, but
It is okay if there are steps in the polymerization process where it is not added. Monomers consumed in polymerization and molecular weight regulators such as hydrogen are supplied continuously or intermittently. The position to which it is supplied is not particularly limited, and it may be in the circulation system, the deceleration zone 11, or the fluidized bed. In reaction zone 1, polymer particles grow as the polymerization reaction progresses. In the classification zone 3, polymer particles having a predetermined diameter or more are classified and selected from small polymer particles and solid catalyst particles, and are extracted from an outlet 8. The gas flow rate in the classification zone 3 is such that a gas flow rate of 1 to 2 times the terminal velocity Ut of polymer particles of a predetermined diameter to be classified can be obtained in the portion where classification occurs. Specifically, the classification zone is simply set as described in (a) above, and the cross-sectional area is set to 1/1.5 to 1/1.5 of the cross-sectional area of the reaction zone.
When the area is set to 1/5, the gas flow rate is in the range of 1 to 2 times (Ut×cross-sectional area of the classification zone). When the classification zone is an area where 1 to 10 single-hole plates or perforated plates with a pore area of 1/1.5 to 1/5 of the cross-sectional area of the reaction zone are installed as described in (b) above, each The gas flow rate through the plate is in the range of 1 to 2 times (Ut x pore area of the plate). The gas distribution device 5 supplies a gas amount that satisfies the above conditions, but this gas amount does not stabilize the reaction zone.
If it is insufficient to achieve uniform flow, gas is further supplied from the gas distribution device 4. The unreacted gas that did not react in the reaction zone is 12
enters the circulatory system. The unreacted gas is passed through a cyclone 13 and/or a filter 14 to remove the entrained solid components of the polymer particles.
heat exchanger 1 after increasing the pressure in compressor 15.
It is cooled at 6. This removes the heat of polymerization.
Thereafter, it is supplied to gas distribution devices 4, 5. The positions of the compressor 15 and the heat exchanger 16 can be reversed, but under conditions where part or most of the gas liquefies when cooled within the polymerization pressure range of the present invention, such as propylene. Since it is difficult to pressurize the gas-liquid mixture using the compressor 15, it is preferable to circulate the gas-liquid mixture in the order of the compressor 15 and the heat exchanger 16. The polymer particles separated by the cyclone 13 can be returned to the reactor or removed from the system. Most of the polymerization heat is removed by the heat exchanger 16 as described above, but a jacket 18 provided in the reactor or an internal heat exchanger may also be provided and used in combination. In a fluidized bed in a good fluidized state, heat exchange between the polymer particles and the circulating gas occurs quickly, and the temperature of the circulating gas at the outlet of the fluidized bed almost matches the polymerization temperature of the fluidized bed. Therefore, in order to achieve a given polymerization temperature,
The circulating gas temperature at the reactor inlet is estimated and set in advance by considering the heat capacity of the polymerization gas and the circulating gas flow rate, and then the circulating gas temperature at the reactor inlet is adjusted to achieve the desired polymerization temperature. is preferred. Most of the methods of polymerizing α-olefins in the gas phase that have been proposed so far are continuous polymerizations, but essentially require a multi-stage polymerization process using a composite catalyst containing a solid catalyst. In block copolymerization, etc., the polymer obtained by continuous polymerization is non-uniform among the polymer particles based on the residence time distribution of the catalyst, causing spots to appear in the molded product, which significantly deteriorates the appearance of the molded product. Mechanical properties such as tensile properties and impact strength are significantly reduced. The problem of continuous polymerization can be solved by separating the polymer particles of the target particle size from the polymer particles and catalyst particles having a minute particle size and selectively transferring them from one reactor to the next reactor. We discovered that it is possible and arrived at the present invention. A specific embodiment applied to block copolymerization will be shown. Polymerization is carried out using two or more reactors that are operated continuously and connected in series. As a polymerization operation, catalysts, monomers,
Also included is the provision of molecular weight modifiers and the transport of polymer particles. The first step of the polymerization is carried out in at least one, preferably from 1 to 7, reactors connected in series, comprising at least one, preferably from 1 to 3 reactors having a classification zone. Even one reactor with a classification zone can considerably prevent polymer particles or even solid catalyst particles from being short-circuited and extracted, but by using multiple reactors, highly classified polymer particles can be obtained. be able to. Further, in this step, it is possible to use a known fluidized bed reactor or a fluidized bed reactor equipped with a stirrer in combination, and the combination is not particularly limited as long as the number of reactors is within the above range. The second step of polymerization comprises at least one, preferably one
It is carried out with ~4 reactors connected in series. The reactor used in this step may be a known fluidized bed type reactor or a fluidized bed type reactor equipped with a stirrer without generating a large amount of debris, but preferably at least one reactor, most preferably 1 to 3 reactors. By using a reactor having a classification zone of 1, it becomes possible to further prevent the generation of particles. Further, this step can be carried out by changing the polymerization conditions of the plurality of reactors and the composition of the α-olefin to be polymerized. In addition, by using a reactor with a classification zone, α-
Even when homopolymerization and random copolymerization of olefins are carried out continuously, the catalyst components are prevented from being short-circuited and extracted, so the catalyst components can be used efficiently, and at the same time, the catalyst components remain in the polymer. There is also the effect that there is less catalyst residue. The method of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited only by these Examples. The results of Examples and Comparative Examples are shown in Tables 1 to 3, and the physical property values in the tables were measured according to the following criteria. Melt index ASTM D1238-57T Bending stiffness ASTM D747-58T Vikatsu softening point ASTM D1525 Brittle temperature ASTM D746 Falling weight impact strength: A 1 mm (thick) injection molded sheet was placed in a Dupont impact tester, and the tip was radial.
A striking core with a 6.3mm ball was brought into contact with the ball, and a 1.5Kg weight was allowed to fall naturally onto it at different heights to find the maximum energy that would not cause damage.
Measurements were performed at 20°C and -10°C. Tensile test: Stress at yield point (YS), stress at break (US), and elongation at break (UE) were measured in accordance with ASTM D638-68T. The intrinsic viscosity (hereinafter abbreviated as [η]) was measured at 135°C using tetralin solvent. To measure the number of particles, a film with a thickness of 30μ was formed using a T-die extruder, and the number of particles with a diameter of 50μ or more was counted and converted to number/CC. According to the study results of the present inventors,
When it was 1000 or less, the surface gloss of the formed product was good. The appearance of the molded product was observed by molding a sheet with a thickness of 1 mm and a length and width of 16 cm using an injection molding machine. Example 1 (1) Synthesis of catalyst In an autoclave equipped with a 200° stirrer, hexane was added.
45.5 and TiCl ₄ 11.8 and the solution was −
While maintaining the temperature at 10 to -5°C, a solution consisting of 43.2 parts of hexane and 13.5 parts of diethylaluminium chloride was added dropwise over 3 hours with stirring. The reaction mixture was then held at -10 to 0°C for 15 minutes, then heated to 65°C for 2 hours, and further heated to 65°C.
It was kept under stirring for 2 hours at °C. The reaction mixture then separates the solid (abbreviated as reduced solid) from the liquid phase.
The hexane was removed after washing six times with 50 g of hexane. The resulting reduced solid was suspended in 92% hexane and 19.6% diisoamyl ether was added thereto. After stirring this suspension at 35°C for 1 hour, the obtained solid (abbreviated as ether treated solid)
was separated from the liquid phase and the hexane was removed after washing six times with 50 g of hexane. To the resulting ether-treated solid was added a 40% by volume solution of TiCl ₄ in hexane, and this suspension was
The mixture was stirred at 70°C for 2 hours. The resulting solid was then separated from the liquid phase and
After washing with hexane 10 times, the hexane was removed and drying was performed. The solid obtained in this way is referred to as a TiCl ₃ solid catalyst (). (2) Propylene-ethylene block copolymerization As shown in Figure 2, three fluidized bed reactors were connected in series to carry out propylene-ethylene block copolymerization continuously. As shown in Figure 1, reactors (A) and (B) are fluidized bed reactors with an internal volume of 1 m ³ and a classification zone with three plates with an open area ratio of 20% installed at the bottom. . Reactor (C) is a fluidized bed reactor without a lower classification zone. In the reactor (A), 3 g/hr of titanium trichloride solid catalyst (), 30 g/hr of diethylaluminum chloride, 5.6 g/hr of triethyl aluminum, and 1.9 g/hr of methyl methacrylate were used as catalysts.
Propylene and hydrogen were also fed continuously at a rate of g/hr. The catalyst components were fed into the fluidized bed, and the other catalyst components were fed from the top of the fluidized bed. The polymer particles were extracted from the lower part of the classification zone of the reactor (A) together with a portion of the circulating gas and transferred to the reactor (B). In addition, propylene and hydrogen were continuously supplied to the reactor (B). Then, after the polymer particles were transferred to the reactor (c), ethylene, propylene, and hydrogen were continuously supplied. The polymerization conditions are shown in Table 1.

【table】

[Table] During the polymerization period, the reactors (A), (B), and (C) used compressors installed in the circulation system to maintain the circulating gas flow rates at 80, 120, and 120 m ³ /hr, respectively. This was in the range of 2 to 3 times the flow rate of the polymer particles. The reaction ratio of ethylene/propylene in reactor (C) was 56/44 (molar ratio) based on material balance.
In addition, as a result of sampling a small amount of polymer from the outlet of reactors (B) and (C) and measuring [η],
They were 1.80 and 2.65 (g/dl), respectively. In order to confirm the classification effect of polymer particles, we sampled polymer particles at the outlet of the reactor (A) and measured the particle size distribution. As a result, particles of 300 or less were 0.1% by weight.
It was hot. The result measured in a reactor without a classification effect in Comparative Example 1, which will be described later, was 2.0% by weight.
The number of microparticles was reduced to about 1/20, indicating that the method of the present invention has an extremely large classification effect. The obtained polymer particles were extruded into strands using an extruder with the addition of known additives, and then made into pellets.The physical properties of the particles were measured and the results are shown in Table 3. Comparative Example 1 Propylene was produced under the same conditions as in Example 1, except that a 400 fluidized bed reactor without a classification zone was used in place of the reactors (A) and (B) used in Example 1. Ethylene block copolymerization was carried out. Table 3 shows the physical properties of the obtained polymer. In Example 1, there were few spots and the appearance and physical properties of the molded product were satisfactory, but when compared with Example 1, Comparative Example 1 shows that the amount of spots measured on the film was extremely large. In addition, when a 1 mm sheet was injection molded, significant uneven gloss occurred on the surface and many white spots were observed inside. In addition, it can be seen that major physical properties such as falling ball impact strength, impact whitening area, and tensile properties are extremely low. Example 2 (1) Synthesis of catalyst 200ml of hexane in an autoclave with a stirrer
and TiCl ₄ 13.5, and the solution was heated to -10 ~
While maintaining the temperature at -5°C, a solution consisting of 35% hexane and 16.5% diethylaluminium chloride was added dropwise over 4 hours with stirring. The temperature was then raised to 105°C, and stirring was further continued at 105°C for 2 hours. The resulting solid was separated from the liquid phase by standing at room temperature, and further washed 6 times with 50 ml of hexane to obtain a heat-treated solid. The resulting heat-treated solid was suspended in 120 ml of toluene, to which was added 26 ml of di-n-butyl ether.
Then, 28 kg of iodine was added and stirred at 95°C for 1 hour. The solid obtained by standing at room temperature was separated from the liquid phase, washed six times with 50 ml of hexane, and then dried. The solid thus obtained is
TiCl ₃ solid catalyst (). (2) Propylene-ethylene block copolymerization As shown in Figure 3, four fluidized bed reactors each having an internal volume of 1 m ³ were connected in series to carry out propylene-ethylene block copolymerization continuously. reactor
(E) and (F) have the same classification band as Example 1,
Moreover, reactors (D) and (G) are reactors that do not have a classification zone at the bottom. The catalyst was supplied to the reactor (D) in the same manner as in Example 1, except that the TiCl ₃ solid catalyst () was used instead of the TiCl ₃ solid catalyst (), and propylene was polymerized in the reactors (D) and (E). Then, copolymerization of propylene and ethylene was carried out in reactors (F) and (G). Transfer from reactor (D) to (E) uses pressure difference,
Transferred with circulating gas from reactor (E) to (F) and (F)
From (G), the polymer particles and most of the circulating gas were separated using a cyclone and then transferred. The polymerization conditions are shown in Table 2.

[Table] Comparative Example 2 Propylene-ethylene block copolymerization was carried out continuously in the same manner as in Example 2 except that the classification zones of reactors (E) and (F) were removed. Table 3 shows the physical properties of the obtained polymer. In Example 2, there were no particular problems in the appearance and physical properties of the molded product. Comparing Comparative Example 2 with Example 2, the amount of particles was extremely large, and significant gloss unevenness occurred on the surface of the injection molded product. In addition, physical properties such as impact strength and tensile properties are extremely low.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 shows an example of a fluidized bed reactor in which the present invention is practiced. 1: Reaction zone, 2: Perforated plate or single hole plate for classification, 3: Classification zone, 4: Gas distribution device, 5: Gas distribution device, 6: Solid catalyst component supply port, 7: Interpolant, 8: Polymer outlet, 9: organometallic compound and electron donating compound supply port, 10: hydrogen gas supply port, 11: deceleration zone, 12: final reaction gas outlet, 1
3: Cyclone, 14: Filter, 15: Compressor, 16: Heat exchanger, 17: Propylene gas inlet, 18: Jacket, 19: Ethylene and α
- Olefin inlet A: fluidized bed level. Figures 2 and 3 show embodiments of block copolymerization of propylene with ethylene and/or other alpha-olefins.

Claims (1)

[Claims] 1. Using a Ziegler-Natsuta catalyst, in a fluidized bed reactor or a fluidized bed reactor equipped with a stirrer,
In a method of continuously polymerizing or copolymerizing α-olefin in substantially the absence of a liquid medium, the reactor has a classification zone, and the temperature of the reaction system is kept at 30 to 100°C and the pressure is 1~50Kg/ ^cm2
A continuous gas phase polymerization method for α-olefin, characterized by maintaining conditions in which α-olefin is not substantially liquefied within the range of (G). 2 Using a Ziegler-Natsuta catalyst, in a fluidized bed reactor or a fluidized bed reactor with a stirrer,
In a method of copolymerizing α-olefin in a continuous manner substantially in the absence of a liquid medium, polymerization is performed such that propylene alone or ethylene and/or butene-1 copolymerized with propylene is 6 mol% or less. A block copolymerization method comprising a first step of copolymerizing with propylene and a second step of one or more steps of polymerizing so that ethylene and/or butene-1 copolymerized with propylene is 10 mol% or more, the first step being Polymerization is carried out by connecting one or more reactors in series, including at least one reactor having a classification zone, and the temperature of the reaction system is 30 to 100°C, and the pressure is 1 to 50 kg/kg.
1. A continuous gas phase polymerization method for α-olefin, characterized in that conditions are maintained in which α-olefin does not substantially liquefy within the range of cm ² (G). 3 Fluidization initiation speed of α-olefin polymer particles
3. The method according to claim 1, wherein the polymerization is carried out in an upward flow of gas in the range of 1.5 to 10 times the Umf. 4 Claim 1, characterized in that the polymerization is carried out in an upward flow of gas in a range of 2 to 6 times Umf.
or the method described in paragraph 2. 5. The method according to claim 1, wherein the α-olefin has 2 to 8 carbon atoms. 6. The method according to claim 5, wherein the α-olefin is ethylene, propylene, butene-1, 4-methylpentene-1. 7 In the first step, the reactor having a classification zone is
Claim 2, characterized in that a total of 1 to 7 reactors are connected in series, and the second step has 1 to 4 reactors connected in series.
The method described in section.