KR840000371B1 - Process for producing polyethylene by continuous multi-stage polymerization - Google Patents

Abstract

Multi-stage polymerization process for polyethylene is conducted by combinating two polymerization systems; (a) hydrogen and ethylene are supplied into the hydrocarbon solvent at 50-120≰C and 5-7kg/cm2 where the mole ratio of ethylene to hydrogen in the vapor phase is 0.5-6.0 and ethylene amt. used is 30-80% of total supply; (b)hydrogen and ethylene are supplied at 30-100≰C and 5-70kg/cm2 where ethylene to hydrogen mole ratio is 0.001-0.5 and ethylene amt. is 20-70% of total supply. Ziegler type catalyst is needed for the above reaction.

Description

Method for producing polyethylene by continuous multistage polymerization

The present invention relates to a process for the production of polyethylene by continuous multistage polymers. In the present invention, polyethylene refers to a small amount of other α-olefins copolymerizable with ethylene in addition to the homopolymer of ethylene, such as propylene, butene-1, hexene-1,4-methylpentene-1 or butadiene, dicyclopenta. It also contains dienes such as dienes and copolymers.

In the field of extrusion molding and hollow molding, which are the main uses of polyethylene, as a high molecular weight (low melt index), polyethylene having a suitable strength and easy processing is required. Low melt index polyethylene has excellent strength, but has a drawback of poor fluidity during molding. As a means to solve this problem, polyethylene having a high molecular weight distribution is suitable for injection molding, but a polyethylene having a wide molecular weight distribution is desired as polyethylene used for extrusion molding or blow molding. In the case of blow molding a polymer having a high molecular weight distribution, the extrusion pressure is increased at the time of molding so that the molding is impossible, and the appearance of the product is remarkably damaged by the generation of streaks and patterns. In the case of extrusion molding, it is accompanied by a fatal adverse effect by excessively increasing the extrusion pressure, increasing the instability of the molding, and significantly lowers the commodity value. In order to solve these problems, the molecular weight distribution of the polymer is broadened, thereby improving processing productivity and obtaining a product having excellent appearance.

As a method of expanding the molecular weight distribution, there are methods such as adding a third component to the polymerization system, mixing and using two kinds of compounds of the organoaluminum compound as one component of the catalyst, and using a catalyst having various polymerization active points. Producing a sufficiently wide polymer is not necessarily easy. On the other hand, the multistage polymerization method is known as a means of making the molecular weight distribution width large and arbitrarily adjusting, but the method is not satisfactory. For example, by combining a supported catalyst component and an organometallic compound, a continuous multi-stage polymerization that produces a low molecular side polymer in a first step, then releases gas from the polymerization system and a polymer side polymer in a second step. The law is published in Japanese Patent Application No. 51-47079. The method is a high temperature melting polymerization having a polymerization temperature of 120 to 250 ° C., and the use of a solvent sufficient to dissolve the polymer requires a considerable amount of solvent. In addition, the special public office 48-42716 discloses a method in which the polymerization system is released after the completion of the polymerization of the first stage, the gaseous gas is released, the new polymerization conditions are set, and the polymerization of the second stage is performed. The polymerization method is remarkably bad in polymerization productivity.

Moreover, as a manufacturing method by the multistage superposition | polymerization which makes a polymer side by a front end (1st stage), and a low molecular side by a rear end (2nd stage), special publications 46-11349, 54-7488, and 54-32588 are known. ought. In Special Publication No. 46-11349, polymerization is carried out at a pressure of 10 kg / cm 2 (gauge pressure) or less in an inert solvent, using a catalyst obtained by combining a trivalent titanium compound and an organoaluminum compound, which is not required to be supported on a carrier. The method of making it is shown. In this method, the catalyst is limited in terms of using a trivalent titanium compound that does not require a carrier, and in the embodiments shown, the polymerization pressure is 6 kg / cm 2 (gauge pressure) or less. This low polymerization pressure significantly lowers the productivity of the polymer, and furthermore, this method is a discontinuous production process and does not specifically describe the industrially advantageous continuous polymerization method. Japanese Patent Application Laid-Open No. 54-7488 shows that the first stage polymerization is carried out in a liquid-filled state using a supported catalyst, but in this method, it is extremely difficult to control the molecular weight of the resulting polymer. In Japanese Patent Application Laid-Open No. 54-32588, it is indicated that the inert gas is forcibly supplied to the first stage polymerizer to increase the total pressure, and the polymer of the polymer side polymer is produced by the second stage polymerization in the first stage polymerization to make the low molecular side polymer. Excess inert gas has the disadvantage and difficulty of making sufficiently low molecular polymers immediately after entering the second stage polymerization system as they are not consumed or removed.

On the other hand, the inventors of the present invention are reaction products of conventional trivalent metal halides with hydroxides, oxides, carbonates of divalent metals, double salts containing these, or hydrates of divalent metal compounds (hereinafter referred to as solid products (I)). The catalyst component carrying the present invention is studied to solve the drawbacks of the conventional continuous multistage polymerization by using a combination of the solid product (I), the solid product (II) prepared from the polysiloxane and the transition metal compound and the organoaluminum compound. It was found that this can be done, and various studies have led to the completion of the production method of the present invention.

That is, an object of the present invention is to provide a production method in which the above-described conventional problems in the continuous multistage polymerization of polyethylene are solved to obtain polyethylene having a wide molecular weight distribution.

The production method by the continuous multistage polymerization of polyethylene of the present invention comprises a solid product (I) obtained by reacting a trivalent metal halide with a hydroxide oxide, a carbonate, a double salt containing the same, or a hydrate of a divalent metal compound, In the presence of a catalyst obtained by combining a polysiloxane and a final solid product (II) prepared on a transition metal compound of Group 4a or Group 5a and an organoaluminum compound, a) and b) characterized by producing by combining the polymerization system.

a) of ethylene to hydrogen in the gas phase of the polymerizer under conditions of a polymerization temperature of 50 ° C. or more and less than 120 ° C. and a polymerization pressure of 5 to 70 kg / cm 2 in a state where a gaseous phase is present in the upper part of the polymerizer in a saturated hydrocarbon solvent. The polymerization system (L) which supplies hydrogen so that molar ratio may exceed 6.0 and it may be 6.0 or less, and supply 30 to 80% of ethylene of the total ethylene feed amount.

b) The molar ratio of ethylene to hydrogen in the gas phase of the polymerizer in a gaseous phase at a polymerization temperature of 30 ° C. or higher and 100 ° C. or lower and a polymerization pressure of 5 to 70 kg / cm 2 is in a range of 1 to 0.001 or more and 0.5 or less. The polymerization system (H) which supplies hydrogen so that it may supply 20 to 70% of ethylene of the total ethylene amount.

In addition, if necessary, a small amount (10 mol% or less relative to ethylene) of the α-olefin can be supplied to the (L) and / or (H) polymerization system to produce a copolymer of ethylene and the α-olefin. In that case, it is preferable that the molar ratio of the sum total of the number-of-moles of ethylene and (alpha) -olefin, and the molar ratio of hydrogen become said mole ratio of a) and / or b /.

In the manufacturing method of this invention, a low molecular side polymer is produced | generated in the polymerization system (L), and a polymer side polymer is produced | generated in the polymerization system (H). The combined order of the polymerization system (L) and the polymerization system (H) is not particularly limited. That is, continuous multistage polymerization in which the low-molecular-side polymer is used as the polymerization system (L) as the first stage polymerization system, and the polymer-side polymer is produced as the polymerization system (H) as the second stage polymerization system (hereinafter referred to as continuous multistage (LH) polymerization). ], Continuous multistage polymerization in which the polymer stage-side polymer is used as the polymerization system (H) and the low-molecular-side polymer is produced as the polymerization system (L), followed by continuous multistage (HL) polymerization. Called.

It is possible to use the above two procedures. In this case, the selection of a process is preferably appropriately determined according to the necessity, and in the present invention, a polymer of equivalent quality can be obtained by employing any of them.

Continuous multistage (LH) polymerization starts superposition | polymerization by supplying a catalyst to the 1st-stage polymerization system (L). The polymerization is carried out in a saturated hydrocarbon solvent in a state where a gaseous phase is present in the upper part of the polymerization reactor. It is performed under the conditions of 50 kg / cm 2. The molecular weight of the resulting polymer is controlled by supplying ethylene and hydrogen such that the molar ratio of ethylene to hydrogen in the gaseous phase of the polymerizer exceeds 1 to 0.5 and falls within the range of 6.0 or less. This is adjusted. In this case, the molecular weight of the polymer obtained is the weight average molecular weight (Mw), and the amount of the polymer corresponding to 2 × 10 ⁴ to 2 × 10 ⁵ is controlled by 30 to 80% ethylene feed of the total ethylene feed.

After completion of the first stage polymerization by the polymerization system (L), the polymer suspended in the solvent is led to a pressure zone of 0.1 to 30 kg / cm 2, and at least one of hydrogens having released the first stage polymerization system in a state dissolved in the solvent. The part is taken out of the polymerization system. At least one portion of the removed hydrogen is reused in the polymerization system L in the first stage. The low zone of pressure is usually designed in the middle of each stage, but it is also possible to combine one into the other polymerization system. The difference in pressure drop between the first stage polymerization system and the low pressure zone is determined by the amount of hydrogen required in the polymerization system H in the second stage.

The polymer suspended in the solvent from which most of the hydrogen is removed is led to the polymerization system H in the second stage by a transfer means such as a transfer pump. The polymerization is carried out on the polymerization vessel under the conditions of the newly set polymerization temperature of 30 ° C. or higher and 100 ° C. or lower (preferably 40 ° to 90 ° C.) and a polymerization pressure of 5 to 70 kg / cm 2 (preferably 10 to 50 kg / cm 2). It is performed in a state where a part exists. The molecular weight of the polymer produced is controlled by causing the molar ratio of ethylene to hydrogen in the gaseous phase to fall within the range of from 0.001 to 0.5 to 0.5, and supplying ethylene and hydrogen. The molecular weight of the polymer obtained in the second stage polymerization corresponds to 2 × 10 ⁵ to 8 × 10 ⁵ with respect to the weight average molecular weight. The amount of polymer produced is controlled by an ethylene feed of 20 to 70% of the total ethylene feed. Usually, although the molecular weight of a 2nd stage is adjusted with hydrogen etc. which were dissolved in the solvent, it is also possible to supply newly.

Continuous multistage (HL) polymerization starts superposition | polymerization by supplying a catalyst to the polymerization system (H) of a 1st stage. The polymerization is carried out in a saturated hydrocarbon solvent in a state where a gaseous phase is present in the upper part of the polymerization reactor. The polymerization temperature is 30 ° C. to 100 ° C. (preferably 40 to 90 ° C.), and the polymerization pressure is 5 to 70 kg / cm 2 (preferably 8). To 78 kg / cm 2 and more preferably 11 to 50 kg / cm 2). The molecular weight of the resulting polymer is controlled by supplying ethylene and hydrogen in a molar ratio of ethylene to hydrogen in the gaseous phase portion of the polymerizer in the range of 1 to 0.001 or more and 0.5 or less. In this case, the molecular weight of the obtained polymer corresponds to 2x10 ⁵ to 8x10 ⁵ with respect to the weight average molecular weight. The amount of polymer produced is controlled by an ethylene feed of 20 to 70% of the total ethylene feed.

The polymer suspended in the solvent obtained in the polymerization system (H) in the first stage is transferred to the polymerization system (L) in the second stage as it is, but may be transferred after separating components such as hydrogen as necessary. The transfer method is performed by a forced transfer means such as a transfer pump. The polymerization system L of the second stage is under the newly set polymerization conditions, that is, the polymerization temperature is 50 ° C. or more and less than 120 ° C. (preferably 70 ° C. to 100 ° C.), and the polymerization pressure is 5 to 70 kg / cm 2 (preferably 8 to 70 kg). / Cm 2, more preferably 11 to 50kg / cm 2), and polymerization is carried out in a state in which a gas phase portion is present on the polymerization reactor. The molecular weight of the resulting polymer is controlled by allowing the molar ratio of ethylene to hydrogen in the gaseous phase to fall within the range of 6.0 up to 0.5 or more and feeding ethylene and hydrogen. The molecular weight of the polymer obtained here corresponds to 2 * 10 <^4> -2 * 10 <^5> with respect to a weight average molecular weight. The amount of polymer produced is controlled by an ethylene feed of 30 to 80% of the total ethylene feed.

In the case of the production method of the present invention, the supply of the catalyst is usually produced only in the first stage polymerization system, but it can also be used in the second stage polymerization system if necessary.

The molar ratio of ethylene to hydrogen in the gaseous phase of the polymerization system (L) and the polymerization system (H) of the present invention and the supply amount of ethylene are determined depending on the use of the finally obtained polymer. For example, in the production of polyethylene for use in films, the polymerization system (L) preferably has a molar ratio of ethylene to hydrogen of preferably from 1: 1.0 to 5.0, more preferably from 1: 1.5 to 4.0, and the ethylene feed is all ethylene 40 to 60%, preferably 50% of the feed amount. In the case of blow molding, the polymerization system (L) has a molar ratio of ethylene to hydrogen of preferably 1: 1.0 to 3.5, more preferably 1: 1.2 to 3.0, and the ethylene supply amount is the total ethylene supply amount. Of 30 to 70% (preferably 50%), the polymerization system (H) is preferably a molar ratio of ethylene to hydrogen is preferably 1: 0.005 to 0.5, more preferably 1: 0.01 to 0.4, 30 to 70% (preferably 50%) of the ethylene feed.

In the multistage continuous polymerization of the present invention, a plurality of polymerizers are usually connected in series, but a plurality of polymerizers may be connected in parallel (or a part of them in parallel) to form a first stage and / or a second stage polymerization system.

As the solvent used for the polymerization of the production method of the present invention, saturated hydrocarbons having 4 to 15 carbon atoms (for example, butane, pentane, hexane, heptane and octane), kerosene and the like are used.

The catalyst used in the preparation method of the present invention is a solid product (I) obtained by reacting a trivalent metal halide with a hydroxide, oxide, carbonate, a double salt containing these, or a hydrate of a divalent metal compound. And a final solid product (II) carrying a transition metal compound prepared from the transition metal compound of Group 4a or 5a of polysiloxane, and an organoaluminum compound.

Examples of the trivalent metal halide are aluminum trichloride (anhydrous) and iron trichloride (anhydrous).

Examples of the divalent metal hydroxides (hereinafter referred to as divalent metal compounds) include, for example, magnesium hydroxide, calcium hydroxide, zinc hydroxide, hydroxides such as manganese hydroxide, oxides such as magnesium oxide, calcium oxide, zinc oxide, and manganese oxide, Complex oxides containing divalent metals such as Mg Al ₂ O ₄ , Mg ₂ SiO ₄ , Mg ₆ MnO ₈ , magnesium carbonate, manganese carbonate, carbonates such as calcium carbonate, SnCl ₂ · 2H ₂ O, MgCl ₂ · 6H Halide hydrates such as ₂ O, NiCl ₂ · 6H ₂ O, MnCl ₂ · 4H ₂ O, KMgCl ₃ · 6H ₂ O, hydrates of complex salts containing oxides and halides such as 8MgO · MgCl ₂ · 15H ₂ O, Hydrates of double salts containing oxides of divalent metals such as 3MgO.2SiO ₂ .2H ₂ O, hydrates of carbonates and hydroxides such as 3MgCO ₃ .Mg (OH) ₂ .3H ₂ O and Mg ₆ Al ₂ (OH) Hydrates of hydroxide hydroxides containing divalent metals such as ₁₆ CO ₃ · 4H ₂ O are recommended.

Solid product (I) is obtained by reacting a trivalent metal halide with a divalent metal compound. 5 to 100 hours in advance as a Ball Mill to allow this reaction. As a vibration mill, it is desired to mix and grind for 1 to 10 hours, and to make it fully mixed. When the mixing ratio of the trivalent metal halide and the divalent metal compound is expressed by the atomic ratio of the divalent metal to the trivalent metal, usually 0.1 to 20 is sufficient, preferably 1 to 10. The reaction temperature is usually 20 to 500 ° C, preferably 50 to 300 ° C. The reaction rate is suitable for 30 minutes to 50 hours, and when the reaction temperature is low, the reaction is carried out for a long time, and the reaction is carried out so that unreacted trivalent metal is not left.

As polyoxane, general formula

It is a linear or cyclic siloxane polymer represented by the above, each R represents a homologous or heterologous residue obtained by bonding to silicon, among them hydrocarbon residues such as hydrogen, alkyl group, aryl group, halogen, alkoxy group or aryloxy group, The thing made from 1 type, such as a fatty acid residue, and these 2 or more types are distributed and couple | bonded in a molecule with various ratio, etc. are used. It is commonly used that each R in the above formula is composed of a hydrocarbon moiety, and specific examples thereof are alkali alkali polymers, for example, octamethyl trisiloxane CH ₃ [Si (CH ₃ ) ₂ O] ₂ Si (CH ₃ ) ₃ , lower weight products such as octaethyl cyclotetrasiloxane [Si (C ₂ H ₅ ) ₂ O] ₄ , and dimethylpolysiloxane [Si (CH ₃ ) ₂ O] _n , ethylpolycyclosiloxane [SiH (C ₂ H ₅₎ O] _n, methylethyl polysiloxanes _{[Si (CH 3) (C} 2 H 5) O] alkyl siloxane polymer such as a polymer, such as _n, again hexahydro-phenyl-cyclopenten tree siloxane [Si (C ₆ Arylsiloxane compounds such as H ₅ ) ₂₀ ] ₃ , diphenylpolysiloxane [Si (C ₆ H ₅ ) ₂ O] _n , and diphenylsiloctamethyltetrasiloxane [(CH ₃ ) ₃ SiO [Si ( CH ₃ ) (C ₆ H ₅ ) O] ₂ Si (CH ₃ ) ₃ , methylphenylpolysiloxane [Si (CH ₃ ) (C ₆ H ₅ ) O] _n, and the like. And other alkyl hydrogen siloxane polymers or haloalkyl siloxane or haloaryl siloxane polymers in which R ₁ is hydrogen or halogen and R ₂ is a hydrocarbon residue such as an alkyl group or an aryl group. Moreover, polysiloxane which each R is an alkoxy or aryloxy group, or a fatty acid residue can also be used in mixture. It is desired that the polysiloxane used is liquid, and the viscosity (25 ° C) is suitable for 10 to 10,000 centipoise, preferably in the range of 10 to 1000 centipoise.

As the transition metal compound, there are titanium, vanadium halides, oxyhalides, alcoholates, alkoxy halides, acetoxy halides, and the like. For example, titanium tetrachloride, titanium tetrabromide, tetraethoxytitanium, tetrabutoxytitanium and monochlorobutoxy Titanium, dichloro butoxytitanium, trichloro monoethoxytitanium, vanadium tetrachloride, oxy trichloride, and the like.

As a specific preparation method of solid product (II), the following example is mentioned.

(1) Simultaneously mix and react solid product (I) with polysiloxane and transition metal compound.

(2) The solid product (I) is mixed with polysiloxane, and the following transition metal compound is added and reacted.

(3) The solid product (I) and the transition metal compound are mixed and the following polysiloxane is added and reacted.

(4) The polysiloxane and the transition metal compound are mixed and the solid product (I) is mixed and reacted with the following mixture.

Either method can be performed in the presence or absence of a solvent.

The mixing ratio of the solid product (I), the polysiloxane and the transition metal compound is 10 to 10,000 g of polysiloxane, preferably 20 to 5000 g, and the transition metal compound is 1 to 1000 g, based on 100 g of the solid product (I). Preferably it is 10-500g, and it is 2-2000g, Preferably it is 5-500g with respect to 100g of polysiloxane. Mixing is suitably -50 ° C to 30 ° C, but is usually mixed at room temperature (about 20 ° C). It is preferable to perform mixing, stirring. After mixing, the mixture is reacted at 30 to 300 ° C, preferably at 50 to 200 ° C for 10 minutes to 30 hours.

In the case where the polysiloxane and the transition metal compound are mixed, and then the solid product (I) is mixed and reacted with the compound, the mixture of the polysiloxane and the transition metal compound should be room temperature before mixing the solid product (I). It is good to make it pass for 1 minute-5 hours at the temperature of 100 degrees C or less (preferably 60 degrees C or less).

After completion of the reaction, the mixture is filtered by a conventional method, and washing is repeated as a solvent to remove the unreacted transition metal compound and polysiloxane, followed by drying. This gives a solid product (II).

Although it is not necessary to use a solvent for the mixing and the reaction in preparation of the solid product (II), in order to make it react uniformly, you may mix or dissolve or disperse | distribute the said component in the solvent previously or arbitrarily. The solvent usage is sufficient even at about 10 times (weight) or less of the total amount of each component. Examples of the solvent used for preparing the solid product (II) include aliphatic hydrocarbons such as hexane, heptane, octane, nonane and tecan, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene, chlorobenzene, dichlorobenzene and trichloro Halogenated aromatic hydrocarbons such as benzene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, tetrachloroethylene and carbon tetrachloride.

Examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, triisobutylaluminum and trihexyl aluminum, dialkylaluminum monochlorides such as diethylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride, and mono Alkoxy alkyl aluminum, such as ethoxy diethyl aluminum and diethoxy monoethyl aluminum, can also be used.

A feature of the present invention is that low-temperature polymerization (slurry polymerization) of less than 120 ° C is possible in the continuous multistage polymerization method of ethylene by using the special polymerization catalyst shown in the present invention. The method of the present invention for this purpose uses less solvent at the time of polymerization as compared to known continuous high temperature dissolution polymerization, and therefore, the polymer concentration can be increased, so the economy is also excellent. As such, there is an advantage that the polymer can be obtained in powder form. In the polymerization of the present invention, it is easy to control the polymerization reaction and also to control the molecular weight. Moreover, the polymer adhesion of the polymerizer wall is extremely small, and there is a characteristic that stable multistage polymerization can be performed for a long time. The catalyst used in the present invention is different from the known catalysts, and has a very high polymerization activity, and it is possible to eliminate the step of removing the catalyst remaining in the polymer, that is, the deliming step, after the completion of the reaction. Another feature of the invention is that the molecular weight distribution of the polyethylene obtained is extremely wide when compared to known continuous high temperature dissolution polymerization. Therefore, since the flow characteristics of the molding is good and the resin pressure is low at the time of molding, high-speed molding is possible, and since the melt fracture does not occur, the appearance of the molding is good. In the case of film production, the formability is stable for a long time because the equatorial strength and opacity, the fisheye is not seen, and the film surface is smooth.

In addition, the volume specific gravity of the polyethylene powder obtained by the present invention is 0.35 to 0.45, and the shape of the powder particles is good, so that the production efficiency per hour and volume of the polymerization reactor is large, and the powder is easily assembled.

Hereinafter, the characteristic of this invention is demonstrated concretely by an Example and a comparative example.

는 중량 평균 분자량이고

은 수평균 분자량이다)은 워터사 제품 GPC-200형의 크로마토그라피에 의해 구한다.The melt fracture in the examples and comparative examples is in accordance with ASTM D-1238 (E).

Is the weight average molecular weight

Silver number average molecular weight) is calculated | required by the chromatography of GPC-200 type | mold by the water company.

The polymer yield is g (g-polymer / g- (II), H ₂ ) of polyethylene per g of solid product (II) obtained in 1 hour or g (g-g of polyethylene per millimolar of ethane atom obtained in 1 hour). Polymer / millimolar-Ti.Hr).

The film is made with a browning film molding machine (50 mm, 75 rpm, manufactured by Prag Co., Ltd.) at a thickness of 10 µm under conditions of a temperature of 180 to 200 ° C. Observe the injection amount of the molten resin during manufacture. The punching impact strength of the obtained film was ASTM-D 781, haze was ASTM-D 1003, and the fisheye measured the number of granular polymer materials having a diameter of 50 µm or more present in the film 1000 cm 2.

Blow molding was performed using a blow molding machine (55 mm ?, 50 rpm, IPB-110) to make a bottle of internal volume of 4 L under conditions of a temperature of 165 to 175 캜 and a cycle time of 3 minutes.

Stress cracking resistance (F ₅₀ value) is performed according to ASTM-D 1693.

Example 1

(1) Preparation of Transition Metal Catalysts

76 kg of magnesium hydroxide and 90 kg of aluminum chloride (anhydrous) are mixed and pulverized with a vibration mill for 5 hours, and then reacted at 150 ° C. for 5 hours. After cooling and pulverizing, a solid product (I) is obtained.

173 kg of titanium tetrachloride and 100 kg of chain dimethylpolysiloxane (viscosity 100 centipoise) are added and mixed in 150 L of toluene, and then 100 kg of the solid product (I) is added thereto and reacted at 110 ° C for 2 hours. After completion of the reaction, filtration was carried out according to the conventional method, and the solid product was washed with hexane until no unreacted titine tetrachloride and unreacted polysiloxane were detected in the filtrate, and the solid product was dried under reduced pressure (II) (hereinafter referred to as solid product ( Weak). The titanium atom is 0.2 mol in 1 kg of the solid product (II). This solid product (II) is used as the transition metal catalyst component.

(2) Multistage (LH) Continuous Polymerization of Ethylene

35 mg of solid product (II) ₁ per hour (0.007 mmol in terms of titanium atoms), 0.3 mmol of triethylaluminum per hour, and hexane at a rate of 3 liters per hour were supplied to a 10 liter first stage polymerizer, and the liquid in the polymerization vessel was supplied. While maintaining the level at 80% and discharging the contents of the polymerizer, the temperature was set at 80 ° C and 360 Nl per hour of ethylene containing 5% (volume%) of butene-1, and hydrogen to ethylene (containing butene) versus hydrogen in the gas phase of the polymerizer. The first stage polymerization was continuously performed by the polymerization system L at a voltage of 40 kg / cm 2 (gauge pressure) while supplying the molar ratio of 1 to 1.5.

After completion of the first stage polymerization, the polymer suspended in the solvent is introduced into a degassing tank maintained at an internal pressure of 2 kg / cm 2, and most of hydrogen and the like dissolved in hexane are separated. The separated hydrogen was recycled and recycled to maintain ethylene to hydrogen at a predetermined ratio in the gas phase of the first stage polymerizer.

The polymer slurry from the degassing tank was introduced into the second stage polymerizer with a total volume of 10 liters and was added at 75 캜 while discharging the contents of the polymerizer so that the liquid level in the polymerizer was maintained at 80% without adding hydrogen and a catalyst. And ethylene were supplied at a rate of 340 Nl per hour, and the second stage polymerization was carried out continuously by the polymerization system (H) at a voltage of 40 kg / cm 2. The molar ratio of ethylene to hydrogen in the gaseous phase of the second stage polymerizer is one to 0.06.

102 kg of polyethylene powders are obtained after stabilizing the above multistage polymerization and drying without deliming. Polymer yield is 24,300 g-polymer / g- (II) .Hr.

25이다.The obtained polyethylene powder was melt index 0.05, volume ratio 0.40, density 0.950, butene content 2.5% by weight,

25.

When the film is produced using this polyethylene powder, the injection amount of the molten resin is 24 kg / Hr. The punching impact strength of the film is 140kg-cm / mm, the haze value is 77%, the fisheye is nine, the surface condition is good and the film performance is practically no problem.

Comparative Example 1

6이다.Except for setting the molar ratio of ethylene (butene-containing) to hydrogen in the gas phase of the polymerizer to 0.14 to 1, the same process as in (2) First stage polymerization of Example 1 was carried out, and the first stage polymerization was performed continuously for 120 hours to carry out Example 1 and 50 kg of polyethylene of the same meltindex 0.05 are obtained. This polyethylene

6.

The production of a film using this polyethylene is satisfactory.

Comparative Example 2

A transition metal catalyst component was obtained in the same manner as in Example 1 (1) except for using dimethyl polysiloxane. The titanium atom in 1 kg of the catalyst component is 0.15 mol. Except for using this catalyst component instead of solid product (II), it carried out multistage continuous polymerization of ethylene similarly to (2) of Example 1, and obtained 20 kg of polyethylene.

이 10이다.This polyethylene

This is 10.

When manufacturing a film using this polyethylene, since a fish eye arises in a film and film forming property is not stabilized, strength is not enough and it is not satisfactory as a film.

Example 2

A 10-liter first stage polymerizer was supplied with 35 mg of solid product (II) per hour, 0.3 mmol of triethylaluminum per hour, and 2.5 liters of hexane per hour at a rate of 2.5 l per hour, and the liquid level in the polymerizer was maintained at 80%. While discharging the contents of the polymerizer, ethylene was supplied at 300 Nl per hour at 85 ° C, and hydrogen was supplied so that the molar ratio of ethylene to hydrogen in the gaseous phase of the polymerizer was 1 to 3.5, and continuously produced by the polymerization system (L) at a voltage of 40 kg / cm 2. Two stage polymerization is performed.

After completion of the first stage polymerization, the polymer suspended in the solvent was introduced into a 5 L degassing vessel maintained at 1.0 kg / cm 2 of internal pressure, hydrogen and ethylene dissolved in hexane were separated, and the separated hydrogen or ethylene was However, ethylene to hydrogen in the gas phase of the polymerizer is maintained at a predetermined ratio and recycled.

The polymer slurry from the degassing tank was introduced into the second 10-stage polymerizer with a total volume of butene at 70 DEG C while discharging the contents of the polymerizer to maintain the liquid level in the polymerizer at 80% without adding hydrogen and a catalyst. Ethylene containing 5% by volume of 1 was supplied at a rate of 315 Nl per hour, and the second stage polymerization was carried out continuously by a polymerization system at a voltage of 30 kg / cm 2. The molar ratio of ethylene (butene-containing) to hydrogen in the gaseous phase of the second stage polymerizer is 1 to 0.01.

Although the above multistage (LH) polymerization is performed continuously for 120 hours, the operation is extremely stable and 91 kg of polyethylene powder is obtained after drying without deliming. Polymer yield is 21,700 g-polymer / g- (II) .Hr, 108,000 g-polymer / mmimolar-Ti.Hr.

30 이다.This polyethylene has a melt index of 0.04, butene content of 2% by weight, volume specific gravity of 0.41, density of 0.950 g / cm 3,

30 is.

When manufacturing a film using this polyethylene, the injection amount of molten resin is 27 kg / Hr, fluidity | liquidity is favorable and film forming state is also stable. The impact impact strength of the film is 180 kg-cm / mm, which is sufficient strength, and the haze value is 81%, which has a suitable degree of opacity, and there are very few fisheyes. The film surface is smooth and good, and has a very good film performance.

Comparative Example 3

은 6이다.Except for setting the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer to 0.16 to 1, the same conditions as in the first stage polymerization conditions of Example 2 were carried out for 120 hours in succession to obtain 43 kg of polyethylene having a melt index of 0.05. But this polyethylene

Is 6.

This polyethylene can produce a film.

[Comparative Example 4]

The same transition metal catalyst component as in (1) of Example 1 was obtained except that dimethyl polysiloxane was not used. The titanium atom in 1 kg of the catalyst component is 0.15 mmol. In Example 2, except that 250 mg of the catalyst component per hour and 1.5 mmol of triethyl aluminum were supplied per hour instead of the solid product (II), the polymerization was carried out in the same manner. However, 72 hours after the start of attaching the polymer to the polymerizer wall, it can be seen that the polymer is attached to the first stage polymerizer wall, and unstable operation of the polymer is found in the obtained polymer. 87 kg of polyethylene is obtained. Polymer yield is 2,900 g-polymer / g- (II) .Hr, 19,000 g-polymer / mmimomol-Ti.Hr.

13이다.Melt index of this polyethylene 0.05, volume ratio 0.25,

13.

When the film is produced using this polyethylene, the injection amount is 12 kg / Hr, and the flowability of the molten resin is very bad, and the film forming state is unstable. The punching impact strength of the film is 80kg-cm / mm, the strength is insufficient, and there are 450 fisheyes and the surface condition is very bad.

[Comparative Example 5]

100 kg of solid product (I) obtained in Example 1 and 100 kg of dimethylpolysiloxane (the same product as in Example 1) were added to 150 L of toluene, and the mixture was reacted at 110 ° C for 2 hours while stirring to remove unreacted dimethylpolysiloxane. 173kg of titanium tetrachloride was added in a state of non-existence and reacted again at 110 ° C for 2 hours. Then in the same manner as in Example 1 to obtain a final product. The content of titanium atoms is 0.14 mole in 1 kg of the highest solid product.

In the same manner as in Example 2, 90 kg of polyethylene was obtained by subjecting the final product to 100 mg per hour and triethylaluminum at 0.6 mmol per hour instead of the solid product (II) ₁ of Example 2. It was. Polymer yield is 7500 g-polymer / g- (II) .Hr, 54,000 g-polymer / mmimolar-Ti.Hr.

16이다.This polyethylene has a melt index of 0.03, a specific volume of 0.34,

16.

When producing a film, the injection amount is 16 kg / Hr and the fluidity is bad. The punching impact strength of the film is 100kg-cm / mm, the strength is insufficient, and there are 100 fish-eyes.

Comparative Example 6

In Example 2, 120 Nl / hr of ethylene was supplied per hour, and hydrogen was supplied so that ethylene-to-hydrogen was 1 to 4.0 in the gaseous phase, and the first stage polymerization was carried out at a total pressure of 25 kg / cm 2, and ethylene containing 3 volumes of butene-1 was 1. 495 Nl per hour, hydrogen was supplied in the same manner as in Example 2 except that the ethylene (including butene) in the gaseous phase portion was supplied to a hydrogen of 0.05 to 1, and the second stage polymerization was carried out at a total pressure of 40 kg / cm 2 Was performed. 91 kg of polyethylene is obtained.

16이다.This polyethylene is melt index 0.03,

16.

Using this polyethylene, the injection amount is 13 kg / Hr when a film is produced. The punching impact strength of the film is 85kg-cm / mm and the number of fish eyes is 600, so it is not good for practical use.

Comparative Example 7

In Example 2, 540 Nl / hr of ethylene was supplied per hour, hydrogen was supplied so that ethylene-to-hydrogen was 1 to 1.6 in the gaseous phase, and the first stage polymerization was carried out at a total pressure of 40 kg / cm 2, 60Nl of ethylene was produced per hour and ethylene to hydrogen in the gaseous phase. A multistage continuous synthesis of ethylene was carried out in the same manner as in Example 2 except that the second stage polymerization was carried out at a total pressure of 10 kg / cm 2 so that the molar ratio of hydrogen was 0.002. 85 kg of polyethylene is obtained.

13이다.This polyethylene has a melt index of 0.05,

13.

Using this polyethylene, the injection amount is 14 kg / Hr when a film is produced. The punch impact strength of the film is 60kg-cm / mm, and there are 500 fisheyes, which is not good for practical use.

Example 3

(1) Preparation of Transition Metal Catalysts

70 g of MgAl ₂ (OH) ₁₆ CO ₃ · 4H ₂ O and 80 g of aluminum chloride (anhydrous) are mixed and ground at the same time by heating at 170 ° C. for 3 hours to obtain a solid product (I).

150 g of trichloromonobutoxytitanium and 100 g of solid product (I) were mixed in 200 ml of toluene, followed by adding 150 g of chain methyl hydrogen polysiloxane (300 centipoise of viscosity) and reacting at 100 ° C for 4 hours. Thereafter, it was washed in the same manner as in Example 1- (1) to obtain a solid product (II), hereinafter referred to as solid product (II) ₃ . The content of titanium atom is 0.24 mmol in 1 g of the solid product (II) ₃ .

(2) Multistage (LH) Continuous Polymerization of Ethylene

30 mg / hour of solid product (II) ₃ , 306 Nl / hour of ethylene containing 2% by volume of propylene, and hydrogen was supplied at 90 ° C. so that the molar ratio of ethylene (containing propylene) to hydrogen in the gaseous phase was 1 to 3.3. The first stage polymerization was carried out in the same manner as in Example 2 except that the polymerization was carried out by the polymerization system (L).

The following steps were carried out in the same manner as in Example 2, followed by 313 l of ethylene containing 1% by volume of propylene and 3% by volume of butene-1 per hour, and hydrogen having a molar ratio of ethylene (containing propylene and butene) to hydrogen in the gaseous phase. The second stage polymerization was carried out by the polymerization system (H) in the same manner as in Example 2 except that the mixture was supplied at 0.009 and carried out at 65 ° C.

Although the following multistage polymerization is performed continuously for 150 hours, operation is very stable, and 112 kg of polyethylene powder is obtained. The polymer yield is 24,900 kg-polymer / g- (II) Hr, 104,000 g-polymer / mmimolar-Ti.Hr.

28이다.This polyethylene has a melt index of 0.03, a volume ratio of 0.40, a density of 0.948 g / cm 2, a content of propylene and butenes in total of 1.8% by weight,

28.

When the film is produced using this polyethylene, the injection amount is 27 kg / Hr. The punching impact strength of the film is 165kg-cm / mm, 80% haze value, 8 fish eyes, and the surface condition is good, so it is very excellent film performance.

Example 4

The first stage polymerization was carried out in the same manner as in Example 2 except that 0.4 mmol of triisobutylaluminum instead of triethylaluminum and the molar ratio of ethylene to hydrogen in the gaseous phase portion of the first stage polymerizer were 1: 2.8. The second stage polymerization was carried out in the same manner, except that the molar ratio of ethylene (containing butene) to hydrogen in the gaseous phase portion of the two-stage polymerizer was 1: 0.03. The polymerization was carried out. 91 kg of polyethylene powder are obtained.

27이다.This polyethylene has a melt index of 0.04, a volume ratio of 0.93, a density of 0.949, butene content of 1.9% by weight,

27.

Using this polyethylene, when producing a film, the injection amount is 25 kg / Hr. The punching impact strength of the film is 160kg-cm / mm, haze value 79%, and six fisheyes. There is no problem in the film in actual use.

Example 5

(1) Preparation of Transition Metal Catalysts

75 g of magnesium oxide and 80 g of aluminum chloride (anhydrous) were mixed in a ball mill for 24 hours to obtain 127 kg of powder.

22이다.This polyethylene has a melt index of 0.30, a specific volume of 0.38, a density of 0.955,

22.

When the bottle is molded by blow molding, the resin pressure is low at the time of molding and high-speed molding is possible, so that the surface of the molded article is good, so that the weight and thin pieces of the molded article are satisfactory.

Comparative Example 8

이 6이다.The same melt index as in Example 5 was carried out in the same manner as in the first stage polymerization of Example 5 (2), except that the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer was set to 0.7. 89 kg of 0.30 polyethylene are obtained. But this polyethylene

This is 6.

It is possible to produce satisfactory bottles by blow molding.

Comparative Example 9

A transition metal catalyst component was obtained in the same manner as in Example (1) except that methyl ethyl polysiloxane was used. The titanium atom in 1 g of this catalyst component is 0.16 mmol. Except for using this catalyst component instead of solid product (II), it carried out multistage polymerization of ethylene similarly to (2) of Example 5, and obtained 2.5 kg of polyethylene.

10이다.This polyethylene

10.

When the bottle is molded by blow molding using this polyethylene, the surface of the molded article is not smooth due to the melt fracture and thin pieces are formed, which is not satisfactory as a bottle.

Example 6

30 mg of solid product (II) ₅ was supplied to a 10 l first stage polymerizer per hour, 0.4 mmol of triisobutylaluminum per hour, and 2 liters of hydrogen per hour to hexane, and the liquid level in the polymerizer was maintained at 80%. While discharging the contents of the polymerizer, the ethylene was supplied at 300 Nl per hour at 80 ° C, and hydrogen was supplied so that the molar ratio of ethylene to hydrogen in the gaseous phase of the polymerizer was 1 to 2.3 and the total pressure was continuously maintained at 30 kg / cm 2. The first stage polymerization was carried out by.

After completion of the first stage polymerization, the polymer suspended in the solvent was introduced into a 5 liter degassing vessel maintained at a pressure of 2 kg / cm 2, and the hydrogen and ethylene dissolved in hexane were separated. Ethylene to hydrogen in the gas phase is maintained at a predetermined ratio and recycled.

The total amount of the polymer slurry from the degassing tank was introduced into the second stage polymerizer having a volume of 10 L and the catalyst was not added. The liquid level in the polymerizer was maintained at 80% to discharge the contents of the polymerizer. It is supplied at a rate of 300 Nl per hour, and the second stage polymerization is carried out continuously in the polymerization system (H) at a total pressure of 20 kg / cm 2. The molar ratio of ethylene to hydrogen in the second stage polymerizer gas phase portion is maintained at 0.09. Hydrogen is supplied as needed.

Although the above multistage polymerization is performed continuously for 150 hours, the operation is very stable and 107 kg of polyethylene powder is obtained after drying without deliming. Polymer yield is 23,800 g-polymer / g- (II) .Hr, 103,3000 g-polymer / mmimolar-Ti.Hr.

25이다.The polyethylene had a melt index of 0.25, a volume specific gravity of 0.41, a density of 0.955 g / cm 3,

25.

In the case of manufacturing hollow bottles using polyethylene, the surface of the molded product is very good since there is no melt fracture during molding and no roughening phenomenon is observed, and the weight of one molded product is 280g and there are few thin pieces and sufficient performance for actual use. It is a bottle with.

Comparative Example 10

은 6이다.Except for setting the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer to 0.6 to 1, the polymerization was carried out in the same manner as in the first stage polymerization of Example 6, followed by one-stage polymerization for 150 hours, and 54 kg of polyethylene having the same melt index 0.25 as Example 6 was prepared. To obtain. But of this polyethylene

Is 6.

It is not possible to produce bottles by blow molding.

Comparative Example 11

In 200 ml of heptane, 100 g of solid product (I) obtained in Example 5- (1) and 100 g of chain methylethylpolysiloxane (same as Example 5) were added thereto, reacted at 80 ° C. for 3 hours with stirring, and then unreacted. 130 g of titanium tetrachloride was added without removing polysiloxane and reacted again at 80 ° C. for 3 hours. Thereafter, the final solid product was obtained in the same manner as in Example 5- (1). The content of titanium atom is 0.16 mmol in 1 g of the final solid product.

Example 6 The solid product (Ⅱ ₅₎ instead of on the final solid product was 90mg used, and in the same manner as in Example 6 except for supplying 0.8 mmol per 1 hour of triisobutylaluminum subjected to multi-stage (LH) Continuous polymerization of polyethylene 105kg of To obtain. The polymer yield is 7,800 g-polymer / g- (II) .Hr.

13이다.This polyethylene has a melt index of 0.28, a specific volume of 0.36,

13.

In the case of producing the hollow bottle, the surface of the molded product is dense, so that the denture is bad, and the weight of one molded product is 230g, and the thin pieces can be seen.

Example 7

(1) Preparation of Transition Metal Catalysts

80 g of manganese chloride (MnCl ₂ · 4H ₂ O) and 70 g of iron trichloride (anhydrous) were mixed and ground in a vibrating ball mill for 2 hours and then reacted at 120 ° C. for 6 hours to obtain a solid product (I). 100 mg of this solid product (I), 100 g of chained ethyl hydrogen polysiloxane (100 centistokes in viscosity), 100 g of vanadium tetrachloride and 200 ml of toluene were simultaneously mixed and reacted at 110 ° C. for 2 hours to give a solid product (II). (II) ₇ )] is obtained. Vanadium content is 0.15 mmol in 1 g of solid product (II) ₇ .

(2) Multistage (HL) Continuous Polymerization of Ethylene

Solid product (II) ₇ Except for supplying 306 Nl per hour of ethylene containing 47 mg per hour, 2% by weight of propylene, and supplying hydrogen at a molar ratio of ethylene (containing propylene) to hydrogen in the gaseous phase at a ratio of 1 to 2.4 at 85 ° C. In the same manner as in Example 6, the first stage polymerization was carried out by the polymerization system (L).

Hydrogen ethylene and propylene separated in the degassing tank are recycled to maintain the molar ratio of the gas phase of the first stage polymerizer at a predetermined ratio.

Ethylene containing 2% by volume of butene-1 is 306 Nl per hour and the molar ratio of ethylene (butene-containing) to hydrogen in the gaseous phase is maintained at 1 to 0.1, except that hydrogen is supplied and, if necessary, carried out at 75 ° C. In the same manner as in Example 6, the second stage polymerization is performed by the polymerization system (H).

The above multistage polymerization is continuously performed for 120 hours to obtain 90 kg of polyethylene powder. Polymer yield is 16000 g-polymer / g- (II) .Hr.

25이다.This polyethylene has a melt index of 0.23, a volume ratio of 0.37, a density of 0.954 g / cm 3, a total content of propylene and butene of 1.5% by weight,

25.

When the bottle is manufactured by blow molding, it does not cause melt fracture during molding and shows no dense phenomenon, so the surface of the molded product is very good, the weight of one molded product is sufficient to 265g, and the strength to withstand stress cracking is 180Hr. This is a bottle with enough performance for practical use.

Comparative Example 12

7이다.45 kg of polyethylene with a melt index of 0.27 was carried out in the same manner as in the first stage polymerization of Example 7, except that the molar ratio of ethylene (containing propylene) to hydrogen in the gas phase of the polymerizer was maintained at 0.1 to 1: 8. To obtain. But this polyethylene

7.

It is not possible to make bottles by blow molding.

Comparative Example 13

In 200 ml of toluene, 100 g of solid product (I) obtained as Example 7 and 100 g of ethyl hydrogen polysiloxane (same as Example 7) were added and reacted at 110 ° C. for 2 hours, whereby unreacted polysiloxane was not removed. In the state, 100 g of vanadium tetrachloride is added and reacted again at 110 ° C. for 2 hours. Thereafter, a solid product was obtained in the same manner as in Example 7. The content of vanadium atom is 0.12 mmol in 1 g of the final solid product.

In the same manner as in Example 7, except that 140 mg / h of the final solid product and 0.96 mmol / h of triisobutylaluminum were supplied per hour instead of the solid product (II) _{7 of} Example 7, the polymer powder 88 kg was obtained by multistage continuous polymerization. To obtain. Polymer yield is 520 g-polymer / g- (II) .Hr.

13이다.This polyethylene has a melt index of 0.03, a specific volume of 0.34,

13.

Blow molding is performed, that is, the surface of the molded product is dense, so the appearance is bad, and the weight of one molded article is insufficient at 225 g, and thin pieces appear.

Example 8

(1) Preparation of Transition Metal Catalysts

110 g of 3MgO.MgCl ₂ · 4H ₂ O and 100 g of aluminum chloride (anhydrous) were reacted for 40 hours while heating to 100 ° C. in a rotary ball mill to obtain a solid product (I).

In 200 ml of xylene, 150 g of octaethylcyclo tetrasiloxane [Si (C ₂ H ₅ ) ₂ O] ₄ (viscosity 10 centy Stokes) and 120 g of oxy trichloride were added and mixed, and 100 g of solid product (I) was added thereto and 120 2 hours at ℃ to thereby obtain a solid product (ⅱ) [hereinafter referred to this solid product (ⅱ) _8]. The vanadium content is 0.18 mmol in 1 g of the solid product (II) ₈ .

(2) Multistage (HL) Continuous Polymerization of Ethylene

In a 10 liter first stage polymerizer, 40 mg of solid product (II) ₈ was fed per hour, 0.35 mmol of triisobutylaluminum per hour, and 2.5 liters per hour of hexane, and the liquid level in the polymerizer was 80%. 315Nl of ethylene containing 5% by volume of butene-1 at 70 ° C for 1 hour and hydrogen were supplied so that the molar ratio of ethylene (containing butene) to hydrogen in the gaseous phase of the polymerizer was set to 0.008 for 1 hour at 70 ° C. Then, the first stage polymerization is carried out continuously by the polymerization system (H) at a total pressure of 30 kg / cm 2.

Subsequently, a total amount of the polymer suspended in the solvent exiting the first stage polymerizer was introduced into the second stage polymerizer having a volume of 20 L using a transfer pump, and the ethylene at 80 ° C. was discharged to discharge the contents of the polymerizer such that the liquid level in the polymer was 80%. 300 Nl per hour, fresh triisobutylaluminum 0.1 mmol per hour, and hydrogen supplied so that the molar ratio of ethylene (containing butenes introduced by the first stage polymerizer) to hydrogen in the gas phase of the polymerizer was 1 to 3.7 and the voltage was 40 kg. The second stage polymerization is carried out continuously by the polymerization system L at / cm 2.

Although the above multistage (HL) polymerization was continuously performed for 120 hours, the operation was very stable, and 90 kg of polyethylene powder was obtained after drying without deliming. Polymer yield is 18,800 g-polymer / g- (II) .Hr, 104,000 g-polymer / mmimolar-V.Hr.

29이다.This polyethylene had a melt index of 0.05, a specific volume of 0.39, a density of 0.949 g / cm 3,

29.

When the film was produced using this polyethylene, the injection amount was 26.5 kg / Hr. The film has a punch impact strength of 175kg-cm / mm, 80% haze, and five fisheyes, which are sufficient for practical use.

Comparative Example 14

In Example 8, 495Nl of ethylene containing 3% by volume of butene 1 was supplied per hour, and hydrogen was supplied such that ethylene (containing butene) to hydrogen in the gaseous phase became 0.02 for 1, and the first stage polymerization was carried out at a total pressure of 40 kg / cm 2. Multi-stage of ethylene in the same manner as in Example 8 except that 120Nl of ethylene per hour and hydrogen were supplied at a molar ratio of ethylene (containing butene) to hydrogen in the gaseous phase to 4.2 per second and subjected to second stage polymerization at a high pressure of 25 kg / cm 2. Continuous polymerization is carried out to obtain 91 kg of polyethylene.

14이다.This polyethylene is melt index 0.04,

14.

The film was produced using this polyethylene, which means that the injection amount is 12 kg / Hr. The film has a punch impact strength of 80kg-cm / mm and 700 fisheyes, which are not practical films.

Example 9

The solid product (II) ₁ 35 mg (0.007 mmol in terms of titanium atoms) per hour, triethylaluminum 0.35 mmol per hour and hexane at 4 L per hour were fed to a 10 liter first stage polymerizer, and While maintaining the liquid level at 80%, the content of the polymerizer was discharged while supplying 350Nl of ethylene per hour and hydrogen at 70 ° C so that the molar ratio of ethylene to the water tank in the gaseous phase of the polymerizer was 0.05 to 1, and at a total pressure of 40kg / ㎠ The first stage polymerization is carried out continuously by the polymerization system (H).

A total amount of the suspension suspended in the solvent from the first stage polymerizer was introduced into the second stage polymerizer having a total volume of 20 liters by using a transfer pump, and the liquid level in the medium pressure reactor was 80% without adding hexane and a catalyst. 370 Nl per hour containing ethylene containing 5% by volume of butene-1 at 80 ° C and hydrogen were supplied so that the molar ratio of ethylene to hydrogen in the gaseous phase of the polymerizer was 1 to 1.6. The second stage polymerization is carried out by L).

The above continuous multi-stage (HL) polymerization was performed continuously for 120 hours, and thus, 105 kg of polyethylene powder was obtained after drying without deliming because the operation was very stable.

25이다.This polyethylene has a melt index of 0.05, a specific volume of 0.40, a density of 0.950,

25.

The film was produced using this polyethylene, that is, the film forming property is stable, and since the film has moderate strength and opacity and the fish eye cannot be seen, the surface state is good and satisfactory.

Comparative Example 15

이 6이다.Except for setting the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer to 0.15 to 1, the same process as in the first stage polymerization of Example 9 was carried out for 120 hours continuously, and 51 kg of polyethylene with a melt index of 0.05 was carried out in the same manner as in Example 9. To obtain. But this polyethylene

This is 6.

This polyethylene cannot be produced satisfactorily.

[Comparative Example 16]

A transition metal catalyst component was obtained in the same manner as in (1) of Example 1 except that no dimethylpolysiloxane was used. Titanium is 0.15 mol in 1 kg of the catalyst components. The catalyst component was used in place of the solid product (II) ₁ and the others were subjected to multistage continuous polymerization of ethylene in the same manner as in Example 9 to obtain 20 kg of polyethylene.

이 10이다. 이 폴리에틸렌을 사용하여 필름을 제조한즉, 필름에 휘쉬아이가 있어서 제막성이 안정하지 않으므로 강도가 부족하여 필름으로서는 만족하지 못하다.This polyethylene

This is 10. When the film was produced using this polyethylene, the film had a whiskey and thus the film forming property was not stable. Therefore, the film was insufficient and therefore not satisfactory as the film.

Example 10

30 mg of solid product (II) ₅ per hour was fed to the first stage polymerizer, 210 N1 per hour of ethylene, hydrogen was supplied so that the molar ratio of ethylene to hydrogen in the gaseous phase of the polymerizer was 1 to 0.1 and ethylene was fed to the second stage polymerizer per hour. Except for supplying 495 Nl and hydrogen so that the molar ratio of ethylene to hydrogen in the gaseous phase of the polymerizer was 1.3 to 1.3, 130 kg of polyethylene powder was subjected to continuous polymerization of ethylene in the same manner as in Example 9 for 150 hours of continuous operation. To obtain.

22이다.This polyethylene has a melt index of 0.30, a specific volume of 0.38, a density of 0.955,

22.

The bottles were molded by blow molding, that is, the resin pressure was low at the time of molding, high speed molding was possible, the surface of the molded article was good, and the weight of the molded article and the shape of the thin pieces were satisfactory.

[Comparative Example 17]

Except for setting the molar ratio of ethylene to hydrogen in the gaseous phase of the polymerizer to 0.8, the same procedure as in the first stage polymerization of Example 10 was carried out and the first stage polymerization was performed continuously for 150 hours to obtain 40 kg of polyethylene having the same melt index 0.30 as in Example 10. To obtain. However, this polyethylene is not possible to make bottles.

[Comparative Example 18]

Except for using methyl ethyl polysiloxane, the transition metal catalyst component similar to (1) of Example 5 is obtained. The titanium atom in 1 g of the catalyst component is 0.16 mmol. Except for replacing the catalyst component with solid product (II) ₅ , in the same manner as in Example 10, ethylene was subjected to multistage continuous polymerization to give 25 kg of polyethylene.

10이다.This polyethylene

10.

Blow molding using this polyethylene, i.e., the surface of the molded article is not smooth due to the melt fracture, and thin pieces are formed, which is not satisfactory as a bottle.

Example 11

(1) Preparation of Transition Metal Catalysts

65 g of hydromagnesite ( ₃ MgCO ₃ · Mg (OH) ₂ · 3H ₂ O) and 70 g of iron trichloride (anhydrous) were mixed and ground for 10 hours in a vibrating mill and reacted at 300 ° C. for 1 hour to obtain a solid product (I).

In 150 ml of 0-dichlorobenzene, 200 g of chain di-n-butyl polysiloxane (viscosity 1,000 centistokes) and 100 g of solid product (I) were added and mixed, 200 g of titanium tetrachloride was added thereto, and reacted at 160 ° C. for 3 hours. Solid product (II) (hereinafter referred to as solid product (II) ₁₁ ) is obtained.

Titanium content is 0.20 mmol in 1 g of solid products (II) ₁₁ .

(2) Multistage (HL) Continuous Polymerization of Ethylene

35 mg of solid product (II) ₁₁ per hour, 0.35 mmol of triethyl aluminum per hour instead of triisobutylaluminum, 2 L per hour of hexane, 310 Nl per hour of ethylene containing 3% by volume of butene-1, hydrogen gaseous phase The first stage polymerization was carried out in the same manner as in Example 8 except that the molar ratio of negative ethylene (containing butene) to hydrogen was set to 0.05 to 1, and the total pressure was 20 kg / cm 2.

Subsequently, 300 N1 per hour of ethylene and hydrogen were supplied so that the molar ratio of ethylene (containing butenes introduced by the single-stage polymerizer) to hydrogen in the gaseous phase became 1 to 3.0 without adding new triethyl aluminum at 85 ° C. The second stage polymerization was carried out by the polymerization system (L) in the same manner as in Example 8 except that the ratio was 35 kg / cm 2.

Although the above multistage (HL) polymerization is performed continuously for 150 hours, operation is very stable and 111 kg of polyethylene powder is obtained after drying without demineralization. Polymer yield is 21,000 g-polymer / g- (II) .Hr, 106,000 g-polymer / mmimolar-Ti.Hr.

26이다.This polyethylene has a melt index of 0.30, a volume specific ratio of 0.38, a density of 0.956 g / cm 3, butene content of 1.2 wt%,

26.

The bottle is manufactured by blow molding using this polyethylene, which does not cause melt fracture during molding and no roughness is observed. The surface of the molded article is very good, and the weight of one molded article is 275g, and there are few thin pieces. The stress cracking property (F ₅₀ inch) is 170Hr, which is a problem-free bottle with practical performance.

Comparative Example 19

In Example 11, 70Nl of ethylene containing 10% by volume of butene-1 was supplied per hour, and hydrogen was supplied such that ethylene (containing butene) to hydrogen in the gaseous phase became one 0.002, and the first stage was provided at a total pressure of 10 kg / cm 2. In the same manner as in Example 11, the synthesis was carried out, ethylene was supplied at 540 Nl per hour, hydrogen was supplied so that the molar ratio of ethylene (containing butene) to hydrogen in the gaseous phase was 1 to 1.7, and the second stage polymerization was carried out at a voltage of 40 kg / cm 2. To multistage continuous polymerization of ethylene to give 109 g of polyethylene.

12이다.This polyethylene is melt index 0.35,

12.

The bottle was prepared by blow molding using polyethylene, that is, the melt fracture occurred during molding, so that the surface of the molded product was poor and the weight of one molded product was 210 g. Difficult to do

Example 12

30 mg / hour of solid product (II) ₅ , 200 Nl / hour of ethylene, and hydrogen were supplied so that the molar ratio of ethylene to hydrogen in the gaseous phase was 1 to 0.07. At 65 ° C., the first stage polymerization was carried out at a total pressure of 15 kg / cm 2 and ethylene 200Nl per hour and hydrogen were supplied in the same manner as in Example 11 except that hydrogen was supplied so that the mole ratio of ethylene to hydrogen in the gaseous phase became 1 to 2.5, and the second stage polymerization was carried out at 90 ° C at a total pressure of 25 kg / cm 2. Multi-stage (HR) continuous polymerization yields 72 kg of polyethylene.

24이다.This polyethylene has a melt index of 0.25, a volume specific gravity of 0.40, a density of 0.954,

24.

Since the bottle was manufactured by blow molding, that is, there was no problem in appearance and almost no thin pieces were seen, the weight of one molded article was 260 g, which is sufficient for practical use.

Claims (1)

In the method for producing polyethylene by continuous multistage polymerization using a plurality of polymerizers in the presence of a solvent and hydrogen using a Ziegler type catalyst, hydroxides, oxides, carbonates, and the like of trivalent metal halides and divalent metals are contained. Solid product obtained by reacting a double salt or a hydrate of a divalent metal compound, and a solid product carrying a transition metal compound prepared from a polysiloxane and a transition metal compound of Group 4a or 5a. A method for producing polyethylene by continuous multistage polymerization formed by combining the polymerization systems of a) and b) shown below in the presence of a catalyst obtained by combining II) and an organoaluminum compound. a) The molar ratio of ethylene to hydrogen in the gas phase of the polymerizer in a saturated hydrocarbon solvent in the presence of a gas phase on the top of the polymerizer, under conditions of a polymerization temperature of 50 ° C. or higher and less than 120 ° C., and a polymerization pressure of 5 to 70 kg / cm 2. Polymerization system (L) which supplies 30-80% of ethylene of the total ethylene supply amount simultaneously supplying hydrogen so that is more than 0.5 to 6.0 or less b) The molar ratio of ethylene to hydrogen in the gas phase of the polymerizer is one to 0.001 under conditions of a polymerization temperature of 30 ° C. or more and 100 ° C. or less and a polymerization pressure of 5 to 70 kg / cm 2 in a state where a gas phase is present in the upper part of the polymerizer. The polymerization system (H) which supplies hydrogen so that it may be 0.5 or more, and supplies ethylene of 20 to 70% of the total ethylene content.