JPS6248682B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a process for producing ethylene-based polymers, which comprises polymerizing ethylene or the like in the presence of a novel catalyst system. It is already known to use catalyst systems consisting of transition metal compounds and organometallic compounds for the low-pressure polymerization of olefins. In addition, as a highly active catalyst,
Catalyst systems containing as one component a reaction product of an inorganic or organic magnesium compound and a transition metal compound are also known. However, in order to obtain higher productivity, it is industrially extremely important to not only have high activity but also to improve the particle size, bulk density, etc. of the polymer particles. At the same time, in response to the diversification of quality,
Currently, it is also required to arbitrarily control the molecular weight distribution of the produced polymer. The present inventors previously disclosed in Japanese Patent Publication No. 52-39714 a reaction product of magnesium metal, an organic hydroxide compound, an organic oxygenated transition metal compound, a halogen-containing transition metal compound, and an aluminum halide, and an organometallic compound. By using a catalyst system consisting of In this respect, it was still insufficient. However, when carrying out polymerizations, a serious problem that usually occurs is reactor fouling (solid polymer deposits on the internal surfaces of the reactor), and the polymerization operation is often stopped and the fouling removed. It was necessary to do so. This is particularly common when producing resins with a wide molecular weight distribution, such as hollow and extrusion brands. In order to solve these problems, for example, methods of adding surfactants etc. to the polymerization system (such as Japanese Patent Application Laid-open No. 105788/1988) or adding substances that are inert and have a mechanical abrasive effect to the polymerization system have been proposed. A method has been proposed (Japanese Unexamined Patent Publication No. 49-8572). However, with these methods, it is not possible to obtain resin of good quality because foreign matter is mixed into the product. Therefore, the present inventors proposed the above-mentioned Japanese Patent Publication No. 52-39714.
In this issue, the aim is to significantly improve the particle properties of the polymer and reduce its adhesion to the polymerization vessel without sacrificing the characteristics of being able to produce a polymer with high activity and a wide molecular weight distribution. year,
As a result of continued intensive studies, the present invention has been completed. That is, the present invention provides ethylene production which involves polymerizing ethylene or a mixture of ethylene and at least one compound selected from the group consisting of α-olefins and dienes in the presence of a catalyst comprising a transition metal compound and an organometallic compound. In the method for producing a based polymer, the catalyst is a transition metal solid catalyst component (A) obtained by reacting the following compounds (i) to (v), (i) from an oxygen-containing organic compound of magnesium and a halogen-containing compound; at least one selected magnesium compound and/or metallic magnesium and a hydroxide organic compound; (ii) at least one titanium compound selected from oxygen-containing organic compounds of titanium and halogen-containing compounds; (iii) oxygen-containing organic compounds of zirconium. (iv) at least one silicon compound selected from polysiloxanes and silanes; (v) at least one halogenated organoaluminum compound; and at least The present invention relates to a method for producing an ethylene polymer, characterized in that a catalyst system comprising an organometallic catalyst component (B) comprising one type of organoaluminum compound is used. The first feature of the present invention is that particle properties are significantly improved. That is, the fine particle content of the polymer can be reduced, the average particle size of the polymer can be increased, and the bulk density of the polymer can be increased. This has extremely great industrial significance, as will be described later. That is, in the polymerization process, the formation of deposits in the polymerization equipment is prevented and the bulk density is high, so especially in the case of slurry polymerization, the slurry concentration can be increased and production efficiency is improved. It is also possible to do so. Furthermore, in the polymer separation and drying process,
The polymer slurry is easily separated and filtered, fine particles of the polymer are prevented from scattering out of the system, and fluidity is improved, thereby improving drying efficiency. Furthermore, during the transfer process, there is no occurrence of bridging within the silo, which eliminates transfer problems. The second feature of the present invention is that it is possible to widen the molecular weight distribution, thereby making it possible to obtain a polymer suitable for hollow molding and film molding, and also to improve the surface properties of molded products. Become. The third feature of the present invention is that the catalyst activity is high;
That is, the weight of the polymer obtained per unit transition metal is very large. Therefore, there is no need to take special measures to remove catalyst residue from the polymer, and problems such as deterioration and coloring during molding of the polymer can be avoided. The metal magnesium and the hydroxide organic compound, the oxygen-containing organic compound of magnesium, and the halogen-containing compound mentioned above (i) used in the preparation of the transition metal solid catalyst component (A) of the catalyst system of the present invention include the following. . First, when using magnesium metal and an organic hydroxide compound, the magnesium metal can be in various forms, such as powder, particles, foil, or ribbon, and the organic compound hydroxide can be in any form. , alcohols, organic silanols, and phenols are suitable. As alcohols, linear or branched aliphatic alcohols, cycloaliphatic alcohols or aromatic alcohols having 1 to 18 carbon atoms can be used. Examples include _CH3OH , _{C2H5OH ,} n-
_C8H17OH , i- _C8H17OH , _{n - C18H37OH ,}

[Formula] Examples include HOCH ₂ CH ₂ OH. Furthermore, as the organic silanol, at least 1
hydroxyl groups, and the organic group is 1 to 12
carbon atoms, preferably 1 to 6 carbon atoms. selected from alkyl groups, cycloalkyl groups, arylalkyl groups, aryl groups, alkylaryl groups, and aromatic groups. For example, the following example can be given:
( _CH3 ) _3SiOH , ( _C2H5 ) _{3SiOH ,} ( _C6H5 ) _{3SiOH ,}
(t- _{C4H9 )} ( _CH3 ) _2SiOH . Furthermore, examples of phenols include phenol, cresol, xylenol, and hydroquinone. In addition, when using metallic magnesium to obtain the solid catalyst component (A) described in the present invention, for the purpose of promoting the reaction, it may be necessary to react with metallic magnesium,
It is preferable to add one or more kinds of polar substances such as iodine, mercuric chloride, alkyl halides, organic acid esters, and organic acids that generate addition compounds. Compounds belonging to oxygen-containing organic compounds include:
Magnesium alkoxides such as methylate, ethylate, isopropylate, decanolate and cyclohexanolate, magnesium alkyl alkoxides such as ethyl ethylate, magnesium hydroalkoxides such as hydroxymethylate, magnesium phenoxides such as phenate, naphthenate, phenanthrenates and cresolates, magnesium carboxylates (optionally hydrated) such as acetate, stearate, benzoate,
phenyl acetate, adipate, sebacate,
phthalates, acrylates and oleates, oxygen-containing organomagnesium compounds further containing nitrogen, i.e. compounds with magnesium-oxygen-nitrogen-organic group bonds in this order, such as oximates, especially butyl oximate, dimethyl glyoximate and Cyclohexyloximate, hydroxamates, hydroxylamine salts, especially N-nitroso-N-phenyl-
Hydroxylamine derivatives, magnesium chelates, i.e., magnesium having at least one normal magnesium-oxygen-organic group bond in this order and further having at least one ligand bond, forming a magnesium-containing heterocycle. Oxygen-containing organic compounds, such as enolates, especially acetylacetonates, such as complexes obtained from phenol derivatives with an electron-donating group in the position ortho or meta to the hydroxyl group, especially 8-hydroxyquinolinates, and also magnesium silanolates. That is, examples include compounds containing magnesium-oxygen-silicon-hydrocarbon group bonds in this order, such as triphenylsilanolate. Of course, this series of oxygen-containing organic compounds also includes compounds containing several different organic groups, such as magnesium methoxyethylate, complex alkoxides of magnesium with other metals, and phenoxides, such as Mg [Al
(OC ₂ H ₅ ) ₄ ] ₂ and Mg ₃ [Al(OC ₂ H ₅ ) ₆ ] ₂ are also included. These oxygen-containing organomagnesium compounds may be used alone or as a mixture of two or more. Examples of halogen-containing magnesium compounds include anhydrous or hydrated magnesium dihalides,
For example, MgCl ₂ , MgCl ₂ .6H ₂ O, MgCl ₂ .4H ₂ O and MgCl ₂ .2H ₂ O, which in addition to the magnesium-halogen bond contain inorganic groups, such as hydroxy groups, bonded to magnesium via oxygen. compounds such as Mg(OH)Cl and Mg(OH)Br, magnesium halides (preferably chloride)
A hydrolysis product containing a magnesium-halogen bond, a mixed composition containing a halogen-containing compound of magnesium and an oxygen-containing compound [Typical examples of these compositions include basic magnesium halides (preferably (chlorides), for example, MgCl ₂・MgO・H ₂ O, MgCl ₂・3MgO・
7H ₂ O and MgBr ₂ , 3MgO, 6H ₂ O, etc.]
can be given. These halogen-containing magnesium compounds may be used alone or as a mixture of two or more. Examples of the oxygen-containing organic compound and halogen-containing compound of titanium (ii) include the following. As an oxygen-containing organic compound, the general formula [TiO _a
A compound represented by (OR') _b ] _n is used. However, in the general formula, R' is the number of carbon atoms, 1 to 20,
Preferably, it represents a hydrocarbon group such as 1 to 10 linear or branched alkyl groups, cycloalkyl groups, arylalkyl groups, aryl groups, and alkylaryl groups. a and b are numbers such that a≧0 and b>0 and are compatible with the valence of Ti, and m is an integer. Above all, a is 0≦a≦1 and m is 1≦m≦
It is desirable to use oxygen-containing organic compounds such as 6. Specific examples include Ti(OC ₂ H ₅ ) ₄ and Ti(O-
n- _{C3H7 ) 4} , Ti(O-i- _{C3H7 ) 4} , Ti(O-n
-C ₄ H ₉ ) ₄ , Ti ₂ O(Oi-C ₃ H ₇ ) ₆ and the like. The use of oxygen-containing organic compounds containing several different hydrocarbon groups is also within the scope of the invention. These oxygen-containing organic compounds of titanium may be used alone or as a mixture of two or more. In addition, as a halogen-containing compound of titanium,
Halides, such as TiCl ₄ , TiBr ₄ , Til ₄ , complex halides of titanium and alkali metals, such as
_K2TiCl6 and _Na2TiCl6 , oxyhalides such _{as TiOCl2} , and halogenoalkoxides _,
For example, Ti(OC ₂ H ₅ ) ₂ Cl ₂ , Ti(OC ₂ H ₅ ) ₃ Cl, Ti
(OC ₂ H ₅ )Cl ₃ , Ti(O-i-C ₃ H ₇ )Cl ₃ , Ti(O
-i-C ₄ H ₉ ) Cl ₃ , Ti (O-i-C ₃ H ₇ ) ₃ Cl, Ti
(O-i _{- C4H9} ) _{2Cl2 is} mentioned. Also within the scope of this invention are halogen-containing organic compounds of titanium containing several different organic groups. These compounds may be used alone or as a mixture. Examples of the zirconium oxygen-containing organic compound and halogen-containing compound in (iii) above include the following. As an oxygen-containing organic compound of zirconium,
A compound represented by the general formula [ZrOc(OR ² ) d]n is used. However, in the general formula, R ²
represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10, such as a straight or branched alkyl group, cycloalkyl group, arylalkyl group, aryl group, alkylaryl group, and c and d are c ≧0 and d
>0, which is compatible with the valence of zirconium, and n is an integer. Above all, c is 0≦
It is desirable to use an oxygen-containing organic compound in which c≦1 and n is 1≦n≦6. Specific examples include Zr(O-n- _C4H9 ) ₄ , _Zr
(OC ₆ H ₅ ) ₄ , Zr (OCH ₃ ) [OC (CH ₃ ) ₃ ] ₃ , Zr
[OZr(OC ₂ H ₅ ) ₃ ] ₄ , etc. Also within the scope of this invention is the use of oxygen-containing organic compounds containing several different hydrocarbon groups. These oxygen-containing organic compounds of zirconium may be used alone or as a mixture of two or more. In addition, halogen-containing compounds of zirconium include halides such as ZrCl ₄ , ZrF ₄ , oxyhalides such as ZrOF ₂ , ZrOCl ₂ , and
Halogenoalkoxides, such as Zr(O-n-
C ₄ H ₉ ) Cl ₃ , Zr (O-n-C ₄ H ₉ ) ₂ Cl ₂ , Zr
(OC ₂ H ₄ ) ₃ Cl, Zr (O-i-C ₃ H ₇ ) Cl ₃ , Zr (O
-n- _C3H7 ) _{Cl3 ,} etc. Also within the scope of this invention are zirconium halogen-containing compounds containing several different organic groups. These may be used alone or as a mixture of two or more. As the silicon compound (iv), the following polysiloxanes and silanes are used. As polysiloxane, general formula

[Formula] (In the formula, R ³ and R ⁴ are hydrocarbon groups such as alkyl groups having 1 to 12 carbon atoms, aryl groups, hydrogen, halogen, alkoxy groups having 1 to 12 carbon atoms, allyloxy groups, fatty acid residues, etc. represents an atom or residue that can be bonded to silicon, R ³ and R ⁴ may be the same or different, p usually represents an integer from 2 to 10,000)
One or more types of repeating units represented by
Siloxane polymers with chain, cyclic, or three-dimensional structures that have various ratios and distributions in the molecule (however,
except when all R ³ and R ⁴ are hydrogen or halogen). Specifically, the chain polysiloxane includes, for example, hexamethyldisiloxane, octamethyltrisiloxane, dimethylpolysiloxane, diethylpolysiloxane, methylethylpolysiloxane, methylhydropolysiloxane, ethylhydropolysiloxane, and butylhydropolysiloxane. ,
Hexaphenyldisiloxane, octaphenyltrisiloxane, diphenylpolysiloxane, phenylhydropolysiloxane, methylphenylpolysiloxane, 1,5-dichlorohexamethyltrisiloxane, 1,7-dichlorooctamethyltetrasiloxane , dimethoxypolysiloxane, diethoxypolysiloxane, diphenoxypolysiloxane, etc. Examples of the cyclic polysiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, Examples include triphenyltrimethylcyclotrisiloxane, tetraphenyltetramethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, and octaphenylcyclotetrasiloxane. Examples of polysiloxanes having a three-dimensional structure include those obtained by heating the above-mentioned chain or cyclic polysiloxanes to have a crosslinked structure. These polysiloxanes are preferably in a liquid state for handling purposes, and have a viscosity of 1 to 1 at 25°C.
A range of 10,000 centistokes, preferably 1 to 1,000 centistokes is desirable. However, it does not have to be limited to a liquid form, and a solid substance generally referred to as silicone grease may also be used. Silanes have the general formula HqSi _r R ⁵ _s X _t (where R ⁵
represents a hydrocarbon group such as an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group having 1 to 12 carbon atoms, an allyloxy group, a fatty acid residue, etc., which can be bonded to silicon, and each R ⁵ is different from each other. or may be of the same type, X represents a different or the same type of halogen, q, s and t are integers of 0 or more, r is a natural number, and q+s+t=2r+2. It will be done. Specifically, for example, silahydrocarbons such as trimethylphenylsilane and allyltrimethylsilane, linear and cyclic organic silanes such as hexamethyldisilane and octaphenylcyclotetrasilane, methylsilane, dimethylsilane, trimethylsilane, etc. Organosilane, silicon halides such as silicon tetrachloride and silicon tetrabromide, alkyl and aryl such as dimethyl dichlorosilane, ethyl dichlorosilane, n-butyltrichlorosilane, diphenyldichlorosilane, triethylfluorosilane, and dimethyldibromosilane Alkoxysilanes such as halogenosilane, trimethylmethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, triphenylethoxysilane, tetramethyldiethoxydisilane, dimethyltetraethoxydisilane, dichlorodiethoxysilane, dichlorodiphenylsilane, tribromoethoxy Halo-alkoxy and phenoxysilanes such as silanes, trimethyl-acetoxysilane, diethyl-diacetoxysilane,
Silane compounds containing fatty acid residues such as ethyltriacetoxysilane, etc. The above silicon compounds may be used alone, or two or more types may be mixed or reacted together. As the halogenated organic aluminum compound (v), those represented by the general formula R ⁶ _z AlX _3-z are used. However, in the general formula, R ⁶ is a hydrocarbon group containing 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and X represents halogen and is F, Cl, Br, or I. z is a number satisfying 0<z<3. Preferably R ⁶ is selected from straight chain or branched alkyl, cycloalkyl, arylalkyl, aryl, alkylaryl groups. The above halogenated organoaluminum compounds can be used alone or as a mixture of two or more. Furthermore, trialkyl aluminum having the general formula AlR ⁶ ₃ can also be used in combination. Specific examples of halogenated organoaluminum compounds include Al(C ₂ H ₅ )Cl ₂ , Al
( _C2H5 ) _{2Cl ,} Al ₍ i- _C4H9 ) _Cl2 , etc. As mentioned above, for example, AlCl ₃ + 1/2Al
It goes without saying that a trialkylaluminium, such as (C ₂ H ₅ ) ₃ , can be used in combination, and a reaction product obtained by reacting the two in advance can also be used. The transition metal solid catalyst component (A) of the present invention can be produced by reacting the above-mentioned reactants (i), (ii), (iii), (iv) and (v). These reactions are preferably carried out in a liquid medium. This can therefore be carried out in the presence of an inert organic solvent, especially if these reactants themselves are not liquid under the operating conditions or if the amount of liquid reactants is insufficient. As the inert organic solvent, all those commonly used in the technical field can be used, but aliphatic,
Alicyclic or aromatic hydrocarbons, halogen derivatives thereof, or mixtures thereof,
For example, isobutane, hexane, heptane, cyclohexane, benzene, toluene, xylene, monochlorobenzene, etc. are preferably used. The reaction order of components (i) to (v) of the catalyst component (A) of the present invention is as follows, as long as the addition of the reactant causes a chemical reaction.
Can be in any order. Typical methods include, for example, adding a silicon compound, a zirconium compound, and an aluminum compound sequentially to a mixture of a magnesium compound and a titanium compound, or adding an aluminum compound to a mixture of a magnesium compound, a titanium compound, a zirconium compound, and a silicon compound mixed and reacted at the same time. Examples include a method in which a silicon compound, an aluminum compound, and a titanium compound are sequentially added to a mixture of a magnesium compound and a zirconium compound, but the method is not limited to these methods. The amount of each reactant used in the present invention is not particularly limited, but the atomic ratio of magnesium to titanium is 1:0.01 to 1:20, preferably 1:0.1 to 1:
5. The atomic ratio of magnesium and zirconium is 1:
0.01 to 1:20, preferably 1:0.05 to 1:5, and the atomic ratio of magnesium to silicon is 1:0.01 to 1:
20, preferably select the amount of the reactant to be used so that the atomic ratio of magnesium to aluminum is in the range of 1:0.05 to 1:5, 1:0.1 to 1:100, preferably 1:1 to 1:20. is preferred. However, when polysiloxane is used as the silicon compound, the atomic ratio of silicon to magnesium should be understood to indicate the ratio of the repeating unit represented by the general formula to magnesium (mol to gram atom). The reaction conditions are not particularly critical, but -50°~
at a temperature of 300°C, preferably from 0 to 200°C,
The reaction is carried out for 0.5 to 50 hours, preferably 1 to 6 hours, in an inert gas atmosphere under normal pressure or increased pressure. The thus obtained catalyst component (A) is a particle that is insoluble in the solvent used as a diluent, and may be used as is, but it is generally prepared by a filtration or decantation method.
After removing remaining unreacted substances and byproducts,
After washing several times with an inert solvent, it is suspended in an inert solvent and used. It can also be used which is isolated after washing and heated under normal pressure or reduced pressure to remove the solvent. In the present invention, an organoaluminum compound is used as the organometallic catalyst component (B). As the organic group of the organoaluminum compound of component (B), an alkyl group can be exemplified. As this alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms is used. Specifically, as the organoaluminum compound of the catalyst component (B), for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n
- Examples include decyl aluminum. Particularly preferred is the use of trialkylaluminum having a straight or branched alkyl group having 1 to 10 carbon atoms. In addition to the above, an alkyl aluminum hydride having an alkyl group having 1 to 20 carbon atoms can be used as component (B). A specific example of such a compound is diisobutylaluminum hydride. Also, the number of carbon atoms is 1~
Alkylaluminum halides having 20 alkyl groups, such as ethylaluminum sesquichloride, diethylaluminum chloride or diisobutylaluminum chloride, can also be used. Note that an organoaluminum compound obtained by the reaction of a trialkylaluminum or dialkylaluminium hydride having an alkyl group having 1 to 20 carbon atoms and a diolefin having 4 to 20 carbon atoms, such as a compound such as isoprenyl aluminum, is used. You can also do that. The polymerization of ethylene and the like according to the present invention can be carried out under general reaction conditions of the so-called Ziegler method. In other words, continuous or batch type, 20°~
Polymerization is carried out at a temperature in the range of 200°C, especially in the form of a slurry, at a temperature of 50° to 90°C. The polymerization pressure is not particularly limited, but it is suitable to use a pressure of 1.5 to 50 atm. The polymerization is preferably carried out in the presence of an inert solvent. Any commonly used inert solvent can be used. Particularly suitable are alkanes or cycloalkanes having 4 to 20 carbon atoms, such as isobutane, pentane, hexane, cyclohexane and the like. In carrying out the present invention, the catalyst component (A) is preferably used in an amount corresponding to 0.001 to 2.5 mmol of transition metal atoms per solvent or per reactor, and may be used at a higher concentration depending on the conditions. You can also do that. The organoaluminum compound of catalyst component (B) is solvent 1
The concentration used is from 0.02 to 50 mmol, preferably from 0.2 to 5 mmol per reactor. The monomer used as a raw material in the method for producing an ethylene polymer of the present invention is ethylene or a mixture of ethylene and at least one compound selected from the group consisting of α-olefins and dienes. Here, α-olefin has the general formula R-
CH=CH ₂ (wherein R is a linear or branched, substituted or unsubstituted alkyl group having 1 to 10, in particular 1 to 8 carbon atoms), such as propylene , 1-butene, 1-pentene, 4-methyl-1-pentene, 1-octane, and the like. Furthermore, examples of the dienes include butadiene, isoprene, and the like. The amount of the α-olefin and diene to be polymerized is suitably a relatively small amount that is normally known and can modify the properties of polyethylene. The ethylene polymers obtained by the production method of the present invention include polyethylene, ethylene-α-olefin copolymers, ethylene-dienes copolymers, and ethylene-olefin-dienes copolymers. In the present invention, the molecular weight of the polymer can be adjusted by known means, such as by allowing an appropriate amount of hydrogen to be present in the reaction system. The present invention will be illustrated below using Examples, but the present invention is not limited to these Examples in any way. In addition, in the examples and comparative examples, HLMI/
MI is High Load Melt Index (HLMI,
It is the ratio of the melt index (MI, according to ASTM D-1238 Condition E) to the melt index (MI, according to ASTM D-1238 Condition F) and is a measure of molecular weight distribution. HLMI／
It is considered that the larger the MI value, the broader the molecular weight distribution. The activity is expressed as the amount (g) produced per 1 g of the sum of titanium and zirconium contained in the catalyst component (A). The average particle size is determined by plotting the particle size distribution on probability log paper and reading the particle size at a distribution probability of 50%. Example 1 [Production of solid catalyst component (A)] 32.2 g (0.42 mol) of 1-butanol was placed in a 1.6 capacity autoclave equipped with a stirring device.
Additionally, 0.5g of iodine and 4.86g of metallic magnesium powder.
g (0.2 gram atom), and Ti (O-
After adding 27.2 g (0.08 mol) of nC ₄ H ₉ ) ₄ and further adding 200 ml of hexane, the temperature was raised to 80° C., and the mixture was stirred for 1 hour under a nitrogen blanket while removing generated hydrogen gas. Subsequently, the temperature was raised to 120°C and reaction was carried out for 1 hour. Then at 120°C 15.3 g of dimethylpolysiloxane (viscosity 50 centistokes at 25°C)
(0.2 gram atom of silicon) was injected with nitrogen,
The reaction was carried out at 120°C for 1 hour. The temperature dropped to 60℃,
After slowly adding 30.3g (0.13mol) _{of ZrCl4} ,
The temperature was raised to 120°C again and an aging reaction was carried out for 1 hour. Next, 471 ml of a 50% hexane solution of ethylaluminum dichloride was added over 3 hours at 45°C. After all additions were made, the temperature was raised and stirred at 60°C for 1 hour. Hexane was added to the product and the product was washed 15 times by decantation. Thus, the solid catalyst component (A) suspended in hexane
A slurry containing 61.4 g of solid catalyst component (A) was obtained. A part of it was collected, and after removing the supernatant, it was dried in a nitrogen atmosphere and analyzed. Ti6.9%, Zr16.9
It was %. [In the case of ethylene] Purge the interior of a stainless steel electromagnetic stirring autoclave with an internal volume of 2 with sufficient nitrogen, and add hexane to the autoclave.
1.2 was prepared and the internal temperature was adjusted to 80°C. Then, 0.4 g (2.0 mmol) of triisobutylaluminum as catalyst component (B) and solid catalyst component
(A) A slurry of the solid catalyst component (A) corresponding to 67 mg was sequentially added. After adjusting the internal pressure of the autoclave to 1 atm, 17 atm of hydrogen was added, and ethylene was continuously added for 1.5 hours to carry out polymerization so that the pressure reached 25 gauge pressure. After the polymerization is completed, cool it down, expel unreacted gas,
The polyethylene was taken out, separated from the solvent by filtration, and dried. Melt index 0.21g/10 minutes, HLMI/
MI113, 192g polyethylene with bulk density 0.35g/ ^cm3
was gotten. Production amount per gram of transition metal (hereinafter referred to as activity)
is equivalent to 12,400g, and the proportion of fine particles with a particle size of 105μ or less (hereinafter referred to as fine particle content) is 4.1%.
The average particle size was 400μ. Examples 2 and 3 Catalyst component (A) was produced and ethylene was polymerized in the same manner as in Example 1. However, the amount of dimethylpolysiloxane (viscosity 50 centistokes at 25°C) added was varied. That is, Example 2 Silicon/Magnesium=0.35 (gram atom/gram atom) Example 3 Silicon/Magnesium=3.0 (gram atom/gram atom) Each catalyst was prepared. The results are shown in Table 1. Example 4 In producing the catalyst component (A) in Example 1, the order of reaction of dimethylpolysiloxane and ZrCl ₄ was changed. That is, the same operation as in Example 1 was repeated except that after reacting ZrCl ₄ , dimethylpolysiloxane was added and reacted. Polymerization of ethylene was carried out under the same conditions as in Example 1, and the results are shown in Table 1. Examples 5 to 7 Catalysts were prepared in the same manner as in Example 1. However, in place of the dimethylpolysiloxane used in Example 1, various siloxane compounds were used. That is, in Example 5, methyl phenylpolysiloxane (viscosity at 25° C., 500 centistokes), in Example 6, methyl hydropolysiloxane (viscosity at 25° C., 30 centistokes), and in Example 7, octamethyl cyclotetrasiloxane. was used. Ethylene polymerization was carried out in the same manner as in Example 1 using each catalyst. The results are shown in Table 1. Example 8 32.2 g of 1-butanol was obtained in the same manner as in Example 1.
(0.42 mol), iodine 0.5 g, metallic magnesium powder 4.86 g (0.2 gram atom), Ti (O-n-
27.2g ( _0.08mol ) of _C4H9 ) ₄ and 200ml of hexane
After adding , the temperature was raised to 80°C, and an aging reaction was carried out for 1 hour under a nitrogen blanket while excluding generated hydrogen gas. Lower the temperature to 60℃ and dimethyl diethoxysilane
27.23 g (0.18 gram atom of silicon) was added and reacted for 1 hour. Then 30.3g of ZrCl ₄ at 60℃
(0.13 mol) was slowly added, the temperature was raised again to 120°C, and the aging reaction was carried out for 1 hour. The subsequent operations were carried out in the same manner as in Example 1 to obtain 62.5 g of solid catalyst component (A) containing 5.3% Ti and 15.1% Zr. Polymerization of ethylene was carried out in the same manner as in Example 1. The results are shown in Table 1. Examples 9 and 10 Catalysts were prepared in the same manner as in Example 8, except that dimethyl diethoxysilane used in Example 8 was replaced with the following silane compound. That is, in Example 9, a catalyst was prepared using methyl orthosilicate, silicon/magnesium=0.25 (gram atom/gram atom), and in Example 10, a catalyst was prepared using dimethyl dichlorosilane, silicon/magnesium=1.0 (gram atom/gram atom). Ethylene polymerization was carried out in the same manner as in Example 1 using each catalyst. The results are shown in Table 1. Comparative example 1 1-butanol 32.2g by the same operation as Example 1
(0.42 mol), iodine 0.5 g, metallic magnesium powder 4.86 g (0.2 gram atom), Ti (O-n-
27.2g ( _0.08mol ) of _C4H9 ) ₄ and 200ml of hexane
After adding , the temperature was raised to 80°C, and an aging reaction was carried out for 1 hour under a nitrogen blanket while excluding generated hydrogen gas. Next, without adding any silicon compound, the temperature was lowered to 60°C, 30.3 g (0.13 mol) of ZrCl ₄ was slowly added, and then the temperature was raised to 120°C again to perform an aging reaction for 1 hour. Then, at 45°C, 471 ml of a 50% hexane solution of ethylaluminum dichloride was added over 3 hours. After all additions were made, the temperature was raised and stirred at 60°C for 1 hour. It was washed with hexane to obtain a slurry of solid catalyst component (containing 56.8 g of solid catalyst component). A part of it was collected, the supernatant liquid was removed, and then dried under a nitrogen atmosphere and analyzed, it was found that Ti5.9% Zr15.7%
It was hot. Polymerization of ethylene was carried out in the same manner as in Example 1. As a result, the activity was 12000g/g (Ti + Zr),
MI0.22, HLMI/MI80. Also, the bulk density is
0.25 g/cm ³ , which is extremely low compared to the above example, and the fine particle content is 65.2%, which is 65.2% compared to the above example.
There were significantly more. Furthermore, the average particle size was 80 μm, which was significantly inferior. Example 11 [Production of solid catalyst component (A)] 46.3 g (0.136 mol) of Ti(O-nC ₄ H ₉ ) ₄ and Zr were placed in a 1.6 capacity autoclave equipped with a stirring device.
(O−nC ₄ H ₉ ) ₄ ·nC ₄ H ₉ OH, 80.2 g (0.180 mol), dimethyldiethoxysilane 29.6 g (0.2 mol), and anhydrous magnesium chloride 19.04 g (0.2
After adding 200 ml of hexane, the temperature was slowly raised to 120°C, and the reaction was carried out for 2 hours under a nitrogen blanket. The temperature was lowered to 45°C, and 824 ml of a 50% hexane solution of ethylaluminum dichloride was added over 3 hours. After everything was added, the temperature was raised and stirred at 60°C for 1 hour. The subsequent operations were performed in the same manner as in Example 1 to obtain a slurry containing 79.5 g of solid catalyst component (A). This catalyst component
Analysis of (A) revealed that Ti was 8.0% and Zr was 15.9%. Polymerization of ethylene was carried out in the same manner as in Example 1, and the results are shown in Table 2. Example 12 In a 1.6 capacity autoclave equipped with a stirring device, 80.2 g (0.18 mol) of Zr(O-nC ₄ H ₉ ) ₄ ·nC ₄ H ₉ OH, 15.22 g (0.1 mol) of methyl orthosilicate and anhydrous magnesium chloride are added. After adding 19.04 g (0.2 mol) and further adding 200 ml of hexane, the temperature was slowly raised to 120°C and reaction was carried out for 2 hours under a nitrogen blanket. The temperature was lowered to 45°C, and 589 ml of a 50% hexane solution of ethylaluminum dichloride was added over 3 hours. Next, add 34.7 g (0.10 mol) of Ti(O−nC ₄ H ₉ ) ₄
After adding at 45℃ for 30 minutes, the temperature was increased to 60℃, and then the temperature was increased to 60℃.
The mixture was stirred for 1 hour. The subsequent operations were carried out in the same manner as in Example 1 to obtain a slurry containing 64 g of solid catalyst component (A). This catalyst component
Analysis of (A) revealed that Ti was 7.3% and Zr was 17.5%. Polymerization of ethylene was carried out in the same manner as in Example 1, and the results are shown in Table 2. Example 13 In a 1.6 capacity autoclave equipped with a stirrer, 27.2 g (0.06 mol) of Ti(O-nC ₄ H ₉ ) ₄ and 30.6 g of dimethylpolysiloxane (viscosity 50 centistokes at 25° C.) (0.4 g atom of silicon) are added. ), Mg
(OC ₂ H ₅ ) ₂ 22.9 g (0.2 mol) and hexane 200
ml was added, the temperature was raised to 120°C, and the mixture was stirred for 2 hours. Next, the temperature was lowered to 60℃, and 22.4g of _ZrCl4 (0.096
After slowly adding mol), the temperature was raised to 120°C again and an aging reaction was carried out for 1 hour. Furthermore, 412 ml of a 50% hexane solution of ethylaluminum dichloride was added over 3 hours at 45°C. The subsequent operations were carried out in the same manner as in Example 1 to obtain a slurry containing 57 g of solid catalyst component (A). This catalyst component
Analysis of (A) revealed that Ti was 5.7% and Zr was 16.0%. Polymerization of ethylene was carried out in the same manner as in Example 1, and the results are shown in Table 2. Example 14 In an autoclave with a capacity of 1.6 and equipped with a stirring device, 56.1 g (0.13 mol) of Zr (O-nC ₄ H ₉ ) ₄ ·nC ₄ H ₉ OH and 22.9 g (0.2 mol) of Mg (OC ₂ H ₅ ) ₂ were added. ) and 200 ml of hexane were added, the temperature was raised to 120°C, and the mixture was stirred for 2 hours under a nitrogen blanket. Furthermore, 27.3 g (0.2 gram atom of silicon) of methylphenylpolysiloxane (viscosity at 25°C: 100 centistokes) was introduced under pressure with nitrogen, and the mixture was stirred at 120°C for 1 hour. 45
The temperature was lowered to ℃ and the ethylaluminum dichloride
353 ml of 50% hexane solution was added over 3 hours.
Next, after adding 15.1 g (0.08 mol) of TiCl ₄ , the temperature was increased to 60°C.
The mixture was heated to 60°C and stirred for 1 hour. The subsequent operations were performed in the same manner as in Example 1 to obtain a slurry containing 61 g of solid catalyst component (A). The catalyst component (A)
When analyzed, it was found that Ti was 6.5% and Zr was 17.2%. Polymerization of ethylene was carried out in the same manner as in Example 1, and the results are shown in Table 2. Example 15 Ethylene polymerization was carried out in the same manner as in Example 1 using the slurry containing 106 ml of the solid catalyst component (A) produced in Example 1, but the hydrogen pressure was 27 atm and the total pressure was 30 atm. The internal temperature was 90°C. As a result of polymerization, the activity was 13100g/g (Ti +
Zr), bulk density 0.35g/cm ³ , fine particle content 3.7%,
MI was 2.9 g/10 min, and HLMI/MI was 107. On the other hand, almost no deposits were observed on the inner wall of the autoclave after recovering the polyethylene (the deposits were
(0.01g or less). Comparative Example 2 Ethylene polymerization was carried out in the same manner as in Example 15, except that the slurry containing 113 mg of the solid catalyst component prepared in Comparative Example 1 was used. As a result, the activity is
19400g/g (Ti+Zr), bulk density is 0.32g/cm ³ , fine particle content is 69.3%, MI is 3.5g/10min,
HLMI/MI was 76. A large amount of deposits was observed on the inner wall of the autoclave, and 0.92 g of deposits was collected.

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【table】

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【table】 [Brief explanation of the drawing]

FIG. 1 is a flow chart describing the steps for preparing a catalyst used in the present invention.

Claims (1)

[Claims] 1. Polymerizing ethylene or a mixture of ethylene and at least one compound selected from the group consisting of α-olefins and dienes in the presence of a catalyst consisting of a transition metal compound and an organometallic compound. In the method for producing an ethylene polymer, the catalyst includes a transition metal solid catalyst component (A) obtained by reacting the following compounds (i) to (v), (i) an oxygen-containing organic compound of magnesium and a halogen-containing compound; (ii) at least one titanium compound selected from oxygen-containing organic compounds of titanium and halogen-containing compounds; (iii) oxygen of zirconium; at least one zirconium compound selected from containing organic compounds and halogen-containing compounds, (iv) at least one silicon compound selected from polysiloxanes and silanes, and (v) at least one halogenated organoaluminum compound, and , the method for producing an ethylene polymer, characterized in that a catalyst system consisting of an organometallic catalyst component (B) consisting of at least one organoaluminum compound is used.