JPH0424362B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an ethylene copolymer, which comprises copolymerizing ethylene and an α-olefin having 3 or more carbon atoms in the presence of a novel catalyst system. It has been known to copolymerize ethylene and an α-olefin having 3 or more carbon atoms using a magnesium-supported Ziegler catalyst to obtain an ethylene copolymer having a relatively low density. When obtaining an ethylene copolymer, a solution polymerization method in which polymerization is carried out using a hydrocarbon solvent at a temperature higher than the melting point of the copolymer produced is used because of its relatively easy operability. However, when obtaining an ethylene copolymer with a sufficiently large molecular weight using solution polymerization, the concentration of the copolymer in the solvent must be kept low to prevent the solution viscosity from increasing, which significantly impairs productivity. . In addition, a high-temperature, high-pressure method in which polymerization is carried out at a pressure of 200 atmospheres or higher and a temperature higher than the melting point of the copolymer is also used to produce ethylene copolymers. for example,
Although JP-A-56-18607 proposes a catalyst with improved activity, it is difficult to obtain an ethylene copolymer with a sufficiently large molecular weight even with this high temperature and high pressure method. In addition, this method requires a large amount of energy to achieve high temperature and high pressure, which poses a problem in productivity. On the other hand, slurry polymerization is not subject to molecular weight restrictions and is easy to polymerize, with a density of 0.900 to 0.945 g/cm ³
Obtaining an ethylene copolymer having the following properties is advantageous in terms of both process operation and productivity. However, when producing an ethylene copolymer with a relatively low density, the slurry polymerization method increases the amount of polymer components that are solubilized in the solvent and causes the polymer particles to swell with the solvent, resulting in a decrease in bulk density or polymerization. It has drawbacks such as adhesion to the vessel wall. In order to improve this drawback, there is a known method of preventing rod wetting by using a low boiling point solvent having 3 to 5 carbon atoms. It is necessary to compress, cool and liquefy. The present invention aims to provide a method for easily and stably producing a relatively low density ethylene copolymer by a slurry polymerization method that overcomes the various drawbacks as described above and is not subject to molecular weight restrictions. This is the purpose. In order to achieve this purpose, it is necessary to
The catalyst suitable for the high-temperature and high-pressure method proposed in Publication No. 18607 and the catalyst intended for high activity proposed in JP-A-55-40745 are applied to the production of ethylene copolymers by the slurry polymerization method. However, it does not overcome the above-mentioned drawbacks. The present inventors previously proposed Japanese Patent Application Laid-Open No. 56-155205.
In the presence of the catalyst system described in the publication, hexane,
When a relatively low-density ethylene copolymer is produced by a slurry polymerization method using a relatively high-boiling hydrocarbon such as heptane as a solvent, the swelling of the copolymer particles by the solvent is extremely small, and therefore, the swelling of the copolymer particles due to the solvent is extremely small, resulting in a drop in the polymerization vessel wall. However, there was still room for improvement in this catalyst system in terms of copolymerizability of α-olefins having 3 or more carbon atoms and catalytic activity. Therefore, as a result of further research and consideration regarding this catalyst system, the problems of copolymerizability and catalytic activity were solved, and the present invention was completed. That is, the present invention involves the process of ethylene and an α-olefin having 3 or more carbon atoms at a polymerization temperature below the melting point of the copolymer and at a pressure below 50 atmospheres in the presence of a catalyst consisting of a transition metal compound and an organometallic compound. When producing an ethylene copolymer having a density of 0.900 to 0.945 g/cm ³ by copolymerization, at least one member selected from (1) metallic magnesium and alcohol (2) tetraalkoxytitanium is used as component A. and (3) a product obtained by reacting at least one silicon compound, and (4) a solid component obtained by reacting at least one halogenated organoaluminum compound, and (5) at least one silicon compound. This is a method for producing an ethylene copolymer using a catalyst system consisting of a solid catalyst component obtained by treatment with a certain type of titanium tetrahalide compound and at least one component selected from organoaluminum compounds as component B. Examples of the metal magnesium and alcohol used in the above (1) for producing the solid catalyst component A of the catalyst system of the present invention include the following. Magnesium metal can be used in various forms, such as powder, particles, foil or ribbon. As alcohols, linear or branched aliphatic alcohols, cycloaliphatic alcohols or aromatic alcohols having 1 to 18 carbon atoms can be used. Examples include methanol, ethanol, n-
Examples include butanol, n-octanol, n-stearyl alcohol, cyclopentanol, and ethylene glycol. In addition, when metallic magnesium is used to obtain the solid component described in the present invention, substances that react with metallic magnesium or produce adducts, such as iodine and dichloride, are added in order to accelerate the reaction. Polar substances such as dimercury, alkyl halides, organic acid esters, and organic acids,
It is preferable to add them singly or in combination of two or more. As the tetraalkoxytitanium in (2) above, a compound represented by the general formula Ti(OR') ₄ is used.
However, in the general formula, R' has 1 to 20 carbon atoms,
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. Specific examples include Ti( _{OC2H5 ) 4} , Ti(O-
n- _{C3H7 ) 4} , Ti(O-i- _{C3H7 ) 4} , Ti(O-n-
_{C4H9 )4 ,} etc. The use of tetraalkoxytitanium containing several different hydrocarbon groups is also within the scope of the invention. Furthermore, it is also within the scope of the present invention to use these alone or as a mixture of two or more. As the silicon compound in (3) above, the following polysiloxanes and silanes are used. As polysiloxane, general formula

[Formula] (wherein R ² and R ³ 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) represents an atom or residue that can engage with silicon, such as, R ² and R ³ may be the same or different, and p is usually 2 to 10,
A siloxane polymer having a chain, cyclic or three-dimensional structure containing one or more types of repeating units (representing an integer of 000) in various ratios and distributions within the molecule (however, All R ² and
(Except when R ³ is hydrogen or halogen)
can be given. 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 Examples include siloxane, diethoxypolysiloxane, and diphenoxypolysiloxane. 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. As a polysiloxane with a three-dimensional structure,
For example, the above-mentioned chain or cyclic polysiloxane may be made to have a crosslinked structure by heating or the like. These polysiloxanes are desirably liquid in handling, and desirably have a viscosity at 25° C. of 1 to 1000 centistokes, preferably 1 to 1000 centistokes. 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 H _q Si _r R ⁴ _s X _t (wherein,
R ⁴ represents ^a hydrocarbon group such as an alkyl group having 1 to 12 carbon atoms or an aryl group, a group capable of bonding to silicon such as an alkoxy group having 1 to 12 carbon atoms, an allyloxy group, or a fatty acid residue; Silicon compounds may be different or the same, X represents a halogen of the same or different, q, s and t are integers of 0 or more, r is a natural number, and q+s+t=2r+2 can be given. Specifically, silahydrocarbons such as trimethylphenylsilane and allyltrimethylsilane, linear and cyclic organic silanes such as hexamethyldisilane and octaphenylcyclotetrasilane, and organic silanes such as methylsilane, dimethylsilane, and trimethylsilane are used. Silane, silicon halides such as silicon tetrachloride and silicon tetrabromide, dimethyldichlorosilane, diethyldichlorosilane, n-butyltrichlorosilane, diphenyldichlorosilane,
Alkyl and arylhalogensilanes such as triethylfluorosilane, dimethyldipromosilane, alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, diphenyldiethoxysilane, tetramethyldiethoxydisilane, dimethyltoteraethoxydisilane , silane compounds containing haloalkoxy such as dichlorobutoxysilane, dichlorodiphenylsilane, tripromoethoxysilane, and fatty acid residues such as phenoxysilane, trimethylacetoxysilane, diethyldiacetoxysilane, and ethyltriacetoxysilane. The above silicon compounds may be used alone, or two or more types may be mixed or reacted together. As the halogenated organoaluminum compound in (4) above, those represented by the general formula R ⁵ _z AX _3-Z are used. However, in the general formula, R ⁵ is 1 to
a hydrocarbon group containing 20, preferably 1 to 6 carbon atoms, where X represents halogen, F, C
, Br or I. z is a number satisfying 0<z<3. Preferably R ⁵ is straight chain or branched alkyl,
cycloalkyl, arylalkyl, aryl,
selected from alkylaryl groups. The above halogenated organoaluminum compounds can be used alone or as a mixture of two or more. Specific examples of halogenated organoaluminum compounds include A(C ₂ H ₅ )C ₂ , A(C _2
H5 ) _2C , A ₍ i- _C4H9 ) _C2 , etc.
The solid component of the present invention can be produced by reacting the reaction product obtained by reacting the above-described reactants (1), (2), and (3) with reactant (4). These reactions are preferably carried out in a liquid medium. Therefore, the reaction can 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, any solvent commonly used in the art can be used, including aliphatic, alicyclic or aromatic hydrocarbons, their halogen derivatives, or mixtures thereof, such as isobutane, hexane, etc. ,
Heptane, cyclohexane, benzene, toluene, xylene, monochlorobenzene and the like are preferably used. The reaction order of the reactants (1), (2), and (3) may be any order as long as a chemical reaction occurs. For example, a method of adding a silicon compound to a mixture of magnesium metal, an alcohol, and a tetraalkoxytitanium compound, a method of simultaneously mixing magnesium metal, an alcohol, a tetraalkoxytitanium compound, and a silicon compound, a method of adding a silicon compound to a mixture of magnesium metal, an alcohol, and a silicon compound, and a method of adding a silicon compound to a mixture of magnesium metal, alcohol, and a tetraalkoxytitanium compound; Possible methods include adding a titanium compound. The product thus obtained is reacted with a halogenated organoaluminum compound to obtain a solid component. There is no particular restriction on the amount of the reactants (1)(2)(3)(4) used in the present invention, but the ratio of magnesium atoms to titanium atoms is preferably 1:0.01 to 1:20, preferably 1:0.1 to 1:5, the ratio of magnesium atoms to silicon atoms is 1:20 or less, preferably 1:5 or less, and the ratio of magnesium atoms to aluminum atoms is 1:
It is preferable to select the amount of the reactant to be used in a range of 0.1 to 1:100, preferably 1:1 to 1:20. However, when polysiloxane is used as the silicon compound, the atomic ratio of magnesium to silicon should be understood to indicate the ratio of magnesium atoms to the repeating unit represented by the general formula (gram atoms to moles). Reaction conditions are not particularly limited, but -50 to 300
The reaction is carried out at a temperature of 0.degree. C., preferably 0 to 200.degree. C., for 0.5 to 50 hours, preferably 1 to 6 hours, under normal pressure or elevated pressure in an inert gas atmosphere. The solid components thus obtained are particles insoluble in the solvent used as a diluent and are removed by filtration or decantation to remove remaining unreacted substances and by-products, and then washed several times with an inert solvent. , suspended in an inert solvent and subjected to a contact reaction with the reactant (5). Examples of the tetrahalogenated titanium compound (5) include titanium tetrachloride and titanium tetrabromide. Examples include titanium tetraiodide. Among these compounds, titanium tetrachloride is particularly preferred. The reaction conditions between the solid component and the tetrahalogenated titanium compound are not particularly limited, but are -50 to 150
The reaction is carried out at a temperature of 0.degree. C., preferably 0 to 100.degree. C., for 0.1 to 50 hours, preferably 0.2 to 6 hours, in an inert gas atmosphere under normal pressure or elevated pressure. The amount of reactant (5) used in the above reaction is:
The ratio of titanium atoms in reactant (2) to titanium atoms in reactant (5) is 1:0.1 to 1:20, preferably 1:0.1 to
It is preferable to select a ratio within the range of 1:10. The catalyst component A thus obtained may be used as it is, but is generally used after removing and washing remaining unreacted substances and the like, and then suspending it in an inert solvent. It is also possible to use products obtained by washing, isolating, and heat-treating under normal pressure or reduced pressure to remove the solvent. In the present invention, as the catalyst component B, an organoaluminum compound is used. As the organic group 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, examples of catalyst component B include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-decylaluminum, and the like. Particularly preferred is the use of trialkylaluminum having a straight or branched alkyl group having 1 to 10 carbon atoms. In addition, as component B, an alkyl aluminum hydride having an alkyl group having 1 to 20 carbon atoms can be used. 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 leysoprenyl aluminum, may be used. You can also do it. In carrying out the present invention, the amount of catalyst component A used is preferably equivalent to 0.001 to 2.5 mmol of titanium atoms per solvent or per reactor internal volume, and may be used at a higher concentration depending on the conditions. You can also. The organoaluminum compound of catalyst component B is added per solvent or per reactor internal volume,
It is used in concentrations of 0.02 to 50 mmol, preferably 0.2 to 5 mmol. In the method for producing an ethylene copolymer of the present invention, the number of carbon atoms used for copolymerization with ethylene is 3.
The above α-olefin has the general formula R-CH
= _CH2 (wherein, R is 1 to 10, preferably 1 to 8
Examples include α-olefins represented by linear or branched alkyl groups having 5 carbon atoms. Specific examples include propylene, 1-butene, 1-bentene, 4-methyl-1-bentene, 1-hexene, and 1-octene. Copolymerization can also be carried out using a mixture of two or more of the above α-olefins. The density of the obtained ethylene copolymer is 0.900~
In order to achieve 0.945 g/ ^cm3 , the copolymerization ratio of α-olefin should be about 0.2 to 20% by weight, especially about 0.3 to 15% by weight, although it varies depending on the type of catalyst and the type of α-olefin. It is necessary to choose. The copolymerization of ethylene and α-olefin according to the present invention can be carried out under general reaction conditions of so-called slurry polymerization. That is, continuous or batchwise polymerization temperature below the melting point of the copolymer;
Particularly preferably, the copolymerization is carried out at a temperature of 90 to 50°C. The above copolymerization is preferably carried out in the presence of an inert solvent, but is not limited thereto. As the inert solvent, commonly used ones can be used. Particularly suitable are alkanes having 4 to 10 carbon atoms, such as n-butane, isobutane, pentane, hexane, heptane and the like. Among the above-mentioned solvents, good results can be obtained according to the method of the present invention even when relatively high-boiling point solvents such as hexane and heptane are used. Furthermore, it is also possible to carry out so-called solvent-free polymerization in which a comonomer of an α-olefin having 3 or more carbon atoms is used as a solvent without using an inert solvent. α-olefins that can be used for this purpose include:
For example, 1-butene, 1-pentene, 4methyl-1
-Pentene, 1-hexene, etc. The polymerization pressure during copolymerization is not particularly limited, but a pressure in the range of 1.5 to 50 atmospheres is suitable. In the present invention, the molecular weight of the copolymer can be adjusted by known means, such as by allowing an appropriate amount of hydrogen to be present in the reaction system. The copolymerization according to the method of the present invention can also be carried out in two or more stages with different polymerization conditions. The method of the present invention uses ethylene and α-carbon atoms having 3 or more carbon atoms.
When producing an ethylene copolymer with a density of 0.900 to 0.945 g/cm ³ by copolymerizing olefin with a slurry polymerization method, even when obtaining a relatively low density polymer, swelling with a solvent is necessary. There are very few
Therefore, the method of the present invention is based on a precursor catalyst that can obtain a polymer that does not adhere to the walls of a polymerization vessel, and has been improved to enhance copolymerizability and catalytic activity toward α-olefin. Since it is used as a catalyst, the following effects can be obtained. (1) Good copolymerizability with α-olefins having a prime number of 3 or more, so only a small amount of α-olefin is needed for copolymerization, making it easy to produce ethylene copolymers with low densities of 0.945 g/cm ³ or less. can be manufactured. (2) Since the catalyst activity is extremely high, that is, the amount of polymer produced per unit weight of the catalyst component or the polymer yield per unit amount of transition metal is large, molded products can be formed without the need to remove catalyst residues in the polymer. Problems such as coloring and deterioration can be avoided. (3) Even when producing low-density ethylene copolymers, the swelling of the polymer particles by the solvent is extremely small, and therefore the particles do not stick to the walls of the polymerization vessel, so stable slurry polymerization can reduce the molecular weight. A low-density ethylene copolymer with a sufficiently large amount can be easily produced. (4) The solvent used during slurry polymerization does not need to be limited to low boiling point solvents, and relatively high boiling point solvents such as hexane and heptane can be used without any problems, so by using the latter, the pressure in the polymerization vessel can be increased. can be suppressed, and equipment safety and maintenance can be advantageously led. The present invention will be illustrated below using Examples, but the present invention is not limited to these Examples in any way. Example 1 <Production of solid component> A glass flask 1 equipped with a stirring device was sufficiently purged with nitrogen while stirring, and then 2.4 g (0.1 mo) of metallic magnesium and Ti (O-n-C _{4 H9} ) ₄
68 g (0.2 mo) was added thereto, and then 15.6 g (0.21 ml) of n-butanol was added dropwise at 90°C over 2 hours.
Subsequently, the temperature was raised to 140°C and the reaction was continued for 2 hours.
Then diphenyldiethoxylan 27.2g (0.1mo
) was added over 20 minutes and reacted at 140°C for 2 hours.
Thereafter, 170 ml of hexane was added while slowly cooling the temperature. The reaction product was a homogeneous solution containing almost no insoluble matter. Add 177 ml (0.6 mo) of a 50% hexane solution of ethylaluminum dichloride to this homogeneous solution at 45°C.
was added over 2 hours. After everything was added, the temperature was raised to 60°C and stirring was continued for 30 minutes. Hexane was added to the product, and the product was washed 7 times by decanting to obtain a solid component.
A portion of it was collected, dried under a nitrogen atmosphere, and analyzed, and the titanium content was found to be 16.5%. <Production of catalyst component A> Add 76 g of titanium tetrachloride as a titanium halide to the hexane slurry containing the solid component.
(0.4 mo) was added dropwise at 45°C over 30 minutes. The atomic ratio of titanium tetrachloride to titanium in the solid component is 2:
It was 1. After dropping the entire amount, raise the temperature to 60℃,
The reaction was allowed to proceed for 30 minutes. Thereafter, hexane washing was performed in the same manner as in the above method to obtain catalyst component A. When a part of it was analyzed, the titanium content was 18.4%. <Copolymerization of ethylene and 1-butene> A stainless steel electromagnetic stirring autoclave having an internal volume of 2 was sufficiently purged with nitrogen while stirring, and 1.2 parts of hexane was charged, and the temperature was adjusted to 65°C.
Thereafter, 0.69 g (3.5 mmo) of triisobutylaluminum (TIBAL) as catalyst component B and a hexane slurry equivalent to 9.0 mg of solid catalyst component A were successively added. After adjusting the internal pressure of the autoclave to 1 atm, a hydrogen partial pressure of 2.5 atm was added, and then the pressure was increased to 1 atm.
-100 ml of butene was added, and polymerization was carried out for 1.5 hours while continuously supplying ethylene so that the total pressure was 8.5 atm. After the polymerization was completed, it was cooled, unreacted gas was expelled, and the ethylene copolymer was taken out, separated from the solvent by filtration, and dried. 170 g of ethylene copolymer was obtained with a melt index (according to ASTM D-1238) of 2.5 g/10 min and a density (according to ASTM D-1505) of 0.928 g/cm ³ . The amount produced per gram of catalyst component A (hereinafter referred to as catalytic activity) is 19,000g, and 103,000g per gram of titanium.
It was equivalent to In addition, the bulk density is 0.32g/ ^cm3 ,
No polymer adhesion to the autoclave walls was observed. Comparative Example 1 Example 1 using 23.7 mg of the solid component in Example 1 (without addition of titanium halide)
Copolymerization of ethylene was carried out in the same manner. As a result, the melt index was 2.1g/10 minutes, and the density was
150 g of 0.934 g/cm ³ ethylene copolymer was obtained.
The catalytic activity was 6300 g/g, corresponding to 38200 g/g titanium. The results showed that the density was higher and the catalyst activity was lower than in Example 1, and adhesion of polymer on the autoclave wall was observed. Example 2 Using the same catalyst component A and catalyst component B as in Example 1, ethylene and 1-
Copolymerization of putene was carried out. However, in order to further lower the density, the amount of 1-butene used was changed to 150 ml. The polymerization results are shown in Table 1. An ethylene copolymer having a density of 0.922 g/cm ³ was obtained under stable polymerization without any adhesion to the autoclave wall. Example 3 Using the same catalyst component A as in Example 1, ethylene and 1-butene were copolymerized. For copolymerization, use 2 autoclaves as in Example 1, charge 1.2 parts of hexane, and adjust the temperature to 65°C.
After adjusting to
Add 0.25 g (3.5 mmo) and 10.3 mg of solid catalyst component A, hydrogen partial pressure 2.0 atm and 150 ml of 1-butene.
while maintaining the total pressure at 8.0 atm with ethylene.
Polymerization was carried out for 1.5 hours. When the ethylene copolymer was taken out in the same manner as in Example 1, 160 g of a copolymer with a melt index of 0.64 g/10 minutes and a density of 0.920 g/cm ³ was obtained. The catalyst activity corresponded to 15500 g/g. Example 4 Using 28.5 mg of the same catalyst component A as in Example 1,
Copolymerization of ethylene and 1-butene was carried out. Copolymerization was carried out in the same manner as in Example 1, but
As catalyst component B, 0.42 g (3.5 mmo) of diethylaluminium chloride (DEAC), a hydrogen partial pressure of 5.0 atm, and 100 ml of 1-butene were used. Catalytic activity is
5500g/g, melt index 0.49g/10
A polymer having a density of 0.918 g/cm ³ and a bulk density of 0.28 g/cm ³ was obtained. Furthermore, no polymer was observed to adhere to the autoclave wall. Comparative Example 2 Ethylene copolymerization was carried out using 126 mg of the solid component in Example 1. Copolymerization was carried out in the same manner as in Example 4, using 0.42 g (3.5 mmol) of diethyl aluminum chloride as catalyst component B.
), a hydrogen partial pressure of 5.0 atm and 100 ml of 1-butene were added, and the reaction was carried out for 1.5 hours at a total pressure of 11.0 atm and a temperature of 65°C.
As a result, the melt index was 1.9g/10 minutes, and the density was
138 g of 0.923 g/cm ³ ethylene copolymer was obtained. The catalyst activity was 1100 g/g, which was significantly lower than in Example 4, and adhesion of polymer to the autoclave wall and fixation of polymer particles were observed. Examples 5 to 7, Comparative Examples 3 to 4 <Production of solid component> Solid components were produced in the same manner as in Example 1, but after the addition of n-butanol, 20.8 g (0.1 mo) of ethyl orthosilicate was added as a silicon compound. ) was added. The subsequent catalyst manufacturing method was the same as in Example 1. However, in Examples 5 to 7, titanium tetrachloride
38 g (0.2 mo) was used, and this was not used in Comparative Examples 3 and 4. <Copolymerization> As in Example 1, copolymerization of ethylene and 1-butene was performed using two autoclaves.
Examples 5 to 6 and Comparative Example 3 as catalyst component B
In Example 7 and Comparative Example 4, triisobutylaluminum was used, and diethylaluminum chloride was used in Example 7 and Comparative Example 4, respectively. The results are shown in Table-1. The catalyst activity and density in each example were both significantly superior to the corresponding comparative example. Examples 8 to 9 Catalyst backing material A was produced in the same manner as in Example 5, but the silicon compound used was dimethylpolysiloxane (500cst) in Example 8 and methylphenylpolysiloxane (500 cst) in Example 9. 500cst) was used. Copolymerization was carried out in the same manner as in Example 1, using triisobutylaluminum as catalyst component B. As shown in Table 1, the catalyst activity was 14000g/g (Example 8) and 14500g/g, respectively.
(Example 9). Examples 10 to 11 <Manufacture of catalyst component A> The same procedure as in Example 1 was carried out except that the amount of some of the reactant components charged was changed. That is, Ti(O
-n- _C4H9 ) ₄ 13.6g (0.04mo), 74ml of 50% hexane solution _of ethylaluminum dichloride
A catalyst was produced in the same manner as in Example 1, except that 38 g (0.2 mo) of titanium tetrachloride and 38 g (0.2 mo) of titanium tetrachloride were used. <Copolymerization> Ethylene and 1-butene were copolymerized in the same manner as in Example 1, but as catalyst component B, Example
In Example 10, trimethylaluminum was used, and in Example 11, diethylaluminum chloride was used. The results are shown in Table-1.

【table】

[Table] Comparative Example 5 In producing the solid component of Example 1, an experiment was conducted without using the silicon compound corresponding to component (3) and the tetrahalogenated titanium compound corresponding to component (5). That is, a glass flask 1 equipped with a stirring device was sufficiently purged with nitrogen while stirring, and then 2.4 g (0.1 mol) of metallic magnesium and Ti (O-n-
C ₄ H ₉ ) ₄ 68g (0.2 mol) was added, and then n-
15.6 g (0.21 mol) of butanol was added dropwise over 2 hours. Subsequently, the temperature was raised to 140°C and the reaction was continued for 2 hours. After that, while slowly cooling the temperature, hexane
170 ml was added to obtain a solution. Add a 50% hexane solution of ethylaluminum dichloride at 45 °C to this solution.
After adding 177 ml (0.6 mol) over 2 hours, 60
The temperature was raised to °C and stirring was continued for 30 minutes. Next, Example 1
Washing was performed in the same manner as above to obtain a solid component. Using this solid component, ethylene and 1-butene were copolymerized in the same manner as in Example 1. That is, after fully purging an autoclave with an internal volume of 2 with nitrogen, charging 1.2 liters of hexane, and adjusting the temperature to 65°C, 0.69 g (3.5 mmol) of triisobutylaluminum as catalyst component B and equivalent to 10.0 mg of the above solid component were added. The hexane slurry was added sequentially. After adjusting the internal pressure of the autoclave to 1 atm, a hydrogen partial pressure of 2.5 atm was added, and then the pressure was increased to 1 atm.
-100 ml of butene was added, and polymerization was carried out for 1.5 hours while continuously supplying ethylene so that the total pressure was 8.5 atm. As a result, 78 g of an ethylene copolymer having a melt index of 1.4 g/10 minutes and a density of 0.933 g/cm ³ was obtained.
The catalytic activity corresponded to 7800 g/g. Moreover, the bulk density was 0.23 g/cm ³ , and it was observed that the polymer was attached to the autoclave wall. The superiority of Example 1 according to the present invention is recognized from these density, catalytic activity, bulk density, and polymer adhesion. Comparative Example 6 An experiment was conducted in the same manner as in Example 1 except that the silicon compound corresponding to component (3) was not used in the production of the solid component in Example 1. That is, 75 g (0.4 mol) of titanium tetrachloride was added to the hexane slurry containing the solid component prepared in Comparative Example 2.
was added dropwise at 45°C over 30 minutes. After the entire amount was added dropwise, the temperature was raised to 60°C and the mixture was reacted for 30 minutes. Thereafter, hexane washing was performed in the same manner as in Example 1 to obtain a solid component. Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 using 10.0 mg of this solid component. As a result, 185 g of an ethylene copolymer with a melt index of 1.2 g/10 minutes and a density of 0.930 g/cm ³ was obtained. The catalyst activity corresponded to 18500 g/g. Also,
The bulk density was 0.22 g/cm ³ and polymer adhesion to the autoclave wall was observed. Comparative Example 7 Using a catalyst system corresponding to the catalyst described in Example 4 of JP-A-56-18607, polymerization was carried out under polymerization conditions applicable to the present application. That is, a glass flask 1 equipped with a stirring device was sufficiently purged with nitrogen while stirring, then 0.5 g of heptane was added, and then 31.9 g (0.335 mol) of anhydrous magnesium chloride and Ti (O-n-C ₄ H ₉ ) ₄
After adding 34 g (0.1 mol) and stirring at 70°C for 1 hour, 19.6 g (0.265 mol) of n-butanol was added and further stirring at 70°C for 1 hour, resulting in 50.3 g of titanium tetrachloride.
(0.265 mol) and 32 g (0.535 mol) of methylhydropolysiloxane (20 centistokes) were added and stirred for 2 hours. The product was washed 5 times with 0.5 heptane to obtain a solid catalyst component. Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 using 10.0 mg of this solid catalyst component. As a result, 177 g of an ethylene copolymer with a melt index of 5.8 g/10 minutes and a density of 0.938 g/cm ³ was obtained. The catalyst activity corresponded to 17700 g/g. Also,
The bulk density was 0.21 g/cm ³ and polymer adhesion to the autoclave wall was observed. These densities,
From catalytic activity, bulk density and polymer attachment,
The superiority of Example 1 according to the present invention is recognized. Comparative Example 8 Polymerization was carried out using a catalyst system corresponding to the catalyst described in Example 5 of JP-A-56-18607 under polymerization conditions applicable to the present application. That is, a glass flask 1 equipped with a stirring device was sufficiently purged with nitrogen while stirring, then 0.5 g of heptane was added, and then 31.9 g (0.335 mol) of anhydrous magnesium chloride and Ti (O-n-C ₄ H ₉ ) ₄
After adding 34 g (0.1 mol) and stirring at 70°C for 1 hour, 19.6 g (0.265 mol) of n-butanol was added and further stirring at 70°C for 1 hour, resulting in 50.3 g of titanium tetrachloride.
(0.265 mol) was added and stirred for 2 hours. Next, add 61g (0.535mol) of triethylaluminum at 40°C.
and further stirred for 2 hours. heptane product
It was washed five times with 0.5 to obtain a solid catalyst component. Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 using 10.0 mg of this solid catalyst component. As a result, 124 g of ethylene copolymer with a melt index of 4.6 g/10 minutes and a density of 0.936 g/cm ³ was obtained. The catalyst activity corresponded to 12400 g/g. Also,
The bulk density was 0.18 g/cm ³ and polymer adhesion to the autoclave wall was observed. Comparative Example 9 In order to demonstrate the superiority of the present invention, an experiment was conducted in which an organoaluminum compound was further added to the components in Comparative Example 7. That is, a glass flask 1 equipped with a stirring device was sufficiently purged with nitrogen while stirring, then 0.5 g of heptane was added, and then 31.9 g (0.335 mol) of anhydrous magnesium chloride and Ti (O-n-C ₄ H ₉ ) ₄
After adding 34 g (0.1 mol) and stirring at 70°C for 1 hour, 19.6 g (0.265 mol) of n-butanol was added and further stirring at 70°C for 1 hour, resulting in 50.3 g of titanium tetrachloride.
(0.265 mol) and 32 g (0.535 mol) of methylhydropolysiloxane (also 20 centistoke) were added and stirred for 2 hours. Next, 61 g (0.535 mol) of triethylaluminum was added at 40°C, and the mixture was further stirred for 2 hours. Heptane product 0.5
was washed five times to obtain a solid catalyst component. Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 using 10.0 mg of this solid catalyst component. As a result, 82 g of ethylene copolymer having a relative index of 5.3 g/10 minutes and a density of 0.937 g/cm ³ was obtained.
The catalyst activity corresponded to 8200 g/g. In addition, the bulk density was 0.19 g/cm ³ , and it was observed that the polymer was attached to the autoclave wall. Comparative Example 10 Polymerization was carried out using a catalyst system corresponding to the catalyst described in Example 1 of JP-A-55-40745 under polymerization conditions applicable to the present application. Specifically, a glass flask (1) equipped with a stirring device was sufficiently purged with nitrogen while stirring, then 0.2 g of heptane was added, and then 9.5 g (0.1 mol) of anhydrous magnesium chloride and Ti (O-n-C ₄ H ₉ ) ₄ 10.2g
(0.03 mol) and then stirred at 70°C for 1 hour, then 5.9 g (0.08 mol) of n-butanol was added and further stirred at 70°C for 1 hour. Next, 0.02 mol of aluminum trichloride was added and stirred for 1 hour. Additionally 3.8 g (0.02 mol) of titanium tetrachloride and 9 g of methylhydropolysiloxane (20 centistokes)
(0.15 mol) were added to each and stirred at 70°C for 2 hours. The product was washed 5 times with 0.5 heptane to obtain a solid catalyst component. Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 using 10.0 mg of this solid catalyst component. As a result, 203 g of ethylene copolymer with a melt index of 2.6 g/10 minutes and a density of 0.933 g/cm ³ was obtained. The catalyst activity corresponded to 20300 g/g. Also,
The bulk density was 0.212/cm ³ and polymer adhesion to the autoclave wall was observed. These densities,
From catalytic activity, bulk density and polymer attachment,
The superiority of Example 1 according to the present invention is recognized. Comparative Example 11 In producing the solid component of Example 1, an experiment was conducted by reversing the catalyst order of the halogenated organic aluminum compound corresponding to component 4 and the tetrahalogenated titanium compound corresponding to 5. That is, a glass flask 1 equipped with a stirring device was sufficiently purged with nitrogen while stirring, and then 2.4 g (0.1 mol) of metallic magnesium and Ti (O-n-
C ₄ H ₉ ) ₄ 68g (0.02mol) was added, and then n-
15.6 g (0.21 mol) of butanol was added dropwise over 2 hours. Subsequently, the temperature was raised to 140°C and the reaction was continued for 2 hours. After that, while slowly cooling the temperature, hexane
170 ml was added to obtain a solution. 75 g (0.4 mol) of titanium tetrachloride was added dropwise to this solution at 45° C. over 30 minutes.
After the entire amount was added dropwise, the temperature was raised to 60°C and the mixture was reacted for 30 minutes. Then, after heating the temperature to 45°C again, add 177 ml of a 50% hexane solution of ethyl aluminum dichloride.
(0.6 mol) was added over 2 hours, the temperature was raised to 60°C, and stirring was continued for 30 minutes. Next, washing was performed in the same manner as in Example 1 to obtain a solid component. Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 using 10 mg of this solid component. As a result, 124 g of an ethylene copolymer having a melt index of 0.8/10 minutes and a density of 0.931 g/cm ³ was obtained. The catalyst activity corresponded to 12400 g/g. Also,
The bulk density was 0.22 g/cm ³ and polymer adhesion to the autoclave wall was observed. These densities,
From catalytic activity, bulk density and polymer attachment,
The superiority of Example 1, the contact order according to the invention, is recognized. Comparative Example 12 An experiment was carried out in the same manner as in Example 1, except that in the production of the solid component of Example 1, the silicon compound of component (3) was brought into contact last. That is, diphenyldiethoxysilane was added to the hexane slurry containing the solid component prepared in Comparative Example 3.
26g (0.1mol) was added dropwise at 45°C over 30 minutes. After the entire amount was added dropwise, the temperature was raised to 60°C and the mixture was reacted for 30 minutes. After that, hexane cleaning was performed in the same manner as in Example 1.
A solid component was obtained. Copolymerization of ethylene and 1-butene was carried out in the same manner as in Example 1 using 10.0 mg of this solid component. As a result, 73 g of ethylene copolymer with a melt index of 3.6 g/10 minutes and a density of 0.937 g/cm ³ was obtained.
The catalyst activity corresponded to 7300 g/g. Moreover, the bulk density was 0.23 g/cm ³ , and it was observed that the polymer was attached to the autoclave wall.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing the catalyst adjustment process.

Claims (1)

[Claims] 1. In the presence of a catalyst consisting of a transition metal compound and an organometallic compound, ethylene and α having 3 or more carbon atoms
- In producing an ethylene copolymer having a density of 0.900 to 0.945 g/cm ³ by copolymerizing with olefin at a polymerization temperature below the melting point of the copolymer and a polymerization pressure below 50 atmospheres, component A (1) at least one compound selected from magnesium metal and alcohol, (2) tetraalkoxytitanium, and (3) a product obtained by reacting at least one silicon compound; (5) a solid catalyst component obtained by treating with at least one tetrahalogenated titanium compound and an organoaluminum compound as component B; A method for producing an ethylene copolymer, the method comprising using a catalyst system comprising at least one type.