JPS6026407B2 - Method for producing ethylene copolymer - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a low-density ethylene copolymer by polymerizing ethylene and a small proportion of Q-olefin having 3 or more carbon atoms. It is known that when ethylene and a small proportion of Q-olefin are copolymerized using a Ziegler type catalyst, an ethylene copolymer having a density comparable to that of high-pressure polyethylene can be obtained. Generally, since the polymerization operation is easy, it is advantageous to employ high-temperature melt polymerization in which polymerization is performed using a hydrocarbon solvent at a temperature higher than the melting point of the copolymer to be produced. However, when trying to obtain a copolymer with a sufficiently large molecular weight, the viscosity of the polymerization solvent increases, so the polymer concentration in the solution is reduced to 4.
・There is a drawback that copolymer productivity per polymerization vessel must be low because the copolymer must be washed. On the other hand, when attempting to obtain the above-mentioned low-density ethylene copolymer by the slurry polymerization method that is often used in the production of high-density polyethylene, the copolymer easily dissolves or swells in the polymerization solvent, resulting in an increase in the viscosity of the polymerization solution. However, there were disadvantages in that not only the slurry concentration could not be increased but also continuous operation for a long time was impossible due to the adhesion of the polymer to the polymerization vessel and a decrease in the high density of the polymer. Furthermore, the resulting copolymer was sticky, which caused problems in terms of quality. Several methods have been proposed to overcome these drawbacks by using multi-stage polymerization. For example, according to Samurai Sekisho 51-52487, a special fixed catalyst component called a co-pulverized product of magnesium halide, titanium compound, and aluminum halide ether is used, and the amount of the component per night is A method is disclosed in which ethylene of 5 or more is prepolymerized and then copolymerized in a low boiling hydrocarbon having a boiling point of 4 to 0 or less. However, this method has limitations on the polymerization solvent that can be used. Also, Tokuseki Showa 52-
121 Sousaisen has proposed a method that uses a similar polymerization solvent and performs a complicated three-stage polymerization, but it has drawbacks such as limitations on the polymerization solvent and the need for complicated polymerization operations. . Further, Tsubaki Batsu No. 12408Y/1987 discloses a method in which 5M or more of ethylene is pre-coated with a supported catalyst per night, and then copolymerization is carried out in the polymerization solvent. In addition to the above-mentioned drawbacks, this method produces too much ethylene homopolymer in the prepolymerization, so that fish eyes are unavoidable when the copolymer is used in film applications. The present inventors are able to use relatively high-boiling point solvents such as hexane and heptane, which are often used in olefin polymerization, and can also produce high-density and large copolymers with simple polymerization operations. After studying the slurry polymerization method, we found that the purpose could be achieved by strictly specifying the catalyst components and the amount of prepolymerization. That is, the present invention uses a catalyst formed from a titanium catalyst component supported on a magnesium compound and an organoaluminum compound 'B' to convert ethylene and a small proportion of Q-olefin having 3 or more carbon atoms into iopi0 or less. Copolymerization is carried out at a temperature of 0.900 to 0.90%. In a method for producing a bulk ethylene copolymer, (A
-1) Those with a specific surface area of 40 mm/ta or more, an average particle diameter in the range of 5 to 200 mm, and a geometric standard deviation of particle size distribution of less than 2.1, and/or (A-2) Using a catalyst having a specific surface area of 80 mm or more and containing an organic acid ester of 0.1 to 7 times the mole of titanium, 0.01 to 40 mm of ethylene as a titanium catalyst component is used prior to copolymerization. This is a method for producing an ethylene copolymer, characterized in that the copolymerization is carried out after polymerizing the ethylene copolymer. The titanium catalyst component supported on a magnesium compound used in the present invention must meet one or both of the following requirements. That is, (A-1) the specific surface area is 40〆/ta or more, the average particle diameter is in the range of 5 to 200A, and the geometric standard deviation of the particle size distribution. 2) It must have a specific surface area of 80/g or more and contain an organic acid ester of 0.1 to 7 moles of titanium.
A titanium catalyst component that satisfies the requirements of (1) has a specific surface area of 40/ta or more, preferably 60/ta or more, an average particle height in the range of 5 to 200, and a geometrical particle size distribution. standard deviation. The average temperature is less than 2.1, preferably 1.95 or less. Here, a light transmission method was used to measure the particle size distribution of titanium catalyst component particles. Specifically, 0.0 in an inert solvent such as decalin
The catalyst component is diluted to a concentration of around 1 to 0.5%, placed in a measurement cell, and the cell is illuminated with a narrow light to continuously measure the intensity of light passing through the liquid in a settled state with particles. Measure the particle size distribution. Standard deviation based on this particle size distribution. It is determined from the lognormal distribution function. Note that the average particle diameter of the catalyst is shown as a weight average diameter, and the particle size distribution was calculated by sieving within a range of 10 to 20% of the weight average particle diameter. These titanium catalyst components preferably have relatively regular shapes such as spherical, ellipsoidal, and flaky shapes. In order to obtain these titanium catalyst components, a magnesium compound having the above shape with an average particle size in the range of 5 to 200 mm and a geometric standard deviation of particle size distribution of less than 2.1, preferably 1.95 or less is produced. It is preferable to suspend this in an excess liquid titanium compound or a hydrocarbon solution of a titanium compound and support the titanium compound. Alternatively, by selecting the reaction conditions between the titanium compound and the magnesium compound, it is preferable to form particles with a narrow particle size distribution such that the average particle size and particle size distribution of the catalyst component to be produced satisfy the above ranges. Methods for producing such catalyst components are described, for example, in Samurai Ko No. 50-3227, Chikai No. 49-6599,
Hakamakai No. 52-3859, Japanese Patent Publication No. 52-107704
No., Mochiseki No. 53-21093, etc.
Alternatively, it can be obtained by reacting a Glyal compound and a silicate ester, and in some cases, further reacting a halogenating agent with a titanium compound. Generally, it is known to co-pulverize a magnesium compound and a titanium compound to produce a titanium catalyst component supported on a magnesium compound, but in many cases the specific surface area is small, the particle size distribution is wide, and the shape is irregular, so it cannot be used as is. It cannot be used and requires operations such as classification. If a copolymer that does not satisfy the condition (A-2) and has a particle size outside the above range is used, a high-density copolymer cannot be obtained. Even if the titanium catalyst component does not satisfy the condition (A-1), it has a specific surface area of 80〆/ta or more, and the organic acid ester is 0.0% of titanium.
It can be used in the present invention if it is contained in an amount of 1 or 7 moles. In this case, it is more preferable if the condition (1) is also satisfied. The organic acid ester-containing titanium catalyst component is useful for the highly stereoregular polymerization of Q-olefins such as propylene, and its production method is summarized, for example, in Tokoseki No. 1, 1983-30. Alternatively, it can be obtained by reacting a reaction product of a Grignard compound and a silicate ester with an organic acid ester and, in some cases, a halogenating agent, and then reacting with a magnesium compound.
As disclosed in the above applications, the magnesium compounds used in the synthesis of the titanium catalyst component include magnesium halides, alkoxymagnesium, allyloxymagnesium, magnesium oxide, magnesium hydroxide, magnesium carbonate, hydrotalcite, and Grignard compounds. , and many other compounds. In some cases, magnesium metal is used. In addition, the titanium compounds used in the synthesis of titanium catalyst components are often tetravalent titanium compounds, and titanium tetrahalides or titanium alkoxy halides are often used, and among them, titanium tetrahalides such as titanium tetrachloride are used. Most commonly used. In order to support titanium on a magnesium compound, it is often carried out with the help of one or more types of various electron donors, organometallic compounds, silicon compounds, and the like. The titanium catalyst component corresponding to (A-1) above usually contains 0.5 to 15% by weight of titanium, particularly 1 to 10% by weight, and has a titanium/magnesium (atomic ratio) of 1'2 to 1/100. , especially 1/3 none, 1/50, halogen/titanium (molar ratio) in the range of 4 none, 200, especially 6 none, 100. Further, its specific surface area is usually 40/ta or more, particularly 60/ta or more. In addition, the titanium catalyst component corresponding to the above yA- contains 0.4 to 12% by weight of conventional titanium, particularly 0.6 to 1% by weight, and no magnesium titanium (atomic ratio) of 1/2. 1/100, especially 1/4
The halogen titanium (atomic ratio) is in the range of 5 to 200, especially 6 to 100, and the organic acid ester/titanium (molar ratio) is in the range of 0.1 to 7, preferably 0.2 to 6. The specific surface area is usually 80 or more, preferably 100 or more, and 800 or more. In addition, organic acid esters include aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, aromatic carboxylic acid esters,
Lactol, carbonate ester, etc. can be used. More specifically, methyl acetate, butyl acetate, vinyl acetate, and plastic. Aliphatic carboxylic acid esters such as ethyl pionate, isopropyl butyrate, cyclohexyl acetate, phenyl acetate, pendyl acetate, methyl chloroacetate, methyl methacrylate, methyl laurate, methyl stearate, alicyclic esters such as methyl cyclohexanecarboxylate Carboxylic acid ester, methyl benzoate, ethyl benzoate, isopropino benzoate;
/, n-butyl benzoate, vinyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl toluate,
Ethyl toluate, methyl anisate, ethyl anisate,
Examples include aromatic carboxylic acid esters such as dimethyl phthalate and methyl chlorobenzoate, lactones such as y-butyrolactone, 6-valerolactone, coumarin, and phthalide, and carbonic acid esters such as ethylene carbonate. These do not necessarily need to be used themselves during the synthesis of the titanium catalyst component, and may be formed into organic acid esters during the synthesis process, for example, by reacting a compound having an alkoxyl group with an acid halide. The organoaluminum compound B contains at least one AI in the molecule.
- Compounds having carbon bonds are available, for example (i)
General formula: R'(OR2)nHp (where RI and R2 are hydrocarbon groups usually containing 1 to 19 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. × is halogen, m is 0<mmi3, n is OSn<3, p is 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3) organoaluminum compound, 'ii1 general formula MIAIR; (where MI is L
i, Na, k, and RI is the same as above);
i) A compound of aluminum and magnesium can be mentioned. Examples of the organoaluminum compounds belonging to (i) above include the following. General formula RimAI(OR2)3-m (where RI and R2 are the same as above; m is preferably the number of 1.5Sm-3). General formula RimAIX3-m (where RI is the same as above, X is halogen, m is preferably 0<m<3), general formula RimAIH3-m (here RI is the same as above, m is preferably 2Sm <3), general formula R
imAI (OR2) gunwale q (here RI and R2 are the same as before.
<3, and m+n+q=3). (In the aluminum compounds belonging to il, more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum, triisof. In addition to alkylaluminum sesquialkoxides such as , ethylaluminum sesquiethoxide, and butylaluminum sesquibutoxide, R is AI(OR2)■
Partially alkoxylated alkyl aluminum halides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquichloride, etc., with an average composition of Alkylaluminum sesquihalogenides such as bromide, partially halogenated alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc., diethyl aluminum hydride, dibutyl Dialkyl aluminum hydrides such as aluminum hydride, partially hydrogenated alkylaluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy Partially alkoxylated and halogenated alkyl aluminums such as bromides. Also, (i'') as a similar compound,
It may also be an organoaluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom. Examples of such compounds include (C2day5)2AION(C2
Examples include 5) 2, (C4 ratio) 2NOA1 (C4 ratio) 2, and so on. Compounds belonging to (ii) above include LiA1(C2
Day 5) 4, LiA1 (C7 day, 5) 4, etc. can be exemplified. Among these, it is particularly preferable to use trialkyl aluminum and/or alkyl aluminum halide. In the present invention, ethylene is prepolymerized in an inert hydrocarbon solvent using the above A and B components, and the titanium catalyst component 1 is
0.01 to 40 evenings, preferably o. A polyethylene of 0.02% and 10%, more preferably 0.05% and 5%, is produced. The amount of this prepolymerization must be strictly regulated; if this amount is greater than the above range, not only will a high-density copolymer not be obtained, but it will also cause the formation of fish eyes, which is undesirable. Inert hydrocarbon solvents used for prepolymerization include propane, butane, n-bentane, iso-pentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene, etc. aliphatic hydrocarbons, cyclobentane,
Alicyclic hydrocarbons such as methylcyclobesotane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as methylene chloride, ethyl chloride, ethylene chloride, and chlorobenzene. Examples include hydrogen, among which aliphatic hydrocarbons, particularly aliphatic hydrocarbons having 4 to 10 carbon atoms, are preferred. In prepolymerization, titanium catalyst component A is converted into titanium atoms from 0.001 to 500 per inert solvent per night.
mmol, particularly preferably 0.005 to 200 mmol, and the organoaluminum compound B is
It is preferable to use such a ratio that the I/Ti (atomic ratio) is from 0.1 to 1000, particularly from 0.5 to 500. The temperature of prepolymerization is between 130 and 90, especially 0 and 90%.
A temperature of 70°C is preferred. Hydrogen may be allowed to coexist in the preliminary combination, if necessary. In the present invention, ethylene and Q-olefin having 3 or more carbon atoms are copolymerized using a catalyst premixed with ethylene, and the density is 0.900 to 0.0.
Group 5: Manufacture tanoji copolymer. Q-olefins having 3 or more carbon atoms include propylene,
Those having less than 1 carbon number are preferred, such as 1-ptene, 1-bentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-octadecene. and the number of carbons is 3
Particularly suitable are none and those with a density of 10. The copolymerization is carried out at a temperature of 100 qo or less, preferably from 40 to 85° C., under conditions in which the copolymer does not melt. The copolymerization is carried out in such a way that the amount is usually at least 10 N moss, preferably at least 5 P moss. Copolymerization is carried out in the form of slurry polymerization in a hydrocarbon medium or gas phase polymerization in the absence of liquid hydrocarbons. In particular, the present invention can exhibit even more remarkable effects when applied to slurry polymerization. As the hydrocarbon medium, the above-mentioned inert hydrocarbons or Q-olefins are used. Particularly preferred are aliphatic hydrocarbons, with those having 3 to 12 carbon atoms being particularly preferred. In particular, a great advantage of the present invention is that good results can be obtained even when using solutions with boiling points exceeding 40 qC. The catalyst concentration in slurry monopolymerization is 0.001 mmol to 1 mmol, preferably 0.003 mmol to 0.1 mmol in terms of titanium atoms of titanium catalyst component A, per liquid phase, and organoaluminum compound. B is usually aluminum/titanium (atomic ratio)
is in the range of 2 to 2000, preferably 10 to 1000. In order to obtain a density within the above range, it is necessary to contain about 0.2 to 30% by weight, especially about 0.3 to 25% by weight of Q-olefin in the polymer, although it varies depending on the type of catalyst and the type of Q-olefin. Just force it. Therefore, depending on the polymerization pressure, polymerization temperature and other polymerization conditions. - It is sufficient to determine the olefin supplier. The polymerization pressure is generally about 1 to 100 k9/eq. In order to control the molecular weight of the copolymer, a molecular weight regulator such as hydrogen can be added to the polymerization system. Alternatively, organic acid esters, other electron donors, and compounds such as boron, silicon, and tin may be present for the purpose of increasing catalytic activity or adjusting the molecular weight distribution of the copolymer. These are organic aluminum compound B and adducts, fin compounds,
It can also be used in the form of a reactant. The copolymerization of the present invention may be carried out in two or more stages under different conditions. Example 1 <Catalyst synthesis> Hexane 400 was prepared by dehydrating and purifying 1 mol of commercially available metallic magnesium in a nitrogen stream.

In addition to [, 1.2 mol of tetraethoxysilane was added and the temperature was raised to 6,500 ℃ below Nawa Azusa. After raising the temperature, a small amount of methyl iodide and iodine were added dropwise, followed by n
-After dropping 1.2 mol of butyl chloride over 2 hours,
I prayed for 3 hours at 7000. After the reaction was completed, it was washed repeatedly with hexane. Subsequently, 0.25 mol of ethyl benzoate was added and the mixture was reacted at 6°C for 1 hour. After extracting the top solution, 10 mol of titanium tetrachloride was added and the reaction was carried out at 120 qo for 2 hours. After extracting the titanium tetrachloride, titanium tetrachloride was further reacted under the same conditions to carry out titanium loading. After the reaction was completed, the solid portion was washed repeatedly with hexane. When the composition of the obtained solid was analyzed, it was found that each solid had T.
It was 9 for i29, 05 for M scale, 9 for CI650 and 87 for ethyl benzoate. The average particle diameter of the Ti catalyst component was 18.6 mm, with a geometric standard deviation of the particle size distribution. Noma】. 51, and the specific surface area was 230〆/unit. <Polymerization> The Ti catalyst component obtained by the above method is calculated as 3 Ti atoms.
The catalyst was diluted with dehydrated and purified hexane to a concentration of 1 hmol/hmol, and triethylaluminum was added to it.
It was added at a rate of 2 mmol per lmmol of i atoms. Subsequently, ethylene was supplied at normal pressure and 4 picoC, and 0.32 days of ethylene was reacted per night of the Ti catalyst component. Separately, put the dehydrated and purified solvent hexane IZ into the autoclave, and after purging the inside of the autoclave with nitrogen, add 1.8 hmol of triethylaluminum and 0.0 hmol of the catalyst pretreated with ethylene in terms of titanium atoms. 01 mmo
Add l, then insert hydrogen lk9/ji, and make Zensho 5k
9/ 1-butene 7. Polymerization was carried out at 65 qo for 2 hours while continuously adding ethylene containing 20 hol %, yielding 283 qo of ethylene copolymer with a cage specific gravity of 0.43 q/w and a melt index of 1.1. The density of the obtained copolymer was 0.927 m/m, and the amount of dissolved polymer in the solvent hexane was 3.8 wt%. Examples 2 to 19 When using the catalyst prepared by the method of Example 1 and changing the ethylene pretreatment conditions,
Tables 1-1 and 1-2 show examples in which the polymerization solvent for ethylene and Q-olefin was changed and the type of Q-olefin was changed under various conditions. Table 1-I *I Et: Ethyl, *2 1Bu: Isobutyl ■Funeya/Kihoro S To* Koputo S/Tokata Hina Ura Hina Ju■ Toyashitsu← Kunibata Ki/Tomozuchi Implementation Examples 20 to 24 Catalyst components> Catalysts were synthesized using the method of Example 1 using various esters instead of ethyl benzoate, and after pretreatment with ethylene in exactly the same manner as in Example 1, Example 1 Copolymerization of ethylene and 1-butene was carried out under the same polymerization conditions. The results obtained are shown in Table 2. Table 2 Example 25 <Catalyst Synthesis> 2 moles of commercially available anhydrous magnesium chloride were suspended in 4 mol of dehydrated hexane in a nitrogen stream, and 12 moles of ethanol was added dropwise over 2 hours while the mixture was heated to 70 oo. The mixture was reacted for 1 hour. To this was added dropwise 5.85 mol of diethyl aluminum chloride at room temperature, and the mixture was stirred for 2 hours. Subsequently, 3 mol of titanium tetrachloride was added dropwise, and the reaction was carried out at room temperature for 2 hours. After the reaction was completed, the solid portion produced was washed repeatedly with hexane. The composition of the obtained solid was 9/2 solid with Ti spots, 9 with CI590.
There were 185 p/t solids, Mg 185 p/t solids, and 155 p/t solids as OEt basis. In addition, the specific surface area of the solid catalyst is 225〆/ter solid, and the average catalyst particle size is 1
6.6 peaks, the geometric standard deviation of the particle size distribution of catalyst particles is 1.6
It was 9. <Polymerization> 2 Dehydrated and purified solvent hexane 1 in the autoclave
After filling the autoclave and purging the inside of the autoclave with nitrogen, add triethylaluminum 2. 0.015 hmol of the above solid catalyst was added in terms of titanium atoms, and the catalyst was pretreated while inserting 20 mol of ethylene under normal pressure. The pretreatment corresponds to 4.4 nights of ethylene per night of titanium catalyst component. Next, the temperature inside the autoclave was raised to 65 oo, hydrogen 1.0k9/base was added, and the total pressure was increased to 4k9.
Polymerization was carried out at 65° C. for 1 hour while continuously adding ethylene containing 6.3 hol% of 1-butene to give ethylene with a bridge specific gravity of 0.37 hol% and a melt index of 0.3. Copolymer 262 was obtained. Its density was 0.929 m/m, and the dissolved polymer in the solvent hexane was 5.1 wt%. Example 26 <Catalyst Synthesis> Commercially available magnesium hydroxide 2k9 having a specific surface area of 67 mm/h was suspended in water, and the mixture was heated to 500 rpm using a homomixer having a turbine stator with a content of 20 mm. Concentration treatment was performed for 1 hour under the condition of /m. Subsequently, this water slurry of magnesium hydroxide was poured into Azusa 8.
When the temperature was raised to 0oC and a two-fluid nozzle with a diameter of 0.254 was used, spherical magnesium hydroxide was obtained using a mist dryer in parallel flow with hot air at 20,000 °C.
Next, a splitting operation was performed to obtain a section of 20 mm to 63 mm. The magnesium hydroxide thus obtained had a specific surface area of 86 mm/h and was spherical in shape. Twenty grams of the spherical magnesium hydroxide obtained by the above procedure were inserted into 300 ml of titanium tetrachloride, and a reaction was carried out at 135 qC for 2 hours. After the reaction was completed, titanium tetrachloride was extracted, and then washed repeatedly with hexane. When the obtained solid was analyzed for its composition, it was found that, in terms of Ti atoms, 19:2, magnesium: 360, and chlorine: 290 were supported per solid. The average particle diameter of the catalyst component obtained was 36〃, the geometric standard deviation of the catalyst particle size distribution. The specific surface area of the catalyst was 92〆/unit. <Polymerization> The Ti catalyst component obtained by the above method is calculated as 2 Ti atoms.
The catalyst was diluted with dehydrated and purified hexane to a concentration of 0 hmol/hmol, and triethylaluminum was added to the diluted hexane.
3 hmol was added per lmmol of i atom. Subsequently, ethylene was supplied at a normal pressure of 4,000 yen, and 0.40 yen of ethylene was reacted per 1 yen of the titanium catalyst component, thereby pretreating the catalyst with ethylene. Separately, after purging the inside of the autoclave sufficiently with nitrogen, tethylaluminum 2. 0.0 mol of titanium atoms was added to the catalyst pretreated with ethylene, followed by 1.5 mol of hydrogen.
When polymerization was carried out at 60°C for 2 hours while continuously adding ethylene containing 7.5 hol% of 1-butene at a total pressure of 7k9/base, the bulk specific gravity was 0.36. 213 pieces of ethylene copolymer with a melt index of 0.73 were obtained. The density of the obtained ethylene copolymer was 0.931 m/m, and the dissolution of the polymer in the solvent hexane was 4.9 m/m. is t%
Met. Example 27 <Catalyst synthesis> Electron donor, organoaluminium,
It was reprocessed with titanium tetrachloride and used as a catalyst. First, 30 tons of the titanium catalyst component obtained by the method of Example 26 was placed in a three-necked flask that had been sufficiently purged with nitrogen, and 15 tons of kerosene was added.
Added 0 birds. Ethyl benzoate was added dropwise thereto at a reaction temperature of 30 qC in an amount 4 times the mole (47.8 hmol) of Ti supported on the catalyst obtained by the method of Example 26, and the mixture was heated at 30 qC for 1 hour. Subsequently, 1/2 mole of ethyl benzoate of diethylaluminum chloride was added dropwise under the reaction condition of 3000°C, and the mixture was heated at 30°C for 1 hour after the dropwise addition. Thereafter, the solvent, kerosene, was extracted by the diagonal method, and after washing twice with 150 ml of kerosene, 150 ml of titanium tetrachloride was added, and the reaction was carried out at 13 ml of kerosene for 2 hours. It was then washed repeatedly with hexane. When the obtained solid was analyzed for composition, it was found that Ti atoms per night were 20:9, chlorine: 310:9, and Mg: 33
0 o, ethyl benzoate was loaded with 42M. The average particle diameter of the obtained catalyst was 37r, and the geometric standard deviation of the catalyst particle size distribution. The specific surface area of the 1.4 stop catalyst is 90〆/
It was evening. <Polymerization> The Ti catalyst component obtained by the above method was diluted with dehydrated hexane to a concentration of 20 hmol/Ti atom, and triethylaluminum was added to this at a concentration of 3 hmol/lmmol of Ti atoms.
Added. Subsequently, ethylene was added to the reactor at normal pressure of 40 qC, and 0.4 ethylene was reacted per titanium catalyst component to pre-treat the catalyst with ethylene. Separately, after purging the inside of the autoclave sufficiently with nitrogen, 2. skin mol, 0.02 hmol of the catalyst pretreated with ethylene in terms of titanium atoms was added, followed by 1.5 hmol of hydrogen.
When polymerization was carried out at 6000 for 2 hours while continuously adding ethylene containing 7.5 hol% of 1-butene, the bulk specific gravity was 0.40. An ethylene copolymer 355 with a melt index of 10 was obtained. The density of the obtained ethylene copolymer was 0.928 m/m, and the amount of dissolved polymer in the solvent hexane was 4.4 wt.
%Met. Example 28 <Catalyst synthesis> 1 containing 0.1 mol of n-butylmagnesium chloride
00' n-butyl ether solution was inserted into a flask, and it was added dropwise to it in a N2 stream at room temperature for 1 hour, and then the temperature was slowly raised to 65C0 to 65oo
It reacted for 1 hour. The obtained solid magnesium compound was washed repeatedly with hexane. Subsequently, 0.02 ol of ethyl benzoate was added, and the reaction was allowed to proceed for 1 hour at Machio. After the obtained solid was separated in a furnace, 15 ml of titanium tetrachloride was added per solid per night, and the mixture was reacted at 110 qo for 2 hours. After the reaction was completed, it was washed repeatedly with hexane. Composition analysis of the obtained solid revealed that Ti24 female and Mg2 per solid overnight.
On the evening of the 15th, the CI was 640 o, and the ethyl benzoate was 82 mo. Also, the average particle size of the catalyst is 18.3-, the geometric standard deviation of the catalyst particle size distribution. The specific surface area of the 1.68 catalyst is 18
It was 7/7 evening. <Polymerization> 2 Dehydrated and purified solvent hexane 1 in the autoclave
After filling the autoclave with sufficient nitrogen, add triethylaluminum 2. 0.015 hmol of the above solid catalyst in terms of titanium atoms was added, and the catalyst was pretreated while inserting ethylene at 3 C under normal pressure. The amount of pretreatment corresponds to 7.1 nights of ethylene per night of catalyst. Next, the temperature inside the autoclave was raised to 6,500, hydrogen was added at 1.5 k9/c, and ethylene containing 8.5 hol% of 1-butene was continuously added at a total pressure of 6 k9/c. When polymerization was carried out at 65°C for 2 hours while adding, the bulk specific gravity was 0.39 m/kg and the melt index was 2.
294 ethylene copolymers of No. 5 were obtained. The density of the obtained ethylene copolymer was 0.929 mm/block, and the amount of dissolved polymer in the solvent hexane was 4.7 wt%. Example 29 <Catalyst synthesis> Commercially available anhydrous magnesium chloride 20 and ethyl benzoate 6
．． 0' in a nitrogen atmosphere into a stainless steel container with an internal volume of 800' and containing a stainless steel (SUS-302) ball with a diameter of 15 mm, Co-pulverization was carried out for 50 hours using a vibrating mill device. The obtained solid treated product was suspended in titanium tetrachloride and reacted at 10 and 0 for 2 hours, and then the solid components were separated in a furnace and washed repeatedly with hexane. When the composition of the obtained solid catalyst component was analyzed, it was found that 9 of Ti21 and 10 of M chick per solid one night were analyzed.
9, chlorine 670, and ethyl benzoate.
In addition, the catalyst average particle size of the obtained Tj catalyst component was 17.8 French, and the geometric standard deviation of the catalyst particle size distribution. The specific surface area of the Noma 2.2 catalyst was 185〆/unit. <Polymerization> After performing a pretreatment equivalent to 5.5 nights of ethylene per night of catalyst in the same manner as in Example 28, copolymerization of ethylene and 1-butene was performed in the same manner as in Example 28. As a result, an ethylene copolymer having a high specific gravity of 0.34 and a melt index of 1.1 was obtained. The density of the obtained ethylene copolymer was 0.932 m/g, and the amount of dissolved polymer in the solvent hexane was 3.1 wt%.
Met. Comparative Example 1 <Catalyst Synthesis> 20 kg of commercially available anhydrous magnesium chloride was placed in a stainless steel spade (SUS-302) ball with a diameter of 15 mm in a nitrogen atmosphere.
The mixture was placed in a stainless steel container with an internal volume of 800 M and a diameter of 10 m, containing 100 oz of solids, and pulverized for 5 s in a vibrating mill with a capacity of 70 ml. The obtained solid treated product was suspended in titanium tetrachloride and
After reacting for 2 hours at 0.00 °C, the solid components were separated and washed repeatedly with hexane. . When the composition of the obtained solid catalyst component was analyzed, it was found that Tilo's o, M
g235 female, chlorine 730mc. Also obtained T
The average catalyst particle diameter of the i catalyst component is 12.2 peaks, and the geometric standard deviation of the catalyst particle size distribution. 2.31, the specific surface area of the catalyst is 55
It was evening. <Polymerization> In exactly the same manner as in Example 1, the catalyst was pretreated with ethylene in an amount equivalent to 0.36 hours per night of catalyst. When copolymerization of ethylene and 1-butene was carried out using the pretreated catalyst under the same conditions as in Example 1, an ethylene copolymer with a bulk specific gravity of 0.21 y/m and a melt index of 2.5 was obtained. I got the evening. The density of the obtained ethylene copolymer is 0.939 m/m, and the dissolved polymer in the solvent hexane is 19.9 m/m. t% of powder, and the bulk specific gravity and yield were very poor. Comparative Example 2 <Catalyst Synthesis> Commercially available anhydrous magnesium chloride 23, titanium tetrachloride 2.
4th night, aluminum chloride-diphenylene complex 4.
It was inserted into a stainless steel container with an internal volume of 800 mm and containing a stainless steel ball of 15 mm in diameter in a nitrogen atmosphere for 5 nights, and was heated for 2 hours using a vibration mill device with a capacity of 7 G. Shattered. When the composition of the obtained solid was analyzed, it was found that the solid had 20 o's of Ti, 10 females of M, and 640 CI's per night. Moreover, the catalyst average particle diameter of the obtained Ti catalyst component was 13.8r,
Geometric standard deviation of catalyst particle size distribution. The specific surface area of the catalyst was 29〆/〆/〆. <Polymerization> As in Example 1, the catalyst was pretreated with ethylene equivalent to 0.41 sulfur per night of catalyst. When copolymerization of ethylene and 1-butene was carried out using the pretreated catalyst under the same conditions as in Example 1, an ethylene copolymer of 125 I got the evening. The density of the obtained copolymer is 0
．． The amount of polymer dissolved in the solvent hexane is 10. The yield was low, and the bulk specific gravity was also poor. Comparative Example 3 When copolymerization of ethylene and 1-butene was carried out using the catalyst prepared by the method of Example 25 under the same conditions as in Example 25 without pretreatment with ethylene, a high specific gravity of 0.30 An ethylene copolymer 203 with a melt index of 1.3 was obtained. The density of the obtained copolymer was 0.931 m/g, and the amount of dissolved polymer in the solvent hexane was 9. t%, which decreased with bulk specific gravity and solid polymer yield. Example 3
500 μl of sodium chloride as a catalyst dispersant was placed in the autoclave (equipped with a rope sieve) and the system was sufficiently purged with nitrogen. Raise the temperature of the system, and at 7 pm, 4-methylbentene-1, 5.5
Ethylene gas containing 6 mol % was supplied at 60 plates/hour and hydrogen was supplied at 10 plates/hour while maintaining the pressure at 5k9/G. Tj pretreated with 2.5 mmol of triisobutylaluminum and ethylene from Example 1
It was added to the system in an amount of 0.02 9-atoms in terms of atoms. Polymerization was carried out for 1 hour by supplying gas at 7,000 ℃ while maintaining the above flow rate and pressure of 5k9/g. The yield of the obtained ethylene copolymer was 106 mm, bulk specific gravity was 0.3 M/10', MI was 1.0 mm/10', and the density of the polymer was o. It was 928 evening/earth. Comparative Example 4 <Catalyst synthesis> 2 moles of commercially available anhydrous magnesium chloride were suspended in 5 dehydrated hexane in a nitrogen stream, 12 moles of ethanol was added dropwise over 2 hours while holding a light, and then 1 mole of ethanol was added at room temperature. I reacted in time. To this, 5.4 mol of diethyl aluminum chloride was added dropwise at room temperature, and the mixture was stirred for 2 hours. Next, titanium tetrachloride 15
After adding mol, the temperature of the system was raised to 80 qo, and the reaction was carried out for 3 hours with stirring. The generated solid portion was separated by sieving and washed repeatedly with purified hexane. moreover,
By removing the coarse particles by classification, the average particle diameter of the catalyst was 2.1 French, and the geometric standard deviation of the particle size distribution of the catalyst particles was obtained. In the evening, 1.87 liters of catalyst was obtained. The composition of the obtained solid was 67 o/ter solids as Ti atoms, MO as CI atoms, 180 9/ter solids as Mg atoms, OE
There were 95 9/ter solids present in each case. Further, the specific surface area of the solid was 240m. <Polymerization> Polymerization was carried out under the conditions of Example 25.

Claims (1)

[Claims] 1. (A) A titanium catalyst component supported on a magnesium compound. and (B) using a catalyst formed from an organoaluminum compound, ethylene and a small proportion of α-olefin having 3 or more carbon atoms are copolymerized at a temperature of 100°C or less to obtain a density of 0.900 to 0.945 g/cm. In the method for producing an ethylene copolymer of ^3, as component (A), (A-1) has a specific surface area of 40 m^2/g or more, an average particle size in the range of 5 to 200 μ, and a geometric particle size distribution. Using a material with a standard deviation σg of less than 2.1 and/or (A-2) a material having a specific surface area of 80 m^2/g or more and containing an organic acid ester of 0.1 to 7 moles as much as titanium, Titanium catalyst component (A) prior to copolymerization
A method for producing an ethylene copolymer, characterized in that the polymerization is carried out after 0.01 to 40 g of ethylene is polymerized per 1 g.