JPS6349686B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for continuous polymerization of olefins using a highly active catalyst. Olefins are produced using a catalyst consisting of a catalyst component derived from a magnesium halide to which an electron donor has been added, a halogen compound of silicon or tin, and a transition metal compound, and an organometallic compound catalyst component of a metal from Group 1 to Group 3 of the Periodic Table. A method for polymerizing these compounds has already been proposed by the present applicant (for example, Japanese Patent Publication No. 1796/1983 and Japanese Patent Publication No. 25517/1989). In these proposals, a transition metal compound supported on a magnesium compound is prepared prior to polymerization, and by using this in combination with an organometallic compound of a metal from Groups 1 to 3 of the periodic table, highly active polymerization of olefins is possible. It was hot. The present inventors further investigated the catalyst system and found a method that allows highly active polymerization to be carried out without performing a preliminary supporting reaction in continuous polymerization. According to this new polymerization method, it is possible to produce a polymer (or copolymer) with a narrow molecular weight distribution, and it is also possible to produce a copolymer with a narrow composition distribution and excellent transparency. be. Accordingly, an object of the present invention is to provide a method for continuous polymerization or copolymerization of olefins, which omits the supporting reaction conventionally used in highly active catalysts using magnesium compounds. Another object of the present invention is to provide a method for highly active polymerization of olefins, which makes it possible to produce polyolefins with a narrow molecular weight distribution. Still another object of the present invention is to provide a method for producing a polyolefin, which, when applied to the copolymerization of olefins, can produce a copolymer with a narrow composition distribution and good transparency. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. According to the present invention, (A) a solid component obtained by treating magnesium halide to which an active hydrogen-containing electron donor has been added with a halide of silicon, sulfur, or phosphorus; (B) in the component (A); For one atom of magnesium, 1/
Continuously polymerizing or copolymerizing olefins in the presence of a polymerization catalyst obtained by contacting a liquid Ti compound component corresponding to 2 or less titanium atoms and (C) an organoaluminum compound component. Component (B) is supplied to the polymerization system separately from other components (A) and (C), or at least a portion of component (A), at least a portion of component (B), and
At least a portion of component (C) is preliminarily mixed before being supplied to the polymerization system, and the preliminary mixing is performed with (A).
Provided is a method for continuous polymerization or copolymerization of olefins, which comprises mixing (B) with a mixture of (C) or simultaneously mixing components (A), (B), and (C). . The magnesium halide component of magnesium halide to which an active hydrogen-containing electron donor is added is
In addition to ingredients such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride,
It may be a halogenated magnesium component having a functional group such as an alkoxyl group or an allyloxyl group. Preferred are the above-mentioned magnesium dihalides, particularly preferred is the magnesium chloride component. Magnesium halide to which an active hydrogen-containing electron donor has been added can be produced by contacting the active hydrogen-containing electron donor with magnesium halide. As the magnesium halide, a commercially available product may be used as it is, or another magnesium compound or magnesium metal may be halogenated with a halogenating agent to be described later. As the active hydrogen-containing electron donor, oxygen-containing electron donors such as alcohols, phenols, carboxylic acids, and carboxylic acid amides, and nitrogen-containing electron donors such as ammonia, primary amines, and secondary amines may be used. Can be done. Typical examples of these include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-
Butanol, tert-butanol, n-pentanol, n-hexanol, cyclohexanol, n
-Octanol, 2-ethyl-hexanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, oleyl alcohol, benzyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, n-butyl cellosolve, 1-butoxy-2-propanol Alcohols with 1 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, isopropylphenol, octylphenol, nonylphenol, cumylphenol, naphthol, phenols with 6 to 15 carbon atoms such as methoxyphenol, acetic acid, pyrropion acids, carboxylic acids with 2 to 20 carbon atoms such as butyric acid, lauric acid, oleic acid, and stearic acid, acetate amide,
Carboxylic acid amides having 2 to 15 carbon atoms such as propionic acid amide and benzoic acid amide, methylamine, ethylamine, iso-propylamine, n-
Primary amines having 1 to 20 carbon atoms such as butylamine, n-hexylamine, n-octylamine, n-decylamine, n-octadecylamine, cyclohexylamine, aniline, dimethylamine, diethylamine, methylethylamine, di-n
-propylamine, methyl n-hexylamine,
Representative examples include secondary amines having 2 to 40 carbon atoms such as methyl n-decylamine and dibenzylamine. Two or more of these may be used in combination. To add an electron donor to magnesium halide, generally the magnesium halide and electron donor are brought into contact at a temperature of about 0 to 200°C for about 10 minutes to 48 hours in the presence or absence of an inert solvent. Just let it happen. The amount of the electron donor used is generally 0.1 to 30 mol, preferably 0.5 to 20 mol, particularly preferably 0.5 to 10 mol, per 1 mol of magnesium halide. When the reaction is carried out in the presence of an inert solvent, the electron donor is allowed to act while the magnesium halide is suspended in the inert solvent. Although it varies depending on the type and amount of electron donor, reaction temperature and time, type of inert solvent, etc., the adduct of magnesium halide and electron donor can be obtained in a suspended state in an inert solvent. In some cases, it can be obtained in a state dissolved in an inert solvent, and both can be used in the present invention. In particular, in the present invention, by using a compound dissolved in an inert solvent and reacted with a halogenating agent as described later, it is possible to obtain a polymer with a narrower molecular weight distribution and even narrower composition distribution in the case of a copolymer. Therefore, it is preferable. A method for producing an adduct of magnesium halide and an electron donor that is soluble in an inert solvent is described. For example, when alcohol is used as an electron donor, alcohol is preferably used in an amount of 2.8 or more, preferably about 3 to about 20 moles, particularly preferably about 3 to about 10 moles, per 1 mole of magnesium halide. It will be done. When using an aliphatic hydrocarbon and/or alicyclic hydrocarbon as the hydrocarbon, use alcohol in the above ratio,
Among them, if an alcohol having 6 or more carbon atoms is used, in particular, about 1 mol or more, preferably about 1.5 mol or more, per 1 mol of magnesium halide, it is possible to solubilize magnesium halide with a small total amount of alcohol used. Moreover, it is preferable because it becomes a highly active catalyst component. In this case, for example, if only an alcohol having 5 or less carbon atoms is used, approximately 15 mol or more of the alcohol is required per 1 mol of magnesium halide, and the catalytic activity is also inferior to that of the above system.
On the other hand, if an aromatic hydrocarbon is used as the hydrocarbon, magnesium halide can be solubilized with the amount of alcohol used as described above, regardless of the type of alcohol. Contacting the magnesium halide with the alcohol is preferably carried out in a hydrocarbon medium and is usually about
This is carried out by contacting at a temperature of 65° C. or higher, preferably about 80 to 300° C., more preferably about 100 to about 200° C., for about 15 minutes to about 5 hours, more preferably about 30 minutes to about 2 hours. As a method for synthesizing the adduct in the absence of an inert solvent, there is a method in which magnesium halide is suspended or dissolved in an electron donor and the reaction is carried out under the same conditions as in the presence of an inert solvent. can be mentioned. Another method is to bring the magnesium halide and the electron donor into contact under mechanical grinding conditions. When treating magnesium halide to which an active hydrogen-containing electron donor has been added with a halogenating agent described below, magnesium halide to which an electron donor not containing active hydrogen has been added may coexist; , an active hydrogen-free electron donor may also be present. Examples of such active hydrogen-free electron donors include oxygen-containing electron donors such as ketones, aldehydes, carboxylic acid esters, ethers, carboxylic acid halides, carboxylic acid N,N-dialkylamides, and phosphoric acid esters;
Examples include tertiary amines and nitrogen-containing electron donors such as nitriles. The halogenating agent used in the treatment of magnesium halide to which an active hydrogen-containing electron donor has been added is other than organometallic compounds and transition metal compounds of metals from Groups 1 to 3 of the Periodic Table, and is an active hydrogen-containing electron donor. It is a halogenating agent that can react with the body. Specifically, non-organic halogen compounds of Group 3a elements of the periodic table such as aluminum and gallium;
Periodic table 5a of halogen compounds of group 4a elements of the periodic table such as silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, etc.
Examples include halogen compounds of group elements, halogen compounds of group 6a elements of the periodic table, such as sulfur and selenium, and halogens. More specifically, _AlCl3 , _AlBr3 , Al( _OC2H5 ) _{Cl2 ,} Al
( _OC3H7 ) _{Cl2 ,} Al _{( OC4H9} ) _Cl2 , Al( _OCH3 ) _2Cl ,
Halogen compounds of Group _3a elements of the periodic table such as GaCl3, _SiCl4 , _{CH3SiCl3 ,} ( _CH3 ) _{2SiCl2 ,} ( _CH3O )
_SiCl3 , _{( C2H5O} ) _{2SiCl2 ,} ( _C2H5O ) _{3SiCl ,} halopolysiloxane _{, GeCl4} , (C2H5O)GeCl3 _{, SnCl4 ,}
Halogen compounds of Group 4a elements of the periodic table such as _PbCl4 , NOCl, _PCl5 , _PCl3 , _POCl3 , _SbCl5 , _BiCl3
Halogen compounds of Group 5a elements of the periodic table, such as
Examples include halogen compounds of Group 6a elements of the periodic table such as SOCl ₂ , SO ₂ Cl ₂ , and SeOCl ₂ , and halogens such as chlorine, bromine, and iodine. In order to treat the magnesium halide to which an active hydrogen-containing electron donor has been added with the halogenating agent, a method is adopted in which the halogenating agent is added to and brought into contact with the magnesium halide dissolved or suspended in an inert solvent. is preferable. The amount of the halogenating agent to be used is calculated in terms of halogen atoms per mole of active hydrogen-containing electron donor (including those added to magnesium halide and those existing free, if any) present in the treatment system. , usually 1
It is preferable to set the ratio to be at least atomic, preferably 1.5 to 15 atoms. The treatment temperature varies depending on the type of halogenating agent, but is preferably 0 to 200°C, particularly preferably 20 to 120°C. Through this treatment, part or all of the active hydrogen-containing electron donor added to the magnesium halide is eliminated, resulting in highly amorphous magnesium halide or a complex compound of magnesium halide having a similar structure. It is obtained in solid form as . The solid component thus obtained is used as the catalyst component (A), and a particularly preferred one is a complex compound similar to magnesium chloride in which 0.2 to 1.0 mole of unreacted alcohol is added to magnesium, (110) The half width in surface X-ray diffraction is
It is in the range of 1.0 to 2.3. Normally, the treated solid component is isolated and washed with an inert solvent, but if desired, the treated mixture obtained as a suspension of the solid component can be directly subjected to the polymerization of olefin. You can also do it. As the liquid transition metal compound component (B), a titanium compound or a vanadium compound component is preferred, and a titanium compound is particularly preferred. For example Ti(OR)
_o X _4-o (R is a hydrocarbon group, X is a halogen, 0≦n≦
4) A titanium compound represented by, for example, TiCl ₄ ,
_{TiBr4 , TiI4} , Ti( _OCH3 ) _Cl3 , Ti( _OC2H5 ) _Cl3 ,
Ti(OC ₆ H ₅ ) Cl ₃ , Ti(OC ₂ H ₅ ) ₂ Cl ₂ , Ti
(OC ₃ H ₇ ) ₂ Cl ₂ , Ti(OC ₂ H ₅ ) ₃ Cl, Ti(OC ₆ H ₅ ) ₃ Cl,
Ti(OC ₂ H ₅ ) ₄ , Ti(OC ₃ H ₇ ) ₄ , Ti(OC ₄ H ₉ ) ₄ , Ti
(OC ₆ H ₁₃ ) ₄ , Ti (OC ₆ H ₁₁ ) ₄ , Ti (OC ₈ H ₁₇ ) ₄ , Ti
[OCH ₂ (C ₂ H ₅ ) CHC ₄ H ₉ ] ₄ , Ti (OC ₉ H ₁₉ ) ₄ , Ti
[OC ₆ H ₃ (CH ₃ ) ₂ ] ₄ , Ti (OCH ₃ ) ₂ (OC ₄ H ₉ ) ₂ , Ti
(OC ₃ H ₇ ) ₃ (OC ₄ H ₉ ), Ti (OC ₂ H ₅ ) ₂ (OC ₄ H ₉ ) ₂ , Ti
Examples include (OC ₂ H ₄ Cl) ₄ and Ti(OC ₂ H ₄ OCH ₃ ) ₄ . Other examples of titanium compounds are those with low valence, regardless of their crystal system. Specifically, titanium tetrachloride is reduced with titanium metal to form TiCl ₃・T type, aluminum metal is used to reduce titanium ₃・A type, hydrogen is used to reduce TiCl ₃・H type, (C ₂ H ₅ ) ₃ Al,
Titanium trihalides such _{as TiCl3} reduced with organoaluminium compounds such as ( _C2H5 ) _2AlCl , ( _{C2H5 ) 1.5AlCl1.5} , _Ti ( _{OCH3 ) 3 ,} Ti( OC ₂ H ₅ ) ₃ , Ti
( _OnC4H9 ) _{3 ,} Ti( _OCH3 ) _Cl2・_2CH3OH ,Ti
(OCH ₃ ) ₂ Alkoxytitanium () compounds such as Cl・CH ₃ OH, obtained by hydrogen reduction of TiCl ₃
Examples include TiCl ₂ and the like. Normally solid transition metal compounds such as titanium trichloride and titanium dichloride are treated to become liquid before use. The treatment preferably involves contacting an electron donor such as an alcohol, ether, ester, amine, or ketone, preferably from about 1 to about 24 moles, more preferably from about 3 to about 15 moles, per mole of the transition metal compound. That's fine. In some cases, only a portion of the transition metal compound is dissolved, and in that case, it is preferable to separate and use only the solubilized portion. In addition, as a vanadium compound, VO(OR) _n X _3-n (R and X have the same definition as before, 0≦
Compounds represented by m≦3) or VX ₄ are common, such as VOCl ₃ , VO(OC ₂ H ₅ )Cl ₂ ,
VO(OC ₂ H ₅ ) ₃ , VO(OC ₂ H ₅ ) _1.5 Cl _1.5 , VO
(OC ₄ H ₉ ) ₃ , VO [OCH ₂ (CH ₂ )CHC ₄ H ₉ ] ₃ , VCl ₄
Examples include: As the organoaluminum compound (C), a compound having at least one Al-carbon bond in the molecule can be used, for example, (i) a compound having the general formula R ¹ _n Al (OR ² ) _o
HpXq (where R ¹ and R ² are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different. X is halogen, m is 0<m≦ 3, n is a number of 0≦n<3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3), (ii) general formula M ¹ AlR ¹ ₄ (where
M ¹ is Li, Na, or K, and R ¹ is the same as above), and complex alkylated products of Group 1 metals and aluminum can be mentioned. Examples of the organoaluminum compounds that belong to (i) above include the following. General formula R ¹ mAL
(OR ² ) _3-n (where R ¹ and R ² are the same as above. m
is preferably a number of 1.5≦m<3). general formula
R ¹ mAlX _3-1 (where R ¹ is the same as above, X is halogen, m is preferably 0<m<3), general formula
R ¹ mAlH _3-n (where R ¹ is the same as above, m is preferably 2≦m<3), general formula R ¹ mAl(OR ² )
nXq (where R ¹ and R ² are the same as before, X is halogen, 0<m≦3, 0≦n<3, 0≦q<3 and m
n+q=3). Among the aluminum compounds belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum,
Besides trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, dibutylaluminum butoxy, alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, R ¹ _2.5 Al ( OR ² ) Partially alkoxylated alkyl aluminum halogenides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, with an average composition expressed as _0.5 , etc. , alkyl aluminum sesquihalogenides, such as ethyl aluminum sesquibromide,
Partially halogenated alkylaluminiums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc., dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride , partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as propyl aluminum dihydride, partially alkoxylated and halogenated alkyls such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide It is aluminum. Further, as a compound similar to (i), it may be an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ , Examples include: Further, these exemplified compounds may be used in combination. Examples of compounds belonging to (ii) above include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Among these, it is particularly desirable to use trialkyl aluminum, alkyl aluminum halide, or a mixture thereof. In the present invention, continuous polymerization or copolymerization of olefins is performed using the components (A), (B), and (C) described above. Olefins used for polymerization include ethylene,
These include propylene, 1-butene, 4-methyl-1-pentene, 1-octene, etc., and these can be used not only for homopolymerization but also for random copolymerization and block copolymerization. In copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can be selected as copolymerization components. Polyunsaturated compounds such as butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene
When copolymerizing 2-norbornene, 1,7-octadiene, etc., it may be copolymerized in a proportion of about 0.1 to 5 mol%, preferably about 0.2 to 3 mol%. In this case, the resulting copolymer has an iodine value of about 5 to 30, and can be vulcanized with sulfur. Its vulcanized properties are also excellent, and it can be used as a vulcanized rubber with high strength. The resulting polyolefin may be resinous or rubbery. According to the present invention, it is possible to obtain a polymer with a narrow molecular weight distribution. However, the purpose of the present invention is not limited to this, for example, for the purpose of improving the processability of olefins, polymers with a wide molecular weight distribution are produced by using a molecular weight regulator or by combining two or more different polymerization conditions. You can also get combinations. According to the present invention, when applied to the copolymerization of two or more olefins, it is possible to obtain a copolymer with a narrow composition distribution and good transparency. For example, it can be used to copolymerize ethylene with other α-olefins, propylene with other α-olefins, etc. to produce olefins with good transparency. The polymerization according to the invention is preferably carried out in a hydrocarbon liquid medium. Hydrocarbon liquid media include pentane, hexane, heptane, octane, decane, dodecane,
Aliphatic hydrocarbons and their halogen derivatives such as kerosene; alicyclic hydrocarbons and their halogen derivatives such as cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons and chlorobenzene such as benzene, toluene, and xylene. Examples include halogen derivatives thereof such as. Moreover, the olefin itself used for polymerization can also be used as a liquid medium. The usage ratio of each catalyst component in the polymerization system is transition metal compound component (B)/magnesium halide component.
(A) (molar ratio) in terms of transition metal/magnesium is about 1/2 or less, preferably about 1/3 to about 1/200, particularly preferably about 1/5 to about 1/50, and organoaluminum compound (C ) must be in an amount that will not be deactivated by electron donors that may be contained in component (A), and the aluminum/transition metal atomic ratio is approximately 5.
It is preferable to set the number to about 2000 to about 2000, particularly about 20 to about 500. In addition, for the liquid phase 1 of the polymerization system,
The transition metal inclusion is preferably about 0.0005 to about 1 mmol, more preferably about 1 mmol in terms of transition metal.
It is said to be 0.001 to about 0.5 mmol. It should be noted that if the ratio of component (B) to component (A) exceeds the above range, the catalytic activity per transition metal will decrease, which is not preferable. When supplying the catalyst components to the polymerization system, there are two methods: (A), (B), and (C) are supplied separately; only (B) is supplied separately, and at least a portion of (A) and ( C) A method of premixing and supplying at least a portion of (A), (B), and (C), wherein at least a portion of each of (A), (B, and C) is premixed; Methods include supplying (B) to the mixture, or mixing (A), (B), and (C) simultaneously and supplying the mixture to the polymerization reaction zone. An embodiment in which (A) and (B) are preliminarily mixed has already been proposed by the present applicant. Further, it is not preferable to bring the components (B) and (C) into contact with each other to preliminarily generate a solid transition metal compound, since this will reduce the polymerization activity. The polymerization or copolymerization temperature of the olefin is generally about 20 to about 300°C, preferably about 65 to about 200°C. In particular, in order to produce a polyolefin with good transparency in the copolymer production method, it is preferable to carry out liquid phase polymerization using an inert hydrocarbon medium and select a temperature at which the polyolefin dissolves. For example, ethylene and a small proportion of other α-
When a resinous copolymer is produced by copolymerization with olefin, the melting point of the copolymer
Preferably, the temperature is 200°C. The polymerization pressure is preferably from atmospheric pressure to about 100 kg/cm ² -G, particularly from about 2 to about 50 kg/cm ² -G. In carrying out the present invention, hydrogen, organometallic compounds of Group 2 metals of the periodic table, and/or various electron donors such as alcohols, ethers, esters, amines, Ketones, carboxylic acids, amides, phosphorus compounds, sulfur compounds, acid anhydrides, etc. may also be present. Next, a more detailed explanation will be given with reference to Examples. A continuous polymerization reactor with an internal volume of 200 was used for the polymerization in the following examples. The lines for supplying each catalyst component to the polymerization vessel were arranged to merge with the main line for supplying the polymerization solvent at variable points before reaching the polymerization vessel. Furthermore, each line was equipped with a heat insulating device, so that the charging order, temperature, and contact time of each catalyst component could be changed in each experiment. Furthermore, the molecular weight of the polymer was adjusted by continuously changing the amount of hydrogen supplied. Example 1 1.0 mol of commercially available anhydrous magnesium chloride was suspended in refined kerosene (2) under nitrogen, 3.0 mol of 2-ethylhexanol was added thereto, the temperature was gradually raised while stirring, and the mixture was reacted at 120°C for 2 hours. Ta. The solid disappeared completely and a colorless and transparent liquid was obtained. Even when this solution was cooled to room temperature, no solid precipitated and it remained a colorless and transparent solution. Next, 3.0 mol of silicon tetrachloride was added to this solution, and the mixture was reacted at 50°C for 3 hours. After the reaction was completed, the obtained white powder was washed with refined kerosene from Step 2. When a portion of this solid was dried and subjected to various analyses, it was confirmed that it was a complex compound similar to magnesium chloride with extremely low crystallinity and containing a small amount of 2-ethylhexanol. Ensure that the supply lines for each catalyst component join the main solvent charging line at almost the same point;
From one of them, an equimolar mixture of triethylaluminum and diethylaluminium monochloride was prepared.
36 mmol/hr, and from the other one, the refined kerosene solution of titanium tetrachloride is converted to titanium atoms, 0.45 mmol/hr,
From the other one, the refined kerosene suspension of magnesium component obtained above is converted into magnesium atoms.
4.5 mmol/hr was continuously supplied. At the same time, ethylene was continuously supplied to the polymerization vessel at a rate of 12.0 kg/hr, 4-methyl-1-pentene 12.0/hr, and hydrogen 60/ ^hr . Continuous polymerization was carried out with a residence time of about 1 hour. At this time, the concentration of the copolymer with respect to the solvent hexane was 72.0 g/m, and the polymerization activity was 16000 g-copolymer/mmol-Ti. The density of the obtained copolymer was 0.927 g/cm ³ , MI = 1.98, and the number of isobutyl groups per 1000 carbon atoms was 12.8. When this copolymer was molded into a film with a thickness of 65 μm using a commercially available tubular film molding machine for high-pressure polyethylene (manufactured by Modern Machinery), the haze was 10.1%. Molding conditions are resin temperature 170
℃, screw rotation speed 60 rotations, die diameter 100mmφ,
The die slit width is 1.0 mm. Examples 2 and 3, Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that the method of supplying each catalyst component was changed. The results are shown in Table 1.

[Table] Comparative Example 2 In Example 1, instead of feeding the magnesium component at 4.5 mmol/hr in terms of magnesium atoms, it was fed at 0.675 mmol/hr (at this time, the amount of the catalyst was
Example 1 except that the Mg/Ti molar ratio was 1.5)
Polymerization was carried out in the same manner. The copolymer concentration in the polymerization vessel was 14.4 g/
The polymerization activity was 3200 g-copolymer/mmol-Ti. The MI was 0.82 and the density was 0.942 g/cm ³ . When trying to mold it into a film in the same manner as in Example 1, foaming occurred and the film could not be formed. Examples 4 to 8, Comparative Example 3 Polymerization was carried out in the same manner as in Example 1, except that the transition metal compound (B) and the organoaluminum compound component (C) were changed. The results are shown in Table 2.

[Table] Example 9 Anhydrous MgCl ₂ 0.5 mol essential oil suspension (0.5 mol/
), add 1.5 mol of 2-ethylhexanol,
After reacting at 120℃ for 2 hours to form a colorless and transparent solution, it was cooled to 50℃, 1.0mol of SiCl ₄ was added, and 50
The reaction was carried out at ℃ for 4 hours. After the reaction was completed, the system became a suspension of white powder. Each of the three catalyst supply lines joins the main solvent charge line at almost the same point, and 27 mmol/triethylaluminum is supplied from each of the three catalyst supply lines.
hr, titanium tetrachloride is 0.27 mmol/hr, and the magnesium component obtained above is converted to magnesium atoms.
2.7 mmol/hr was continuously supplied. At the same time, 8 kg/hr of ethylene and 100 kg of hydrogen are supplied to the polymerization vessel.
Polymerization was carried out by continuously supplying the solution at a rate of 30 Kg/cm ² and maintaining the temperature at 140°C. The concentration of the obtained polymer was 60g/, and the polymerization activity was 22.000
g・PE/mmol・Ti. MI is 7.2. Density is
It was 0.967. Examples 10 to 12 Instead of treating the refined kerosene liquid of MgCl ₂ -2-ethylhexanol complex with silicon tetrachloride in Example 1, dimethyldichlorosilane, thionyl chloride, and phosphorus trichloride were used, and the treatment was carried out under the respective conditions. A white magnesium component was obtained, and polymerization was carried out in the same manner as in Example 9 using this. The results are shown in Table 3.

[Table] Example 13 Adding 2.0 mol of n-butanol to a suspension of 0.5 mol of anhydrous magnesium chloride in refined kerosene (Mg0.5 mol/)
The mixture was added dropwise at 30°C over 30 minutes and reacted at 30°C for 2 hours. Next, add 6.0 mol of silicon tetrachloride,
The reaction was carried out at 50°C for 4 hours. After the reaction was completed, the system was a suspension of white powder. After separating the solid and liquid, the solid portion was washed with the refined kerosene from Step 3, and further refined kerosene from Step 2 was added to form a suspension. Continuous polymerization of ethylene was carried out according to the method of Example 9. The concentration of the obtained polymer was 63 g/m, and the polymerization activity corresponded to 23100 g-PE/mmol-Ti. The MI was 5.6 and the density was 0.966. Example 14 Using a glass normal pressure continuous polymerization vessel (overflow type) with an internal volume of 2, dehydrated and purified kerosene was added at 0.4/hr and triisobutylaluminum was added at 0.4/hr.
0.7 mmol/hr, diethylaluminum monochloride 2.3 mmol/hr, 2-ethylhexanol
1.28 mmol/hr, 0.3 mmol/hr when the magnesium component obtained in Example 1 is converted to magnesium atoms,
Ti(OC ₈ H ₁₇ ) ₄ kerosene solution converted to titanium atoms
0.03 mmol/hr was continuously and separately supplied to the polymerization vessel (at this time, the total amount of solvent used to dilute each component was 0.6 mmol/hr).
At the same time, ethylene-propylene mixed gas (ethylene/propylene molar ratio set to 40/60) was supplied into the polymerization vessel at a flow rate of 200/hr, and polymerization was carried out at 90°C. . During continuous polymerization, the polymerization solution was a homogeneous and transparent solution without gel formation. When the resulting copolymer was precipitated with a large amount of methanol, the ethylene-propylene copolymer was
g/hr. The polymerization activity at this time corresponds to 930 g-copolymer/mmol·Ti. The MI of this copolymer is 2.8 and the ethylene content is 75.0mol
It was %. Further, the boiling methyl acetate soluble content of the copolymer was 0.9%, and there was almost no stickiness. Further, the haze of a 1 mm thick sheet of this copolymer was 18%.

[Brief explanation of the drawing]

FIG. 1 is a flowchart illustrating the preparation of a catalyst used in the copolymerization method of the present invention.

Claims (1)

[Scope of Claims] 1 (A) a solid component obtained by treating magnesium halide to which an active hydrogen-containing electron donor has been added with a halide of silicon, sulfur, or phosphorus; (B) component (A); For one atom of magnesium in
Continuously polymerizing or copolymerizing olefins in the presence of a polymerization catalyst obtained by contacting a liquid Ti compound component corresponding to two or less titanium atoms and (C) an organoaluminum compound component. Therefore, component (B) is supplied to the polymerization system separately from other components (A) and (C), or at least a portion of component (A), at least a portion of component (B), and
At least a portion of component (C) is preliminarily mixed before being supplied to the polymerization system, and the preliminary mixing is performed with (A).
A method for continuous polymerization or copolymerization of olefins, characterized by mixing (B) into a mixture of (C), or simultaneously mixing components (A), (B), and (C).