JPS6124404B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved method for producing olefinic polymers. In particular, the present invention relates to a method for producing an olefin polymer having extremely high polymerization activity and excellent mechanical properties and moldability using a novel catalyst system. More specifically, in order to obtain a polymer with high melt flow, even if the molecular weight of the obtained polymer is adjusted using hydrogen or the like during polymerization, the stereoregularity of the polymer does not deteriorate at all. This invention relates to a method for producing olefin polymers using a unique catalyst system. [] Background of the Invention When producing a polymer of olefin (especially propylene), a transition metal halide (generally titanium trichloride) and an organometallic compound (generally an organoaluminum compound) are used as polymerization catalysts. It is well known that catalyst systems obtained from However, when producing polymers using these catalysts, the stereoregularity of the resulting polymers is not necessarily satisfactory, and therefore the resulting polymers contain relatively large amounts of amorphous portions. Not only are the mechanical properties of the polymer poor, the effective utilization of the raw olefin is reduced, and a process for removing the amorphous portion is required at a stage after the completion of polymerization, but also the polymerization activity is low. There are disadvantages such as the need to remove catalyst residue from the produced polymer after the polymerization is completed. On the other hand, a catalyst system obtained from a solid component in which a titanium compound is supported on magnesium halide and an organoaluminum compound (hereinafter referred to as "catalyst system A") has higher polymerization activity than conventional catalyst systems,
It is said that this method has the potential to eliminate the need to remove catalyst residues from polymers. however,
The crystallinity of the resulting polymer is relatively low, and the process can be carried out without removing the amorphous polymer present in the polymer.
When used as is, it is difficult to say that it is satisfactory in terms of practical physical properties. Furthermore, since the polymerization activity per carrier is not necessarily satisfactory, a relatively large amount of magnesium dihalide remains in the produced polymer, which not only corrodes the polymerization equipment and adversely affects the color of the product, but also Since the bulk density of the polymer powder is low, there are drawbacks such as great difficulty in manufacturing. In addition, a catalyst system (hereinafter referred to as "B
Catalyst systems have improved the stereoregularity of polymers compared to the above-mentioned systems when producing polymers with low melt flow indexes, but the molecular weight When producing a polymer with a practical melt flow index by adjustment, the stereoregularity is greatly reduced, and unless the amorphous polymer is removed, it is impossible to obtain a product with practical mechanical properties. Therefore, it cannot be said that it is sufficient to basically simplify the manufacturing process and reduce the manufacturing cost. For example, if we take polypropylene (hereinafter referred to as "PP") as an example, the temperature is 230℃ and the load is 2.16Kg.
A product with a melt flow index (hereinafter referred to as "MFI") of 3 g/10 minutes is not practical because it is difficult to fully demonstrate the inherent advantages of the resin unless the bending rigidity is 11000 Kg/cm ² or higher. but,
When producing PP with this MFI, the n-heptane extraction residue (hereinafter referred to as "HR") of this PP is approximately 94%, and it is necessary to make a product with an HR value lower than this into a practical product. , it is necessary to sufficiently remove low-crystalline PP with an appropriate solvent. [] Object, structure, and effect of the present invention (a) Object and structure of the present invention Based on the above, the present inventors have developed a catalyst having the following performance when polymerizing olefin (especially propylene). In order to obtain the system,
Various considerations were made. (1) The polymerization activity per transition metal is extremely high, and there is no practical problem with the color and odor of the resulting polymer without going through a complicated catalyst residue removal process. (2) Furthermore, the polymerization activity per transition metal ( It has a high polymerization activity (per total solid catalyst), does not cause corrosion of the extruder or clogging of the screen during the polymerization process, and does not cause corrosion of the extruder or clogging of the screen even without removing catalyst residue. (3) The content of amorphous polymer in the obtained polymer is relatively small, and it is not necessary to remove the amorphous polymer in the produced polymer. , in terms of practical physical properties,
A highly crystalline polymer with excellent mechanical properties can be obtained.As a result, (A) (1) a co-pulverized product of an organic compound having a silicon atom-oxygen atom bond and magnesium dihalide; (2) "Tetravalent titanium compound containing at least one halogen atom"
(hereinafter referred to as "titanium-based compounds") and (3) "Si-
O bond, P-O bond, C-OH bond, C-O-
A solid component obtained by contacting an "organic compound having at least one type of bond selected from the group consisting of a C bond, an N-O bond, and an S-O bond" (hereinafter referred to as "M-O compound"). (B) By homopolymerizing or copolymerizing olefins in the presence of a catalyst system obtained from organoaluminum compounds, polymers with not only extremely high polymerization activity but also extremely high stereoregularity can be used in a wide range of MFI fields. The present invention was achieved by discovering that this combination can be achieved. (b) Effects of the present invention (1) Completely different from conventional olefin polymerization catalysts,
Even when the molecular weight of the obtained polymer is adjusted using a molecular weight regulator (generally hydrogen) during polymerization to produce a polymer with a high melt flow, no decrease in HR occurs (for details, see (See Figure 1) Therefore, the MEI range (MFI of 1 to 20 g/10
(min), a polymer with extremely high stereoregularity can be obtained. In other words, taking polypropylene as an example,
As is clear from FIG. 1, the conventional catalyst systems, namely the titanium trichloride-based catalyst system [E in FIG. 1], the A catalyst system [C in FIG. 1] and the B catalyst system [FIG. 1] D], the HR of the resulting polymer decreases rapidly as the MFI increases. The reason for this is generally considered as follows. Polymers contain polymers of various molecular weights and of various stereoregularities, and extraction with boiling n-heptane selectively extracts the less regular parts;
The low-order, high-molecular-weight parts are not extracted, and therefore, in polymers with low MFI (large molecular weight), the low-order parts cannot be completely extracted, whereas the MFI increases (in low-molecular-weight polymers), the low-order parts cannot be completely extracted. As a result, the extraction is performed in a relatively close manner, resulting in an increase in MFI and a decrease in the extraction residue due to n-heptane. In this way, this phenomenon was thought to be rather a natural phenomenon in the production of polyolefins, but surprisingly, in the polymers obtained by the method of the present invention,
Even if you change the MFI in various ways, the HR
No change in value. The cause of this phenomenon is currently unclear, but the catalyst system used in the present invention has a very different activity from conventional catalysts in that it is a type of catalyst that hardly generates high molecular weight, low regularity moieties. It is assumed that it has a point distribution. From the above, the method for producing a polymer according to the present invention has various advantages as shown below. () When olefin is polymerized using catalyst A or catalyst B, low MFI results in high H.
Even though it is R., in the practical MFI area, H.
As a result, when compared as a practical product, the product obtained by the method of the present invention has much better stereoregularity, and therefore has excellent moldability. Polymers with mechanical properties can be obtained. () Particularly during the production of polymers in the practical MFI range, the soluble content in the polymerization medium is much lower, resulting in problems such as adhesion, mutual adhesion, and agglomeration in equipment such as reactors and flash hoppers. By evaporating the polymerization solution or polymerization slurry as it is without removing any amorphous parts, it is possible to solve the problem at once and produce a polymer with good fluidity (free flowing). (2) Even when the low crystallinity portion is removed in some form, the soluble content in the solvent is very small, so it is difficult to remove it using a commonly used solvent. Since only a very small amount is removed by the solvent, the raw material olefin can be used effectively. (3) The polymerization activity of the catalyst system used in the present invention is extremely high, and in particular, the polymerization activity per halogenated titanium compound, which has a close relationship with the coloring, odor, and corrosivity of the resulting polymer, is extremely high. , it is possible to easily obtain a polymer that can be used for normal use without any special operation for removing catalyst residue or post-treatment for inactivating catalyst residue. (4) When the catalyst system used in the present invention is applied to homopolymerization of ethylene, the resulting polymer has a narrow molecular weight distribution. Furthermore, it is possible to easily obtain a polymer that has very little branching, extremely high crystallinity, is suitable for injection molding, and has excellent mechanical properties. Taking the above advantages together, the polymerization method according to the present invention can omit post-treatments such as removal of low crystallinity parts and catalyst residues from the resulting polymer and inactivation of the catalyst residues, and can provide excellent mechanical properties. It can be seen that it is well suited for low cost polyolefin production systems that yield moldable polymers. [] Specific description of the present invention (a) Organic compound having a silicon atom-oxygen atom bond The general formula of the organic compound having a silicon-oxygen atom bond used in the present invention is the following formula [()
Formula, () formula and () formula]. Si(OR ¹ ) _n R ² _o () R ³ (R ⁴ ₂ SiO) _l SiR ⁵ ₃ () (R ⁶ ₂ SiO) _p () In formula (), formula (), and formula (), R ¹ is Hydrocarbon groups selected from the group consisting of saturated or unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups having at most 20 carbon atoms (these are halogen atoms or R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, and the above hydrocarbon groups (which may be substituted ), a hydrogen atom or a halogen atom, m+n is 4 (however, m≠0), l is an integer from 1 to 1000, and p is an integer from 2 to 1000. Representative organic compounds represented by formula () include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetrapropoxysilane, dipropoxydipropyl Silane, tetra-isopropoxysilane, di-isopropoxy-di-isopropylsilane, dimethoxydiethylsilane, diethoxydibutylsilane, tetra-n-butoxysilane, di-n-butoxy-di-n-butylsilane, tetra-secondary -butoxysilane, tetrahexoxysilane, tetraoctoxysilane, trimethoxychlorosilane, dimethoxydichlorosilane, dimethoxydibromosilane, triethoxychlorosilane, diethoxydipromosilane, dibutoxydichlorosilane, dicyclopentoxydiethylsilane, Ethoxydiphenylsilane, 3.5
-dimethylphenoxytrimethylsilane, methylphenyl-bis(2-chloroethoxy)silane, dimethoxydibenzylsilane, tri-n-
Propylallyloxysilane, allyl
Tris(2-chloroethoxy)silane and trimethoxy-3-ethoxypropylsilane are mentioned. In addition, typical organic compounds represented by formula () include hexamethyldisiloxane, octamethyltrisiloxane, tetracosamethylundecasiloxane, 3-hydroheptamethyltrisiloxane, hexaphenyldisiloxane, hexamethyldisiloxane, cyclohexyldisiloxane,
1,3-dimethyldisiloxane, hexaethyldisiloxane, octaethyltrisiloxane,
Hexapropyldisiloxane, 1,3-dichlorotetramethyldisiloxane, 1,3-bis(p-phenoxyphenyl)-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-
allyl tetramethyldisiloxane,
1,3-dibenzyltetramethyldisiloxane, 2,2,4,4-tetraphenyl-2,4
-disil-1-oxacyclopentane, 1.
Mention may be made of 1,3,3-tetramethyldisiloxane, poly(diphenyl)siloxane, poly(methylphenyl)siloxane, poly(hydromethyl)siloxane and hexachlorodisiloxane. Furthermore, typical organic compounds represented by formula () include 1,3,5-trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylchlorocyclotrisiloxane, 1. 3,5-trimethyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,3,5-tribenzyltrimethylcyclotrisiloxane and 1,3,5
-allyltrimethylcyclotrisiloxane. Among these organic compounds having a silicon atom-oxygen atom bond, preferred are alkoxysilanes and low-viscosity polysiloxanes, particularly tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane,
These include diethyldiethoxysilane, methoxytrimethylsilane, trimethoxymethylsilane, hexamethyldisiloxane, octamethyltrisiloxane, dimethylpolysiloxane, methylethylpolysiloxane, and methylphenylsiloxane. (b) Magnesium dihalide Furthermore, the magnesium dihalide used in the present invention is a so-called anhydride that does not contain water of crystallization, and commercially available products generally include:
It is desirable to heat and dry at 200-600°C. Typical examples include magnesium chloride, magnesium bromide and magnesium iodide, with magnesium chloride being particularly preferred. (c) Co-pulverization treatment method and ratio For the co-pulverization treatment with the organic compound magnesium dihalide having a silicon atom-oxygen atom bond, a pulverizer such as a ball mill, a vibrating ball mill, an impact pulverizer, or a colloid mill may be used. Bye. If this process generates a large amount of heat, it may be cooled for operational convenience, but it is usually sufficient to carry out the process at around room temperature. The time required for co-pulverization varies depending on the performance of the pulverizer, so it cannot be absolutely specified, but it is important to note that the time required for co-pulverization is not a simple contact between the organic compound having a silicon atom-oxygen bond and the magnesium dihalide. It is necessary to contact the As an example of the time for this co-pulverization process, if the internal volume is 1
Then, put 50% of the apparent volume of a porcelain ball with a diameter of 1 cm into a container with an inner diameter of 10 cm, and about 20
When co-pulverizing is performed using a vibrating ball mill with an amplitude of 6 mm and a frequency of 30 Hz (Hertz), it takes at least 30 minutes, preferably at least 1 hour. The co-pulverization ratio of the organic compound having a silicon atom-oxygen atom bond to 1 mol of magnesium dihalide is generally 0.005 to 1 mol (the number of moles of repeating units in a polymer, the same applies hereinafter), and in particular, 0.01 to 0.7 mol is preferred. If the co-pulverization ratio of the organic compound having a silicon atom-oxygen atom bond to 1 mol of magnesium dihalide is 0.005 mol or less,
Not only is the polymerization activity of the resulting catalyst system relatively low, but the effect of improving the stereoregularity of the resulting polymer is hardly observed. On the other hand, if the amount is 1 mole or more, the polymerization activity will be greatly reduced. (d) Titanium compound Furthermore, the titanium compound used in the present invention is a tetravalent titanium compound having at least one halogen atom, and its general formula is as shown by the following formula [formula ()]. . TiX ¹ _o (OR ⁷ ) _n ⁽ NR ⁸ R ⁹ ) _l (OCOR ¹⁰ ) _p () In the formula, X ¹ is a chlorine atom, a bromine atom, or an ^iodine atom ^, and ^R10 is an aliphatic, alicyclic, or aromatic hydrocarbon group having at most 12 carbon atoms, and n is 1 to
4, where m, l and p are 0 to 3
, and n+m+l+p is 4. Typical examples of titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, trichlormethoxytitanium, dichlordimethoxytitanium, chlortrimethoxytitanium, ethoxytrichlortitanium, diethoxydichlortitanium, and triethoxychlor. Titanium, trichlorpropoxytitanium, butoxytrichlortitanium, trichlor-N・N-dimethylamino titanium, dichlor-N・N・N′・N′-tetramethyldiamino titanium, trichlor-N・N-diethylamino titanium, trichlortitanium propio and trichlorotitanium benzoate. Among these, titanium tetrahalide and alkoxytrihalogenotitanium are preferred, and titanium tetrachloride, trichloromethoxytitanium and trichloroethoxytitanium are particularly preferred. (e) M-O compounds Furthermore, the M-O compounds used in the present invention include Si-O bonds, P-O bonds, C-OH bonds, C-O-C bonds, N-O bonds and S- O
It is an organic compound having at least one of these bonds. (I) Organic compound having a Si-O bond The organic compound having a Si-O bond is described in the general formula section of representative and preferred examples of organic compounds having a silicon atom-oxygen atom bond. Each of the items listed can be applied. () Organic compound having a P-O bond The general formula of an organic compound having a P-O bond is shown by the following formulas [formula () and formula ()]. X ² lYmp(OR ¹¹ )n () X ² qYrP(O)(OR ¹² )s () In formulas () and (),
The sum of and n or q and r and s is 3 and O≦
l, m<3, O<n≦3, O≦
q, r・s≦3, and R ¹¹ and R ¹² may be the same or different, and are saturated or unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic groups having at most 20 carbon atoms. X ² and Y may be the same or different, hydrogen It is selected from atoms, halogen atoms, hydroxyl groups, and the above hydrocarbon groups (which may be substituted). Typical organic compounds represented by the formula () include ethyl diethyl phosphinite, ethyl butyl phosphinite, ethyl phenyl methyl phosphinite, butyl phenyl vinyl phosphinite, and phenyl dibenzyl phosphinite. night, dimethylethylphosphonite, diphenylethylphosphonite, diethylbenzylphosphonite, diphenylethylphosphonite, diethylbenzylphosphonite, diethyl-2-chloroethylphosphonite, trimethylphosphite, triethylphosphite, tri-n- Propyl phosphite, tri-isopropyl phosphite, allyl phosphite, tri-n-
Butyl phosphite, triphenyl phosphite, tricyclohexyl phosphite, tribenzyl phosphite, tris(3-ethoxypropyl) phosphite, tris(2-
Chlorethyl) phosphite, tricresyl phosphite, diphenylnonylphenyl phosphite, tris(nonylphenyl) phosphite, diphenylisodecyl phosphite, triisodecyl phosphite, tris(2-ethylhexyl) phosphite, ethyl ethylphosphonochloride Dite, phenylethylphosphonochloridite, phenylphenylphosphonochloridite, n-butylphenylphosphonochloridite, diethylchlorophosphite, diphenylchlorophosphite, dioctylchlorophosphite, diethylbromophosphite, dibenzyl chlorphosphite, benzyl chlorphosphite,
Examples include 2-chloroethyldichlorophosphite and hexyldichlorophosphite. Representative organic compounds represented by the formula () include methyldimethylphosphinate, methyldiethylphosphinate, ethyldiethylphosphinate, ethyldipropylphosphinate, ethyldi-n-butylphosphinate, and ethyldiphenylphosphinate. , methyl dicyclohexyl phosphinate, 2-chloroethyl cybenzyl phosphinate, ethyl ethyl phosphonochloridate,
Phenylethylphosphonochloridate, phenylphenylphosphonochloridate, n-butylphenylphosphonochloridate, ethyl ethylphosphonobromidate, diethylmethylphosphonate, diphenylphenylphosphonate, dioctylbutylphosphonate , diethyl phenyl phosphonate, allyl phenyl phosphonate, bis(2-
chloroethyl) phenylphosphonate, diethylcyclohexylphosphonate, diethylbenzylphosphonate, diethylphosphorochloridate, di-n-butylphosphorochloridate, dioctylphosphorochloridate,
Diphenyl phosphorochloridate, dibenzyl phosphorochloridate, dicresyl phosphorochloridate, bis(2-chloroethyl)
Phosphorochloridate, diphenylphosphorobromidate, ethylphosphorodichloridate, n-butylphosphorodichloridate, phenylphosphorodichloridate, benzylphosphorodichloridate, cresylphosphorodichloridate, ethylphosphorodibro midate, triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, tribenzyl phosphate, trihexyl phosphate diethyl phosphate, di-
n-butyl phosphate, diphenyl phosphate, cresyl diphenyl phosphate,
Tricresyl phosphate, tritolyl phosphate, trixyl phosphate, diphenyl mono-O-xenyl phosphate, diphenyl xylenyl phosphate, tris(bromo-chloropropyl) phosphate,
Triethylphosphine oxide, tri-n-
Butylphosphine oxide, triphenylphosphine oxide, diphenylphosphine chloride, ethyl phenylphosphine chloride, diphenyphosphine bromide, methyl phenyl phosphine bromide, dibutyl phosphine chloride, dimethyl phosphine Examples include phosphonic chloride, ethylphosphonic dichloride, propylphosphonic dichloride, butylphosphonic dichloride, phenylphosphonic dichloride, phenylphosphonic dibromide, triphosphonic dichloride and benzylphosphonic dichloride. Among these organic compounds having a P-O bond, in formula (), R ¹¹ is preferably a hydrocarbon group having at most 8 carbon atoms, and particularly preferred is one having 2 or more carbon atoms. .
Among the organic compounds represented by the formula (), preferred are triethyl phosphite,
Examples include triphenyl phosphite, diphenylethyl phosphonite, diethyl ethyl phosphonite, diethyl butyl phosphonite, diethyl phosphite, diphenyl phosphite, dibutyl chlorophosphite, and diphenyl chlorophosphite. Furthermore, in formula (), R ¹² is preferably a hydrocarbon group having at most 8 carbon atoms. Among the organic compounds represented by the formula (),
Preferred are triphenylphosphine oxide, tributylphosphine oxide, ethyldiphenylphosphinate, diphenylmethylphosphonate, phenylphosphorodichloridate, phenylphosphonic dichloridate, propylphosphonic dichloride, triphenyl Examples include phosphate and tributyl phosphate. () Organic compounds having a C-OH bond Organic compounds having a C-OH bond include monohydric and polyhydric alcohol compounds, phenolic compounds, and naphthol compounds, and among alcohol compounds, especially,
Monovalent and polyvalent hydrocarbon groups having 2 to 20 carbon atoms selected from the group consisting of alkyl groups, cycloalkyl groups, and aralkyl groups, and the hydrocarbon groups substituted with halogen atoms and/or alkoxy groups. Alcohol compounds are preferred. Representative examples of preferred alcohol compounds include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, isoamyl alcohol, cyclohexanol, stearyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol,
Examples include glycerin. () Organic compounds with C-O-C bonds Organic compounds with C-O-C bonds include saturated or unsaturated aliphatic, cycloaliphatic, and aromatic hydrocarbon groups (even if partially halogen-substituted). It is a linear or cyclic ether with at most 40 carbon atoms, and typical examples include dimethyl ether, methyl ether,
ethyl ether, diethyl ether, di-n
-Propyl ether, di-iso-propyl ether, di-n-butyl ether, di-iso-butyl ether, di-iso-amyl ether, dioctyl ether, didodecyl ether, allyl ether, iso-butyl vinyl ether, polyethylene Linear aliphatic ethers such as glycol, polypropylene glycol, ethylene glycol dimethyl ether, diethyl cellosolve and benzyl methyl ether; diphenyl ether, di-p-tolyl ether, anisole,
Mention may be made of linear aromatic ethers such as ethoxybenzene, dimethoxybenzene, bromanisole and chloranisole, and cyclic ethers such as furan, tetrahydrofuran, dioxane, coumaron, coumaran and tetrahydropyran. Among them, monofunctional ethers are preferred;
In particular, diethyl ether, di-n-propyl ether, di-isopropyl ether, di-
Preference is given to n-butyl ether, di-isobutyl ether, anisole, ethoxybenzene and diphenyl ether. () Organic compounds having N-O or S-O bonds Organic compounds having N-O or S-O bonds include alkyl groups, cycloalkyl groups, aryl groups and Examples include nitrite ester compounds and sulfite ester compounds having a hydrocarbon group selected from the group consisting of aralkyl groups, particularly nitrite ester compounds and sulfite esters having an alkyl group having at most 8 carbon atoms. type compounds are preferred. Among these nitrite ester compounds, representative examples of suitable ones include methyl nitrite, ethyl nitrite, butyl nitrite, isoamyl nitrite, dimethyl sulfite, and diethyl sulfite. (f) Production of solid components These M-O compounds and titanium-based compounds are the "co-pulverized product of an organic compound having a silicon atom-oxygen atom bond and magnesium dihalide" obtained as described above ( Below “Ingredients”
(1)") is preferable.
Component (1) is brought into contact with a titanium compound, the excess is washed away using a solvent, and then an M-O compound is contacted, or component (1) is brought into contact with a M-O compound, and then A method in which a titanium-based compound is contacted after washing and removing an excess amount using a solvent is not desirable because the effects of the present invention cannot be fully exhibited. Based on the above, component (1) should be added to a mixture of a titanium compound and an M-O compound, or a mixture of the titanium compound and an M-O compound in which the reaction between the two has been completed by a treatment such as heating, or a combination of a titanium compound and an M-O compound. It is preferable to mix the O compound and component (1) together and carry out the contact treatment. The ratio of titanium compound to 1 mol of M-O compound is generally as follows:
The amount is 0.1 to 50 mol, preferably 0.2 to 20 mol.
Particularly suitable is a range of 0.5 to 10 moles that can form a large amount of a quantitative complex compound of the M--O compound and the titanium compound. When performing contact treatment, simply component (1),
It is sufficient to bring the titanium compound and the M-O compound into contact with each other, but in order to produce it efficiently,
It is preferable to apply a method such as stirring the whole in a suitable solvent or co-pulverizing it in a pulverizer in the same manner as described above. The solvent used for the mixing or reaction of the titanium compound and the M-O compound and the solvent for the stirring contact with component (1) include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, benzene, Although aromatic hydrocarbons such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, trichloroethane, trichloroethylene and chlorobenzene can be used, aromatic hydrocarbons are particularly preferred. component
The concentration of the stirring contact with (1) is preferably as high as possible unless there is a problem in operation, and usually 0.005 mol-Ti/l or more is used. The contact temperature is generally -10 to +200°C; at low temperatures, the polymerization activity of the resulting catalyst is low, while at high temperatures, the stereoregularity of the resulting polymer is low, resulting in excellent performance. A temperature of 20 to 120°C is desirable. The contact time is usually 10 minutes or more, and sufficient support is achieved in about 2 hours. Even after contacting for more than 10 hours, no better support was observed. After the above-mentioned contact treatment, it is preferable to wash using an inert solvent (for example, aliphatic hydrocarbons and aromatic hydrocarbons used as solvents in the stirring contact treatment). (g) Organoaluminum compound In producing the catalyst system used in the present invention, the general formula of a typical organoaluminum compound used in combination with the catalyst component (A) produced by the above method is the following formula [ Expression () and Expression ()]. AlR ¹³ R ¹⁴ R ¹⁵ () R ¹⁶ R ¹⁷ Al-O-AlR ¹⁸ R ¹⁹ () In formulas () and (), R ¹³ , R ¹⁴
and R ¹⁵ may be the same or different and are a hydrocarbon group, halogen atom or hydrogen atom having at most 12 carbon atoms, and R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different and have at most 12 carbon atoms. is at most 12 hydrocarbon groups, and at least one of R ¹³ , R ¹⁴ and R ¹⁵ is the hydrocarbon group.
Among these R ¹³ to ^{R 19} , organoaluminum compounds having an alkyl group having 8 or less carbon atoms are particularly preferred. Among organoaluminum compounds represented by the formula (), representative examples include trialkylaluminums such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, etc. and alkylaluminum halides such as diethylaluminum chloride and diethylaluminum bromide.
Alkylaluminum sesquihalides such as ethylaluminum sesquichloride can also be used. Furthermore, representative examples of the organoaluminum compound represented by the formula () include tetraethyldialumoxane, tetrabutyldialumoxane, and the like. Although the catalyst system used in the present invention can be obtained from these organoaluminum compounds and the catalyst component (A), the catalyst system can also be prepared using a reactant or a mixture of these organoaluminum compounds and an electron-donating compound. may be manufactured. The catalyst system obtained from the above catalyst component (A) and an organoaluminum compound can be effective in the polymerization of olefins, but especially in the homopolymerization of propylene and in small amounts (generally at most 20% by weight) of propylene. ) with ethylene or α-olefins (generally having at most 12 carbon atoms), as well as homopolymerization of ethylene with ethylene and a small amount (generally 20% by weight or less) of α-olefins (generally containing at most 12 carbon atoms). (The number is at most 12). Further, a catalyst system obtained by further using an electron-donating compound in the catalyst component (A) and the organoaluminum compound is suitable. This catalyst system is particularly effective in the homopolymerization of propylene or the copolymerization of propylene with ethylene or α-olefin. (h) Electron-donating compound As the electron-donating compound, known substances that are widely used as stereoregularity improvers and particle size distribution improvers for Ziegler and Natsuta type catalysts can be used. However, organic carboxylic acid ester compounds and the above M-
C- shown as an organic compound having an O bond
Preferred are organic compounds having an OH bond, an organic compound having a C-O-C bond, an organic compound having a P-O bond, and an organic compound having a Si-O bond. Among these electron-donating compounds,
Particularly suitable are organic carboxylic acid ester compounds. Representative examples of the organic carboxylic acid ester compounds include aliphatic, alicyclic or aromatic carboxylic acids having at most 20 carbon atoms, and aliphatic, alicyclic or aromatic carboxylic acids having at most 20 carbon atoms. A carboxylic acid ester derived from a monohydric or polyhydric alcohol, and a portion thereof may be substituted with a halogen atom or an alkoxy group. Representative examples of the organic carboxylic acid ester include methyl formate, ethyl formate, methyl acetate, ethyl acetate, aluminum acetate, cyclohexyl acetate,
Aliphatic carboxylic acid esters such as vinyl acetate, butyl acetate, ethyl butyrate, phenyl propionate, furfuryl propionate, diethyl malonate, diethyl succinate, diethyl fumarate, methyl acrylate, methyl methacrylate, and ethylene glycol diacetate. ; alicyclic carboxylic acid esters such as methyl cyclohexanecarboxylate, ethyl norbornenecarboxylate and ethyl 2-furoate; methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, butyl benzoate;
Such as hexyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, ethylene glycol dibenzoate and methyl naphthoate. Examples include aromatic carboxylic acid esters. Among these, aromatic carboxylic acid esters are particularly desirable. () Polymerization conditions, etc. Catalyst component (A) obtained by contacting component (1) with a titanium compound and an M-O compound,
The organoaluminum compound or these and the electron-donating compound may be introduced separately into the polymerization vessel, or two or all of them may be mixed in advance. In particular, it is desirable to mix everything immediately before carrying out the polymerization. Catalyst component (A) for 1 mol of organoaluminum compound in the polymerization system (as titanium atoms)
and electron donating compound (if used) are generally used in a proportion of 0.001 to 1, respectively.
molar and at most 1 molar, especially
0.001 to 0.2 mol and at most 0.7 mol are preferred. The olefin polymerized by the catalyst system obtained as described above has at most the number of carbon atoms.
12 olefins, typical examples of which are ethylene, propylene, butene-1, 4-
Examples include methylpentene-1, hexene-1, octene-1, and the like. In carrying out the present invention, these olefins may be homopolymerized, but two or more types of olefins may be copolymerized (for example, copolymerization of ethylene and propylene). Polymerization can be carried out either in an inert solvent, in a liquid monomer (olefin) or in the gas phase. Further, in order to obtain a polymer having melt flow if practical, a molecular weight regulator (generally hydrogen) may be present. The polymerization temperature is generally from -10°C to 200°C, and practically from room temperature to 170°C. In addition, there are no limitations inherent to this catalyst system with respect to the form of the polymerization reactor, polymerization control method, post-treatment method, etc., and all known methods can be applied. [] EXAMPLES AND COMPARATIVE EXAMPLES The present invention will now be described in more detail with reference to Examples. In the Examples and Comparative Examples, the heptane index (ie, HR) is the amount remaining after extracting the obtained polymer with boiling n-heptane for 6 hours, expressed in %. Melt flow index (MFI) is JIS K-6758-
Measured by 1968. Bending rigidity and tensile yield strength were measured in accordance with ASTM D-747-63 and ASTM D-638-64T, respectively, on pressed pieces obtained in accordance with JIS K-6758-1968. Melt Index (hereinafter referred to as "MI")
was measured according to JIS K-6760. Density is JIS K
-6760. In the simple fractionation method, approximately 3 g of ethylene polymer formed into a film is placed in a 300-mesh wire gauze, placed in a mixed solvent of butyl cellosolve (45% by volume) and xylene (55% by volume), and placed in a vibromixer (Kyoto) at 127.0°C. The mixture was extracted for 5 hours with thorough stirring using an electronics manufacturer (manufactured by Denshi Kogyo Co., Ltd.). At this temperature and solvent composition, all of the ethylene polymer is melted, so only low molecular weight components are extracted without being affected by crystallinity. Therefore, the component remaining in the wire mesh is a high molecular weight ethylene polymer component that is not dissolved in this solvent composition. The remaining high molecular weight components were once dissolved in xylene, precipitated with a large amount of methyl alcohol, collected using a glass filter, and then dried under reduced pressure. The measurement method for short chain branching using infrared absorption spectroscopy is 4255cm determined by infrared absorption spectroscopy.
Using the absorption of ^-1 as an internal standard, the measurement was performed using the absorption of methyl group at 1378 cm ^-1 using the WILLBOURN method [A. Etsuchi. AHWILLBOURN, JOURNAL OF POLYMER
SCIENCE) Vol. 34, p. 569, (1959)]. In each Example and Comparative Example, all compounds (organic solvents, olefins, hydrogen, titanium compounds, magnesium dihalides, M-O compounds, electron-donating compounds, etc.) used in the production and polymerization of catalyst components are essential. Water has been removed. Furthermore, the preparation method and polymerization of the catalyst components were carried out essentially in the absence of moisture and in a nitrogen atmosphere. Example 1 [(A) Production of catalyst component (A)] Anhydrous magnesium chloride (commercially available anhydrous magnesium chloride was heated at about 500°C in a dry nitrogen stream)
(obtained by heating and drying for 15 hours)
20g (0.210 mol) of an organic compound having a silicon atom-oxygen atom bond [hereinafter referred to as "silicon-containing organic compound"], and 6.0 g of tetraethoxysilane [28.8 mmol, hereinafter referred to as "compound (a)"]. was placed in a container for a vibrating ball mill (cylindrical stainless steel, internal volume 1, 10 mm diameter porcelain balls filled to approximately 50% apparent volume). The amplitude is 6
mm, installed on a vibrating ball mill with a frequency of 30Hz, 8
Time pulverization was carried out. Of the obtained homogeneous co-pulverized material, 15 g was placed in a 500 ml flask, and 86.3 g of titanium tetrachloride and 49.5 g of triphenyl phosphate as an M-O compound [hereinafter referred to as "compound ( 1)] at room temperature was added. Stirring and mixing were performed at 65°C for 2 hours. After the obtained solid components were separated by filtration, they were washed with toluene until titanium tetrachloride was no longer detected in the filtrate. After washing, a powdered catalyst component (A) was prepared by drying at 40° C. under reduced pressure.
Chemical analysis of the obtained catalyst component (A) revealed that the content of titanium atoms in this catalyst component was 1.56.
It was in weight%. [(B) Polymerization and physical properties of the produced polymer] In a 3.0 stainless steel autoclave, 40.1 mg of the catalyst component (A) produced by the above method, 0.54 g of triethylaluminum as a trialkylaluminum compound, and an electron-donating compound were placed. as
Add 0.25g of ethyl benzoate, then immediately
Charged 760g propylene and 0.07g hydrogen. Raise the temperature of the autoclave to bring the internal temperature (polymerization system) to 70
It was kept at ℃. After 60 minutes, the content gas was released to terminate the polymerization. As a result, 278 g of powdered polypropylene was obtained. That is, the polymerization activity is 6.933
g/g-catalyst component (A)/hour, 444 Kg/g-Ti/hour. The HR of this polypropylene powder is 96.8
It was %. Without particularly purifying this powder, 100 parts by weight of the powder and 0.15 parts by weight of tetrakis[methylene-3-(3'·5'-di-tertiary-butyl-4'-hydroxyphenyl)] were added as a stabilizer. Propionate] Methane (manufactured by Ciba Geigy, trade name
Irganox 1010), 0.20 parts by weight of distearylthiodipyropionate, and 0.10 parts by weight of calcium stearate were kneaded into pellets using an extruder with an inner diameter of 20 mm and a L/D of 40 at 210°C under a nitrogen atmosphere. Created. The obtained pellets exhibited whiteness and transparency comparable to those of ordinary commercially available products. MFI was 4.4 g/10 min. The flexural rigidity of the pressed plate of this pellet was 13,100 Kg/cm ² and the tensile yield strength was 327 Kg/cm ² , showing excellent physical properties. Examples 2 to 13, Comparative Examples 1 to 3 6.0 g used as the silicon-containing organic compound in producing the co-pulverized product in (A) of Example 1
Instead of compound (a), dichlorodimethoxysilane [hereinafter referred to as "compound (b)"], tetracresylsilane [hereinafter referred to as "compound (C)]", methylphenylpolysiloxane [30℃ Viscosity at temperature
450 centistokes, hereinafter referred to as “Compound (d)”], dimethoxydimethylsilane (hereinafter referred to as “Compound (d)”)
(e)], tetramethoxysilane [hereinafter referred to as "compound (f)"], hexamethyldisiloxane [hereinafter referred to as "compound (g) ⁺ "], and 1,3-dichlorotetramethyldisiloxane. [Hereinafter referred to as “compound
Co-pulverization was carried out in the same manner as in Example 1 (A), except that the amounts of (referred to as "(h)") shown in Table 1 were used. 49.5 g of compound (1) used as the M-O compound in preparing the catalyst component (A) in Example 1 (A)
Instead, triphenyl phosphite [hereinafter referred to as “compound (2)”], diethyl ether [hereinafter referred to as “compound (3)”], tetraethoxysilane [hereinafter referred to as “compound (4)”], ethyl Alcohol [hereinafter referred to as "compound (5)"], diphenyl phosphorochloridate [hereinafter referred to as "compound (6)"], butyl nitrite [hereinafter referred to as "compound (7)"], anisole [hereinafter referred to as " Compound (8)], triethyl phosphite (hereinafter referred to as "compound (9)"), and phenol (hereinafter referred to as "compound (10)") were used in the amounts shown in Table 1. A catalyst component was prepared under the same conditions as in Example 1 (A). For comparison, in experiment number 11, the catalyst component was created without using the M-O compound.
In experiment number 12, a pulverized product was prepared without using a silicon-containing compound, and a catalyst component was produced. Table 1 shows the titanium atom content of each catalyst component obtained as described above.

[Table] Example 1 except that 6.0 g of chlortriethoxysilane was used instead of compound (a) used as the silicon-containing organic compound in producing the co-pulverized product in (A) of Example 1. Co-milling was carried out in the same manner as in 1 (A). Using the above co-pulverized product, and using the co-pulverized product of Example 1
In place of the titanium tetrachloride used as the titanium-based compound in preparing the catalyst component (A) in (A),
Except that 90.6 g of trichloroethoxytitanium was used and 31.4 g of diethyl sulfite was used instead of compound (1) used as the M-O compound.
A catalyst component was prepared in the same manner as in Example 1 (A). The obtained catalyst component [hereinafter referred to as "catalyst component (P)"]
The content of titanium atoms was 2.58% by weight. The same conditions as in (A) of Example 1 except that the same amount of magnesium bromide was used instead of the magnesium chloride used as the magnesium halide in producing the co-pulverized product in (A) of Example 1. A co-pulverized product was prepared. This co-pulverized product was used, and 167.4 g of titanium tetrabromide was used in place of the titanium tetrachloride used as the titanium-based compound when preparing the catalyst component in (A) of Example 1.
A catalyst component was prepared in the same manner as in Example 1 (A). The content of titanium atoms in this catalyst component [hereinafter referred to as "catalyst component (Q)"] was 2.00% by weight. In place of the compound (a) used as the silicon-containing organic compound in producing the co-milled product in (A) of Example 1, 6.0 g of methylhydropolysiloxane (viscosity of 30 centistokes at a temperature of 25°C) was used.
Co-pulverization was carried out in the same manner as in Example 1 (A), except that . Adding 3.12 g of titanium tetrachloride and 2.80 g of diphenyl ether to the obtained co-pulverized product,
Co-pulverization treatment was carried out for 1 hour under the same conditions as in Example 1 (A) [the content of titanium atoms in the obtained co-pulverized product was 2.07% by weight or less, referred to as "catalyst component (R)"]. In place of the co-pulverized product used in producing the above catalyst component (R), 26.0 g of the co-pulverized product obtained in (A) of Example 1 was used, and diphenyl used as the M-O compound was used. Instead of ether,
The co-milling process was carried out as described above, except that 2.24 g of methylphenylpolysiloxane (viscosity 450 centistokes at 25° C.) was used. The obtained co-pulverized product (catalyst component, titanium atom content: 2.24% by weight) is referred to as catalyst component (S). A co-pulverized product was prepared in the same manner, except that the amount of methylphenylpolysiloxane used to obtain the co-pulverized product used in producing the catalyst component (D) was changed to 4.0 g. Using this co-pulverized product, the amount of titanium tetrachloride used was changed to 4.68g, and M
Co-pulverization was carried out under the same conditions as in the production of catalyst component (R), except that 2.98 g of n-octer diphenyl phosphate was used instead of the diphenyl ether used as the -O compound. The content of titanium atoms in the obtained co-pulverized product (catalyst component) was 3.73% by weight
It was hot. Hereinafter, this co-pulverized product will be referred to as the catalyst component (T).
That's what I say. In co-pulverization of (A) in Example 1, 6.0 g of ethyl benzoate and 4.6 g of silicon tetrachloride were used in place of phenylphosphonic dichloride, and compound (1) was added in the preparation of the catalyst component. A catalyst component [hereinafter referred to as "catalyst component (U)" with a titanium atom content of 2.8% by weight] was prepared in the same manner as in Example 1 (A), except that it was not used. Example 1 (B) except that the catalyst system obtained from each catalyst component shown in Table 2 was used in place of the catalyst system used to polymerize propylene in Example 1 (B). ) Polymerization of propylene was carried out under the same conditions as in ). Table 2 shows the yield and polymerization activity of each polypropylene powder obtained. Note that triethylaluminum is shown as compound (a) and diethylaluminum chloride is shown as compound (b). Further, ethyl benzoate is represented as a compound (), ethyl anisate is represented as a compound (), ethyl P-butoxybenzoate is represented as a compound (), and butyl benzoate is represented as a compound (), respectively. Pellets were prepared from each polypropylene powder obtained using the above catalyst system under the same conditions as in Example 1 (B). In addition, (B) of Example 1 was obtained from each pellet.
A press plate was created in the same manner as above. Table 3 shows the HR of each polypropylene powder, the MFI of the pellets, and the bending steel modulus and tensile yield strength of the pressed plates.

【table】

[Table] Example 13 In a 3.0 stainless steel autoclave, 9.7 mg of catalyst component (H), 0.52 mg of triisobutylaluminum [hereinafter referred to as "compound (C)" as an organic aluminum compound], 1 kg of isobutane (inert as a solvent) and 0.19 g of hydrogen were added. After raising the temperature of the autoclave to 85° C., ethylene was supplied while maintaining this temperature, and polymerization was carried out for 3 hours while maintaining the partial pressure of ethylene at 10 atmospheres (gauge pressure) at this temperature. Then, the content gas was released to terminate the polymerization. As a result, 467 g of powdered polymer (ethylene monopolymer) was obtained. In other words, the product efficiency is 48140g/g-
It is a catalyst component (H), and its polymerization activity is 854Kg/g-Ti.
It was time. The resulting powder was mixed with 100 parts by weight of powder and 0.2 parts by weight of 2.6- as a stabilizer without any particular purification.
Di-tertiary-butyl-4-methyl-phenol was kneaded into pellets using an extruder having an inner diameter of 20 mm and an L/D of 40 at a temperature of 180 DEG C. under a nitrogen atmosphere. The obtained pellets had a whiteness comparable to that of ordinary commercially available products. MI of this polymer
is 0.31g/10 minutes and HLMI (load 21.6Kg,
Melt flow index at temperature 1.0℃) is 7.7g/10
(i.e., HLMI/MI was 24.8).
That is, this polymer had a narrow molecular weight distribution. Also, the density of this polymer is 0.9662g/cc
It was hot. Example 14 A mixture of propylene and ethylene was prepared in the same manner as in Example 1 (B), except that 43.8 mg of catalyst component (B) was used as the catalyst component and ethylene was added as a comonomer at a rate of 1.2 g/5 minutes. Copolymerization was carried out. As a result, 290g of powdered propylene and ethylene copolymer (ethylene unit content is 3.5% by weight)
was gotten. That is, the polymerization activity is 6621g/g-
The catalyst component/time is 450Kg/g-Ti/hour. Moreover, the MFI of this copolymer was 7.7 g/10 minutes. Example 15 In place of the catalyst component used in polymerizing ethylene in Example 13, 10.2 mg of catalyst component (K) was used, and in addition, as an electron-donating compound,
Example except that 20mg of diethyl ether was used.
Homopolymerization of ethylene was carried out under the same conditions as in Example 13. As a result, 499 g of polymer (ethylene monopolymer) was obtained. That is, the product activity is 48920 g/g-catalyst component (K), and the polymerization activity is 1140 Kg/g-Ti.hour. The MI of the obtained ethylene monopolymer was 0.33 g/10 minutes,
HLMI was 7.0 g/10 min (i.e. H.
LMI/MI is 21.2). Also, the density is 0.9663g/cc
It was hot. Example 16 Ethylene was heated under the same conditions as in Example 13, except that 11.8 mg of catalyst component (T) was used instead of the catalyst component used in Example 13, and 15.0 g of butene-1 was coexisting as a comonomer. and butene
Copolymerization with 1 was carried out. As a result, 507 g of a powdered polymer (a copolymer of ethylene and butene-1) was obtained. That is, the product quantity is 42.970g/g catalyst component (T), which is 384
Kg/g-Ti・hour. This polyethylene powder was kneaded into pellets using an extruder in the same manner as in Example 13. The obtained pellets exhibited a whiteness comparable to that of commercially available products. The MI of the obtained copolymer was 0.31 g/10 min, and the density was 0.9378.
g/cc. The number of ethyl groups per 1000 carbons in this copolymer was 7. The extracted residue of the obtained copolymer by a simple fractionation method was 16.7% by weight, and the number of ethyl groups per 1000 carbons in this extracted residue was 5.8%.
It was individual. Example 1, Example 3, Comparative Example 2, Comparative Example 3, and Reference Example (0.20 g of AA type titanium trichloride and 0.58 g of titanium trichloride, except that the amount of hydrogen used was changed as shown in Table 4)
Polymerization of propylene was carried out under the same conditions as in Example 1 (B) using a catalyst system obtained from diethylaluminum chloride (g). HR of each obtained propylene powder and pellets made from each polypropylene powder under the same conditions as in Example 1.
MFI is shown in Table 4.

[Table] Table 4 shows the HR of each polypropylene powder obtained using each catalyst system and that of pellets.
Figure 1 shows the relationship with MFI. Figure 1 shows that when propylene is polymerized using the catalyst system used in the present invention, even if the MFI of the resulting polypropylene is increased, the HR of the polypropylene powder hardly changes;
It is clear that when propylene is polymerized using the catalyst systems used in the comparative and reference examples, when the MFI of the resulting polypropylene is increased, its HR is significantly reduced.

[Brief explanation of the drawing]

Figure 1 shows the polypropylene powders obtained using the catalyst systems of Example 1, Example 3, Comparative Example 2, Comparative Example 3 and Reference Example in Table 4.
This is a relationship diagram between HR (vertical axis unit: %) and pellet MFI (horizontal axis unit: g/10 min).

Claims (1)

[Claims] 1 (A)(1)(a) The following general formula [() to ()
An organic compound having a silicon atom-oxygen atom bond represented by the formula] and Si(OR ₁ ) _n R ² _o () R ³ (R ⁴ ₂ SiO) _l SiR ⁵ ₃ () (R ⁴ ₂ SiO) _p ( ) In formula (), formula (), and formula (), R ¹ consists of a saturated or unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having at most 20 carbon atoms. hydrocarbon groups selected from the group (which may be substituted with halogen atoms or alkoxide groups having at most 20 carbon atoms)
, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different, and are the above hydrocarbon group (which may be substituted), a hydrogen atom or a halogen atom, and m+n is 4; Yes (however, m≠0), l is an integer from 1 to 1000, and p is an integer from 2 to 1000. (b) Co-pulverized product with magnesium dihalide (2) Tetravalent titanium compound having at least one halogen atom and (3) Organic compound having at least one type of bond selected from the following group (a) Organic compound having the above silicon atom-oxygen atom bond (b) The following general formula [formula () and ()
^An organic compound having a P-O bond represented by _the following formula ^: X ² _l YmP(OR ¹¹ ) _{o (} ) The sum of and n or q and r and s is 3 and 0
≦1, m<3, 0<n≦3,
o≦q, r・s≦3, R ¹¹ and R ¹²
may be the same or different and have at most 20 carbon atoms and are selected from the group consisting of saturated or unsaturated aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups (halogen No matter how many atoms or carbons there are
20 alkoxy or aryloxy substituents), X ² and Y may be the same or different, and a hydrogen atom,
It is selected from halogen atoms, hydroxyl groups, and the above-mentioned hydrocarbon groups (which may be substituted). (c) monohydric and polyhydric alcohol compounds;
Organic compounds having a C-OH bond selected from phenolic compounds and naphthol compounds (d) Saturated or unsaturated aliphatic, alicyclic aliphatic and aromatic hydrocarbon groups (may be partially substituted with halogen) organic compounds having a C-O-C bond selected from linear and cyclic ethers having at most 40 carbon atoms; and (e) alkyl groups, cycloalkyl groups, aryl groups having at most 8 carbon atoms; and (B) an organoaluminum compound obtained by contacting an organic compound having an N-O or S-O bond selected from a nitrite ester compound and a sulfite ester compound having an aralkyl group or an aralkyl group. An improved method for producing an olefinic polymer, comprising polymerizing an olefin in the presence of a catalyst system obtained from.