JPS6123204B2 - - 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 olefinic polymer that uses a novel catalyst system and has extremely high polymerization activity and excellent mechanical properties and moldability. 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 olefinic polymers using a unique catalyst system. [1] Background of the Invention When producing a polymer of olefin (especially propylene), a transition metal halide (generally titanium trichloride) and an organic 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 amorphous portions, resulting in The mechanical properties of the olefin are poor, the effective utilization of the raw material olefin is reduced, a process for removing the amorphous part is required at a stage after the completion of polymerization, and the polymerization activity is low. Disadvantages include the need to remove catalyst residue from the produced polymer after completion. 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 residue from the polymer. However, the crystallinity of the obtained polymer is relatively low, and it is difficult to say that the polymer has satisfactory practical properties if it is used as it is without removing the amorphous polymer present in the polymer. Furthermore, since the polymerization activity per support 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 specific gravity of the 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 been shown to improve the stereoregularity of polymers compared to those described above when producing polymers with low melt flow indexes, but they have been shown to improve 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, taking polypropylene (hereinafter referred to as ``PP'') as an example, a product with a melt flow index (hereinafter referred to as ``MFI'') of 3g/10 min at a temperature of 230℃ and a load of 216kg has a bending rigidity of Unless it is 11000Kg/cm2 or ^more , it is difficult to fully demonstrate the inherent advantages of the resin, so it is not practical.
When producing PP with this MFI, the n-heptane extraction residue (hereinafter referred to as "HR") of this PP is approximately 94%, and products with an HR value lower than this are not suitable for practical use. 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 studies were conducted. (1) The polymerization activity per transition metal is extremely high, and there is no problem with the color and odor of the polymer obtained for practical use without going through a complicated catalyst removal process. (2) Furthermore, the polymerization activity per transition metal (total It has a high polymerization activity (per solid catalyst) and can be used without the need for a catalyst removal process.
It does not cause corrosion of the extruder or clogging of the screen, and also allows the product (for example, film) to be easily washed. (3) The content of amorphous polymer in the resulting polymer is relatively small, and it can be used for practical purposes without removing the amorphous polymer in the resulting polymer. Due to 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 phosphorus atom-oxygen bond and a magnesium dihalide ( 2) "Tetravalent titanium compounds containing at least one halogen atom" (hereinafter referred to as "titanium-based compounds") and (3) "Si-O, P
-O, C-OH, C-O-C, N-O and S
A catalyst obtained from (B) an organoaluminum compound and a solid component obtained by contacting an organic compound having at least one type of bond selected from the group consisting of -O (hereinafter referred to as an "M-O compound"). We have discovered that by homopolymerizing or copolymerizing olefins in the presence of a polymerization system, it is possible to obtain a polymer that not only has extremely high polymerization activity but also has extremely high stereoregularity across a wide range of MFI fields. Reached. (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 MFI 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, 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. (D)), the HR of the resulting polymer decreases rapidly as the MFI increases.The reason for this is generally thought to be as follows.The polymer has various molecular weights as well as various Extraction with boiling n-butane selectively extracts the low regularity portion, but not the low regularity polymer portion; therefore,
In a polymer with a low MFI (high molecular weight), the low regularity portions cannot be completely extracted, whereas as the MFI increases (the molecular weight decreases), the high molecular weight portion decreases, making extraction difficult. This relatively near-perfection process results in an increase in MFI and a decrease in n-heptane extraction residue. In this way, this phenomenon is considered to be rather natural in the production of polyolefins, but surprisingly, in the polymers obtained by the method of the present invention, even if the MFI is varied, it does not occur at all. , no change in HR value. The cause of this phenomenon is currently not clear, but the catalyst system used in the present invention is a type of catalyst that does not generate any high molecular weight, low regularity moieties, and has a very different activity from conventional types of catalysts. 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. (i) When olefin is polymerized using A catalyst system or B catalyst system, high HR occurs when MFI is low.
However, in the practical MFI area, HR
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 formability and mechanical properties. It is possible to obtain polymers with both properties. (ii) Processes such as adhesion, coagulation, and agglomeration within equipment such as reactors and flash hoppers, due to much lower soluble content in the polymerization medium, especially during the production of polymers in the practical MFI range. By solving the above problems all at once and evaporating the polymerization solution or polymerization slurry as it is without removing any amorphous parts, it is possible to produce a polymer with good fluidity (free flowing). powder can be obtained. (2) Even when the low crystallinity portion is removed in some way, the soluble content in the solvent is very small. Since the amount of raw material olefin is very small, 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 in 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 portions and catalyst residues from the resulting polymer and inactivation of the catalyst residues, and provide excellent mechanical properties. It can be seen that the present invention is highly suitable for low-cost polyolefin production systems to obtain polymers with moldable properties. [] Specific description of the present invention (a) Organic compound having a phosphorus atom-oxygen atom bond The general formula of a typical organic compound having a phosphorus atom-oxygen atom bond used in the present invention is the following formula [() and ())]. X′lYmP ^{(OR 1 )} n () O≦l,
m<3, O<n≦3, O≦q,
r, s≦3, and R ¹ and R ² may be the same or different, and are selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, each having at most 20 carbon atoms. selected from hydrocarbon groups (which may be unsaturated or substituted with halogen atoms or alkoxy or aryloxy having at most 20 carbon atoms);
X' and Y may be the same or different, and are selected from hydrogen atoms, halogen atoms, hydroxyl groups, and the above-mentioned hydrocarbon groups (which may be unsaturated or substituted). Typical hydrocarbon groups represented by formula () include ethyldiethylphosphinite,
Ethylbutylphosphinite, ethylphenylmethylphosphinite, butylphenylvinylphosphinite, phenyldibenzylphosphinite, dimethylethylphosphonite, diphenylethylphosphonite, diethylbenzylphosphonite, diphenylethylphosphonite night,
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-chloroethyl)phosphite, tricresylphosphite, diphenylnonylphenylphosphite, tris(nonylphenyl)phosphite, diphenylisodecylphosphite, triisodecylphosphite, tris(2-chloroethyl)phosphite
-ethylhexyl) phosphite, ethylethylphosphonochloridide, phenylethylphosphonochloridide, phenylphenylphosphonochloridide, n-butylphenylphosphonochloridide, diethylchlorophosphite, diphenylchlorophosphite, Mention may be made of dioctylchlorophosphite, diethylbromophosphite, dibenzylchlorophosphite, benzylchlorophosphite, 2-chloroethyldichlorophosphite and hexyldichlorophosphite. Representative organic compounds represented by the formula () include methyldimethylphosphinate, methyldiethylphosphinate, ethyldiethylphosphinate, ethyldipropylphosphinate, ethyldi-n-butylphosphinate,
Ethyl diphenyl phosphinate, methyl dicyclohexyl phosphinate, 2-chloroethyl dibenzyl phosphinate, ethyl ethyl phosphonochloridate, phenylethyl phosphonochloridate, phenyl phenyl phosphono chloridate, n-butyl phenyl phosphonate nochloridate, ethyl ethyl phosphonobromidite,
Diethyl methyl phosphonate, diphenylphenyl phosphonate, dioctyl butyl phosphonate, diethyl phenyl phosphonate, allyl phenyl phosphonate, bis(2-
chloroethyl) phenylphosphonate, diethylcyclohexylphosphonate, diethylbenzylphosphonate, diethylphosphorochloridate, di-n-butylphosphorochloridate,
Dioctylphosphorochloridate, diphenylphosphorochloridate, dibenzylphosphorochloridate, dicresylphosphorochloridate, bis(2-chloroethyl)phosphorochloridate, diphenylphosphorobromidate, ethylphosphorodichloridate , n-butylphosphorodichloridate, phenylphosphorodichloridate, benzylphosphorodichloridate,
Cresyl phosphorodichloridate, ethyl phosphorodibromidate, 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 phenyl phosphine chloride, diphenyl phosphine bromide, methyl phenyl phosphine bromide, Dibutylphosphonic chloride, dimethylphosphonic chloride, ethylphosphonic dichloride, propylphosphonic dichloride, butylphosphonic dichloride, phenylphosphonic dichloride, phenylphosphonic dibromide, triphosphonic dichloride and benzylphosphonic dichloride can give. In producing the co-pulverized product used in the present invention, among these organic compounds having a phosphorus atom-oxygen atom bond, in formula (), R ¹ is a hydrocarbon group having at most 8 carbon atoms. Preferably, those having two or more carbon atoms are particularly preferable. Among the organic compounds represented by the formula (), preferred examples include triethyl phosphite, triphenyl phosphite, diphenylethyl phosphonite, diethyl ethyl phosphonite, diethyl butyl phosphonite, diethyl phosphite, and diphenyl phosphite. , dibutylchlorophosphite, diphenylchlorophosphite, etc. Furthermore, in formula (), R ² 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. Examples include dichloridate, propylphosphonic dichloride, triphenyl phosphate, and tributyl phosphate. (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 The treatment of magnesium dihalide with the organic compound having a phosphorus atom-oxygen atom bond can be carried out by co-pulverizing them. For co-pulverization, a pulverizer such as a ball mill, vibratory ball mill, impact pulverizer, or colloid mill may be used, but if this process generates a large amount of heat, it may be cooled for operational convenience. However, it is usually sufficient to do this 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 not a simple contact between an organic compound having a phosphorus atom-oxygen bond and a magnesium dihalide, but a close contact between the organic compound and the magnesium dihalide. It is necessary to make contact. As an example of the co-pulverization time, a porcelain ball with a diameter of 1 cm is placed in a container with an inner volume of 1 and an inner diameter of 10 cm with an apparent volume of 50%, approximately 20 g of the material to be crushed is placed, the amplitude is 60 mm, and the vibration frequency is 1 cm. When co-milling is carried out using a vibrating ball mill with a frequency of 30 Hz (hertz), it takes 30 minutes or more, preferably 1 hour or more. The co-pulverization ratio of the organic compound having a phosphorus atom-oxygen bond to 1 mol of magnesium dihalide is generally 0.005 to 1 mol, particularly preferably 0.01 to 0.7 mol. 1
If the co-pulverization ratio of the organic compound having a phosphorus atom-oxygen bond per mole of magnesium dihalide is less than 0.005 mole, not only will the polymerization activity of the resulting catalyst system be relatively low, but also the stereoregularity of the resulting polymer will be affected. Almost no improvement effect was observed. On the other hand, if the amount is 1 mole or more, the polymerization activity will be greatly reduced. (d) Titanium-based compound Furthermore, the titanium-based compound used in the present invention has a general formula represented by the following formula [formula ()]. TiX ² n (OR ³ ) m (NR ⁴ R ⁵ ) l (OCOR ⁶ ) p
() In the formula (), X ₂ is a chlorine atom, bromine atom, or iodine atom, and R ₃ , R ⁴ , R ⁵ and R ⁶ are aliprotected, alicyclic or It is an aromatic hydrocarbon group,
n is a number from 1 to 4, m, l and p are numbers from 0 to 3, and n+m+l+p is 4. Representative examples of titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, dimethoxytitanium dichloride, trimethoxytitanium chloride,
Ethoxytitanium trichloride, diethoxytitanium dichloride, triethoxytitanium chloride, propoxytitanium trichloride, butoxytitanium trichloride, dimethylaminotitanium trichloride, bis(dimethylamino)
Mention may be made of titanium dichloride, diethylaminotitanium trichloride, titanium propionate trichloride and titanium benzoate trichloride. Among these, titanium tetrahalide and titanium alkoxyhalide are preferred, and titanium tetrachloride, methoxytitanium trichloride and ethoxytitanium trichloride are particularly preferred. (e) M-O compounds Moreover, the M-O compounds used in the present invention include Si-O, P-O, C-OH, C-O-
It is an organic compound having at least one C, N-O or S-O bond. (i) Organic compounds having Si--O bonds The general formulas of typical organic compounds having Si--O bonds are shown by the following formulas [formula (), formula (), and formula ()]. Si(OR ⁷ )mRn ⁸ () R ⁹ (R ¹⁰ ₂ SiO)lSiR ¹¹ ₃ () (R ¹² ₂ SiO)p () In formulas (), (), and (), R ¹ has a large number of carbon atoms. Hydrocarbon groups selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups and aral groups (which may be unsaturated or contain halogen atoms or alkoxide groups containing at most 20 carbon atoms) ), and R ₈ ,
R ₉ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different, and are the above hydrocarbon group (which may be unsaturated or substituted), a hydrogen atom, or a halogen atom, and 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, diethoxydiptylsilane, tetra-n-ptoxysilane, di-n-ptoxy-di-n-butylsilane, tetra-secondary -butoxysilane, tetrahexoxysilane, tetraoctoxysilane, trimethoxychlorosilane, dimethoxydichlorosilane, dimethoxydipromosilane, triethoxychlorosilane, diethoxydipromosilane, diptoxydichlorosilane, dicyclopentoxydiethylsilane, Diethoxydiphenylsilane, 3.5-dimethylphenoxytrimethylsilane, methylphenyl-bis(2-chloroethoxy)silane, dimethoxydibenzylsilane, tri-2
-bropylaryloxysilane, allyl tris(2-chloroethoxy)silane and trimethoxy-3-ethoxypropylsilane. 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-disila-
1-oxacyclopentane, 1,1,3,3
-Tetramethyldisiloxane, poly(diphenyl)siloxane, poly(methylphenyl)
Mention may be made of siloxane, poly(hydromethyl)siloxane and hexachlorodine loxane. Furthermore, typical organic compounds represented by formula () include 1,3,5-trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylchlorocyclotrisiloxane, 1, 3,5-trimethyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,3,5-
Mention may be made of tribenzyltrimethylcyclotrisiloxane and 1,3,5-allyltrimethylcyclotrisiloxane. Among these organic compounds having Si-O bonds, preferred are alkoxysilanes and low-viscosity polysiloxanes, particularly tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, methoxytrimethylsilane, These include trimethoxymethylsilane, hexamethyldisiloxane, octamethyltrisiloxane, dimethylpolysiloxane, methylethylpolysiloxane, and methylphenylsiloxane. (ii) Organic compound having a P-O bond In addition, the typical general formula and representative example of an organic compound having a P-O bond are the phosphorus atom-oxygen atom bond used to produce the above-mentioned co-pulverized product. Examples include organic compounds having the following. (iii) Organic compounds having a C-OH bond The organic compounds having a C-OH bond used in the present invention are monohydric and polyhydric alcohol compounds, phenolic compounds, and naphthol compounds, and among alcohol compounds, , in particular a monovalent group having 2 to 20 carbon atoms and having a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aralkyl group, and said hydrocarbon group being substituted with a halogen atom and/or an alkoxy group. Also preferred are polyhydric alcohol compounds. Representative examples of preferred alcohol compounds include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-propyl alcohol.
-butyl alcohol, isobutyl alcohol, secondary-butyl alcohol, tertiary-butyl alcohol, isoamyl alcohol, cyclohexanol, stearyl alcohol,
benzyl alcohol, ethylene glycol,
Examples include propylene glycol and glycerin. (iv) Organic compound having a C-O-C bond The organic compound having a C-O-C bond used in the present invention contains saturated or unsaturated aliphatic, cycloaliphatic, and aromatic hydrocarbon groups (monocarbon groups). It is a linear or cyclic ether having at most 40 carbon atoms, which may be partially substituted with halogen. Typical examples thereof include dimethyl ether, methyl. 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 glycol, polypropylene glycol, ethylene glycol dimethyl ether, diethyl cellosolve and benzyl. Linear aliphatic ethers such as methyl ether; diphenyl ether, di-p-
Mention may be made of linear aromatic ethers such as tolyl ether, anisole, ethoxybenzene, dimethoxybenzene, promuanisole and chloranisole, and cyclic ethers such as furan, tetrahydrofuran, dioxane, coumaron, coumaran and tetrahydropyran. Among these, monofunctional ethers are preferred, particularly diethyl ether, di-n-propyl ether, di-isopropyl ether, di-n-butyl ether, di-isobutyl ether, anisole,
Ethoxybenzene and diphenyl ether are preferred. (v) Organic compound having N-O or S-O bond The organic compound having N-O or S-O bond used in the present invention is an alkyl group or cycloalkyl group having at most 8 carbon atoms. , nitrite ester compounds and sulfite ester compounds having a hydrocarbon group selected from the group consisting of aryl groups and aralkyl groups, in particular sulfite ester compounds having an alkyl group having at most 8 carbon atoms. Ester compounds and sulfite ester 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 phosphorus atom-oxygen atom bond and magnesium dihalide" (hereinafter referred to as "component
(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 use 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 stirring contact with (1) is preferably as high as possible unless there is any operational problem, 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, the aliphatic hydrocarbon and aromatic hydrocarbon used as a solvent 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 Examples include alkyl aluminum hydrides such as hydride, and alkyl aluminum halides such as diethyl aluminum chloride and diethyl aluminum 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 The electron-donating compound is generally Ziegler. Known substances that are widely used as stereoregularity improvers and particle size distribution improvers for Natsuta-type catalysts can be used, but among them, organic carboxylic acid ester compounds and the above-mentioned M-
Preferred are alcohol compounds, ether compounds, organic compounds having a P-O bond, and organic compounds having a Si-O bond, which are shown as organic compounds having an O bond. Among these electron-donating compounds, organic carboxylic acid ester compounds are particularly suitable. Typical 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. It is a carboxylic acid ester derived from a monohydric or polyhydric alcohol of the above group, 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, amyl 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;
Hexyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, dimethyl phthalate, diethyl phthalate,
Mention may be made of aromatic carboxylic acid esters such as diethyl terephthalate, ethylene glycol dibenzoate and methyl naphthoate. Among these, aromatic carboxylic acid esters are particularly desirable. (i) 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 a practically usable melt flow, 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 be explained in more detail below using 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
The index (i.e. MFI) is JIS K-6758
−1968. The bending rigidity and tensile yield strength were determined by ASTM D-747- for the pressed pieces obtained according to JIS K-6758-1968.
63 and ASTM D-638-64T. Melt index (hereinafter referred to as "MI") was measured according to JISK-6760. Density is JIS
Measured by 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 at 127.0°C. (manufactured by Kyoto Denshi Kogyo Co., Ltd.) for 5 hours with thorough stirring. 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 of the compounds used in the production and polymerization of catalyst components (organic solvent, olefin, hydrogen, titanium compound, magnesium dihalide, M-O compound, electron-donating compound, etc.) are essentially The water has been removed. Furthermore, the preparation 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 as an organic compound with a phosphorus atom-oxygen atom bond (hereinafter referred to as "phosphorus-containing organic compound")
6.0 g of phenylphosphonic dichloride [hereinafter referred to as "compound (a)"] was placed in a container for a vibrating ball mill (cylindrical stainless steel, internal volume 1, porcelain balls with a diameter of 10 mm and an apparent volume of approximately 50 %filling)
I put it in. This was attached to a vibrating ball mill with an amplitude of 6 mm and a frequency of 30 Hz, and co-pulverization was carried out for 8 hours. Of the obtained homogeneous co-pulverized material, 15g was
In a 500 ml flask, 86.3 g of titanium tetrachloride and 47.1 g of triphenyl phosphite (hereinafter referred to as "compound (1)") as an M-O compound were mixed and reacted in 125 ml of toluene at room temperature. The resulting solution was added. Stirring and mixing were performed at 65°C for 2 hours. After the obtained solid components were filtered off, they were washed with toluene until titanium tetrachloride was no longer detected in the filtrate. After washing, by drying at 40°C under reduced pressure.
A powdered catalyst component (A) was prepared. Chemical analysis of the obtained catalyst component (A) revealed that the content of titanium atoms in this catalyst component was 1.44% by weight. [(B) Polymerization and physical properties of the produced polymer] In a 3.0 stainless steel autoclave, 38.4 mg of the catalyst component (A) produced by the above method, 0.54 g of triethylaluminum as a trialkyl aluminum compound, and an electron-donating compound were placed. as
0.22g 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, 287 g of powdered polypropylene was obtained. That is, the polymerization activity is 7475
g/g-catalyst component (A)/hour, 519 Kg/g-Ti/hour. The HR of this polypropylene powder is 97.5
It was %. This powder was prepared without further purification, using 100 parts by weight of the powder and 0.15 parts by weight of tetrakis[methylene-3-(3'5'-di-tertiary-butyl-4'hydroxyphenyl)propionate] as a stabilizer. Methane (manufactured by Ciba Geigy, product name Irg)
anox1010), 0.20 parts by weight of distearyl thiodipropionate, and 0.10 parts by weight of calcium stearate were kneaded into pellets at 210°C under a nitrogen atmosphere using an extractor with an inner diameter of 20 mm and L/D of 40. . The obtained pellets exhibited whiteness and transparency comparable to those of ordinary commercially available products. MFI was 3.8 g/10 minutes. The bending rigidity of the pressed plate of this pellet is 13200Kg/ ^cm2 ,
The tensile yield strength was 330 Kg/cm ² and showed excellent physical properties. Examples 2 to 9, Comparative Example 1 When producing the co-pulverized product in (A) of Example 1, instead of 6.0 g of compound (a) used as the limo-containing organic compound, compound (a), Triphenyl phosphate [hereinafter referred to as “compound (b)”], triphenyl phosphite [hereinafter referred to as “compound (c)”]
and triethyl phosphite [hereinafter “compound
Co-pulverization was carried out in the same manner as in Example 1 (A), except that the amounts shown in Table 1-1 were used. In place of the compound (1) used as the M-O compound in preparing the catalyst component (A) in Example 1 (A), tetraethoxysilane [hereinafter referred to as "compound (2)"], dimethyldimethoxy Silane [hereinafter referred to as “compound (3)”], ethyl alcohol [hereinafter referred to as “compound (4)”], phenol [hereinafter referred to as “compound (5)”]
], diethyl ether [hereinafter referred to as "compound (6)"]
], diphenylphosphorochloridate [hereinafter referred to as ``compound (7)''], butyl nitrite [hereinafter referred to as ``compound (8)''], and diethyl sulfite [hereinafter referred to as ``compound (9)'']. A catalyst component was prepared in the same manner as in Example 1 (A), except that the amounts shown in Table 1-1 were used (however, the M-O compound was not used in Comparative Example 1). The titanium atom content (in weight %) of each catalyst component is shown in Table 1-1. Each of the catalyst components obtained above was added to 1-2.
Polymerization of propylene was carried out under the same conditions as in Example 1 (B) except that the amounts shown in the table were used. The yield of each polypropylene powder obtained and the HR of each polypropylene powder are shown in Table 1-2. Furthermore, pellets were prepared from each polypropylene in the same manner as in Example 1 (B). The MFI of each pellet is shown in Table 1-2. In addition, press plates were made from each pellet. The bending rigidity and tensile yield strength of each press plate are shown in Table 1-2.

【table】

[Table] Example 10 In place of the compound (a) used as the phosphorus-containing organic compound for producing the co-pulverized product in (A) of Example 1, 6.0 g of diphenyl octyl phosphate [hereinafter referred to as "compound ( e).
Co-pulverization was carried out in the same manner as in Example 1 (A). 3.12 g of titanium tetrachloride and 0.86 g of tetraethoxysilane [hereinafter referred to as "Compound 10"] were added to the obtained co-pulverized product.
and co-pulverized for 1 hour under the same conditions as above (titanium atom content of the obtained co-pulverized product was 2.63% by weight). Propylene was prepared under the same conditions as in Example 1 (B), except that 37.0 mg of the above catalyst component (co-pulverized product) was used in place of the catalyst component (A) used in Example 1 (B). Polymerization was carried out. As a result, 253 g of powdered polypropylene was obtained. That is, the polymerization activity is 6.838 g/g-catalyst component/time, and 260
Kg/g-Ti・hour. The HR of the obtained polypropylene was 97.3%. Pellets were prepared from this polypropylene powder in the same manner as in Example 1 (B). The MFI of the pellets obtained was 4.4 g/10 minutes. The bending rigidity of the pressed plate of this pellet is
The tensile yield strength was 13300Kg/cm ² and the tensile yield strength was 331Kg/cm ² . Example 11 Example 1 except that 5.0 g of compound (e) was used instead of compound (a) used as the phosphorus-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 (A). Example 1
Compound (1) in which the co-pulverized product obtained above was used instead of the co-pulverized product used in preparing the catalyst component (A) in (A), and was further used as an M-O compound.
A catalyst component (titanium atom content: 22.5% by weight) was prepared in the same manner as in Example 1 (A), except that 49.7 g of triphenyl phosphate was used instead. Polymerization of propylene was carried out under the same conditions as in Example 1 (B), except that 0.24 g of ethyl anisate was used instead of 34.8 mg of the catalyst component and ethyl benzoate used as the electron donating compound. As a result, 275g of powdered polypropylene was obtained.In other words, the polymerization activity was 7902g/g-catalyst component/hour, and 351Kg/time.
g-Ti・time. The HR of the obtained polypropylene was 96.2%. Pellets were prepared from this polypropylene powder in the same manner as in Example 1 (B).
The MFI of the pellets obtained was 5.1 g/10 minutes. The bending rigidity of the pressed plate of this pellet is
The tensile yield strength was 13000Kg/cm ² and 325Kg/cm ² . Example 12 Co-pulverized product prepared in the same manner as Example 1 (A)
Co-pulverization was carried out for 1 hour under the same conditions as in Example 10, except that 1.70 g of Compound (1) was used in place of 26.0 g of Compound 10 used as the MO compound in Example 10. The titanium atom content of the obtained co-pulverized product (catalyst component) was 2.56% by weight. 8.8 mg of the catalyst component obtained above, 0.54 g of triisobutylaluminum (as an organic aluminum compound), 1 kg of isobutane (as an inert solvent) and 0.19 g of hydrogen were added to a 3.0 stainless steel autoclave. . 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, 561 g of powdered polymer (ethylene monopolymer) was obtained. That is, the product productivity was 63,800 g/g-catalyst component, and the polymerization activity was 1,520 kg/g-Ti.hour. 100 parts by weight of the powder and 0.2 parts by weight of 2.
6-di-tertiary-butyl-4-methyl-phenol was extracted using an extractor with an inner diameter of 20 mm and L/D of 40,
Pellets were prepared by kneading at a temperature of 180°C under a nitrogen atmosphere. The obtained pellets had a whiteness comparable to that of ordinary commercially available products. of this polymer
MI is 0.29g/10min, HLMI (load 21.6
kg, melt flow index at temperature 1.0℃) is 7.0g/
It was hot in 10 minutes. (In other words, HLMI/MI is
24.1). That is, this polymer had a narrow molecular weight distribution. Also, the density of this polymer is
It was 0.9663g/cc. Example 13 In place of the titanium tetrachloride used as the titanium-based compound in preparing the catalyst component (A) in Example 1 (A), 90.7 g of ethoxytitanium trichloride was used, and 90.7 g of ethoxytitanium trichloride was used as the M-O compound. A catalyst component was prepared under the same conditions as in Example 1 (A), except that 25.3 g of triester phosphite was used instead of compound (1). The titanium atom content of the obtained catalyst component was 1.32% by weight. Using 43.8 mg of the catalyst component obtained as described above, 1.2 g of ethylene was added as a comonomer.
Copolymerization of propylene and ethylene was carried out in the same manner as in Example 1 (B) except that the mixture was charged at a rate of 5 minutes. As a result, 258 g of powdered propylene and ethylene copolymer (ethylene unit content is 3.8
% by weight) was obtained. That is, the polymerization activity is 5890
g/g-catalyst component/time, 446Kg/g-Ti.
It's time. Also, the MFI of this copolymer is 4.1
g/10 minutes. Example 14 A co-pulverized product was produced in the same manner as in Example 6, except that 20 g of anhydrous magnesium bromide was used instead of the anhydrous magnesium chloride used in producing the co-pulverized product in Example 6. A catalyst component was prepared in the same manner as in Example 6, except that 23.8 g of compound () was used instead of compound (6) used as the M-O compound in preparing the catalyst component in Example 6. The titanium atom content of the obtained catalyst component is
It was 2.1% by weight. Polymerization of propylene was carried out in the same manner as in Example 1 (B), except that 38.1 mg of the above catalyst component was used in place of the catalyst component (A) used in Example 1 (B). As a result, 260 g of powdered polypropylene was obtained. In other words, the polymerization activity is 6822g/g
-Catalyst component/time, which is 325Kg/g-Ti/hour. In addition, the HR of this polypropylene is 97.5
It was %. Pellets were prepared from the obtained polypropylene powder in the same manner as in Example 1 (B). The MFI of the pellets obtained was 3.2 g/10 minutes. The bending rigidity of the pressed plate of this pellet is 13000Kg/cm ²
The tensile yield strength was 328 Kg/cm ² . Example 15 Example 1 except that 4.0 g of compound (e) was used instead of compound (a) used as the phosphorus-containing organic compound in producing the co-pulverized product in (A) of Example 1. A catalyst component was prepared in the same manner as in (A) of Example 1, except that a co-pulverized product was prepared in the same manner as in (A) of Example 1, and the obtained co-pulverized product was used. The titanium atom content of the thus obtained co-pulverized product was 1.38% by weight. Ethylene polymerization was carried out under the same conditions as in Example 12, except that 9.3 mg of the catalyst component obtained as above was used. As a result, 561 g of polymer (ethylene monopolymer) was obtained. That is, the product activity is 60300 g/g-catalyst component, and the polymerization activity is 1457 Kg/g-Ti/hour. The MI of the obtained ethylene monopolymer is 0.25g/
10 minutes and the HLMI was 6.8 g/10 minutes (ie, HLMI/MI was 27.2). Example 16 Example 1 except that 4.0 g of compound (a) was used instead of compound (a) used as the phosphorus-containing organic compound in producing the co-pulverized product in (A) of Example 1. A co-pulverized product was produced in the same manner as in (A). Example 1
When preparing the catalyst component (A) in (A), M-O
62.1 instead of compound (1) used as a compound
g of methylphenylpolysiloxane (viscosity is 25℃
A catalyst component was prepared in the same manner as in Example 1 (A) except that 450 centistokes was used.
The titanium atom content of the obtained catalyst component was 1.54% by weight. In place of the catalyst component used in polymerizing ethylene in Example 12, 9.0 mg of the catalyst component obtained as described above was used, and 20 mg of diethyl ether was used as an electron-donating compound. Ethylene homopolymerization was carried out under the same conditions as in Example 12. As a result, 492 g of polymer (ethylene monopolymer) was obtained. That is, the product activity was 54,700 g/g-catalyst component, and the polymerization activity was 1183 Kg/g-Ti/hour. The MI of the obtained ethylene monopolymer is 0.30g/
10 minutes, and the HLMI was 6.1 g/10 minutes (ie, HLMI/MI was 20.3). Example 17 Example 10 except that 2.0 g of compound (c) was used instead of compound (e) used as the phosphorus-containing organic compound in producing the co-pulverized product in Example 10.
A co-pulverized product was produced in the same manner as above. The obtained co-pulverized product was used, 0.87 g of compound (5) was used instead of compound (2) used as the M-O compound, and the amount of titanium tetrachloride used was changed to 1.76 g. A co-pulverization process was carried out in the same manner as in Example 10 to produce a co-pulverized product (catalyst component). The titanium atom content of the obtained catalyst component was 1.80% by weight. 9.4 mg of the catalyst component obtained as described above was used instead of the catalyst component used in Example 12, and 0.74 g of trihexylaluminum was used instead of the triisobutylaluminum used as the organoaluminum compound. Copolymerization of ethylene and butene-1 was carried out under the same conditions as in Example 12, except that 13 mg of ethyl alcohol was used as the compound and 15.0 g of butene-1 was used as a comonomer. As a result, 472 g of a powdered polymer (a copolymer of ethylene and butene-1) was obtained. In other words, the production unit is 50200
g/g catalyst component and 930 Kg/g-Ti/hour. This polyethylene powder was kneaded into pellets using an extruder in the same manner as in Example 12. The obtained pellets exhibited a whiteness comparable to that of commercially available products. The MI of the obtained copolymer is 0.37
g/10 minutes, and the density was 0.9377 g/cc.
The number of ethyl groups per 1000 carbons in this copolymer was 5. The extraction residue of the obtained copolymer by the simple fractionation method was 18.0% by weight.
The number of ethyl groups per 1000 carbons was 4.1. Comparative Example 2 A catalyst component was prepared in the same manner as in Example 11, except that the compound (e) used as the phosphorus-containing organic compound in producing the co-pulverized product in Example 11 was not used. Homopolymerization of propylene was carried out in the same manner as in Example 11, except that the catalyst component thus prepared was used. As a result, 124 g of powdered polymer was obtained. In other words, the polymerization activity is 960g/g
-Catalyst components and time. The obtained polypropylene HR was 84.2%. Pellets were prepared from this polypropylene powder in the same manner as in Example 1 (B).
The MFI of the pellets obtained was 13.6 g/10 minutes. The bending rigidity of the pressed plate of this pellet is 9300
Kg/cm ² , and the tensile yield strength was 251 Kg/cm ² . Comparative Example 3 During co-grinding, 6.0 g of ethyl benzoate and
A catalyst component was prepared in the same manner as in Example 1 (A), except that 4.6 g of silicon tetrachloride was used and compound (1) was not used in the preparation of the catalyst component. Polymerization of propylene was carried out in the same manner as in Example 1, except that the above catalyst component (titanium atom content: 2.8% by weight) was used instead of catalyst component (A). As a result, 178g of powdered polypropylene (HR is
92.7%) was obtained. That is, the polymerization activity is 3520
g/g-catalyst component/time, 126Kg/g-Ti hour. The obtained powdered polypropylene powder was pelletized in the same manner as in Example 1 (MFI was 5.2 g/10 minutes).
It was created. The pellets had the same degree of whiteness and transparency as common commercially available products. The bending rigidity of the press plate of the obtained pellets is 10800Kg/
cm ² , and the tensile yield strength was 285 Kg/cm ² , showing insufficient mechanical properties. Example 1, Example 2, Comparative Example 2, Comparative Example 3, and Reference Example (0.20 g of AA type titanium trichloride and 0.58 g of titanium trichloride were used, except that the amount of hydrogen used was changed as shown in Table 2.
Polymerization of propylene was carried out under the same conditions as in Example 1 (B) using a catalyst system obtained from diethylaluminum chloride (g). Table 2 shows the HR of each of the propylene powders obtained and the MFI of pellets made from each polypropylene powder under the same conditions as in Example 1.

【table】

[Table] Table 2 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 2, Comparative Example 2, Comparative Example 3, and Reference Example in Table 2.
This is a relationship diagram between HR (vertical axis unit: %) and pellet MFI (horizontal axis unit: g/10 min).

Claims (1)

[Scope of Claims] 1 (A) (1) A co-pulverized product of an organic compound represented by the following formula [formula () and formula ()] having a phosphorus atom-oxygen atom bond and magnesium dihalide, ₁ YmP(OR ¹ )n () X′qYrP(O)(OR ² )s () () In formulas
The sum of and n or q and r and s is 3, and 0≦
1, m<3, 0<n≦3, 0≦
q, r, s≦3, R ¹ and R ² may be the same or different, and have at most 20 carbon atoms selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. selected from hydrogen groups (which may be unsaturated or substituted with halogen atoms or alkoxy or aryloxy groups having at most 20 carbon atoms); X' and Y may be the same or different; It is selected from the above hydrocarbon groups (which may be unsaturated or substituted). (2) A tetravalent titanium compound having at least one halogen atom represented by the following formula [formula ()] and TiX ² n (OR ₃ ) m (NR ⁴ R ⁵ ) ₁ (OCOR ⁶ ) p
() In the formula (), X ₂ is a chlorine atom, a bromine atom, or an iodine atom, and R ³ , R ⁴ ,
R ⁵ and R ⁶ each have a large number of carbon atoms.
12 aliphatic, alicyclic or aromatic hydrocarbon groups, n is a number from 1 to 4, m, 1
and p is a number from 0 to 3, n+m+
1+p is 4. (3) At least one organic compound selected from the following group (a) Represented by the following formula [() or ()]. Organic compound having Si-O bond Si(OR ⁷ ) mR ⁸ n () R ⁹ (R ¹⁰ ₂ SiO) ₁ SiR ¹¹ ₃ () (R ¹² ₂ SiO)p () () formula, () formula and ( ), R ¹ is a hydrocarbon group selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups having at most 20 carbon atoms (these may be unsaturated, halogen atoms, or carbon atoms R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be the same or different, and the above hydrocarbon groups (these may be unsaturated or substituted). ), hydrogen atom or halogen atom, m+n is 4
(however, m≠0) 1 is 1 or
is an integer of 1000, and p is an integer of 2 to 1000. (b) an organic compound having a P-O bond selected from organic compounds having a phosphorus atom-oxygen atom bond used to produce the co-pulverized product; (c) monohydric and polyhydric alcohol compounds;
Organic compounds having a C-OH bond, such as phenolic compounds and naphthol compounds (d) Saturated or unsaturated aliphatic, cycloaliphatic, and aromatic hydrocarbon groups (which may be partially substituted with halogen) (e) alkyl, cycloalkyl, aryl groups and A solid obtained by contacting a nitrite ester compound having a hydrocarbon group selected from the group consisting of aralkyl groups and an organic compound having an N-O or S-O bond selected from sulfite ester compounds. An improved method for producing an olefin-based polymer, comprising polymerizing an olefin in the presence of a catalyst system obtained from a component and (B) an organoaluminum compound.