JPS5840564B2 - Method for producing olefin polymer - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing olefin 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 new catalyst.

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 article relates to a method for polymerizing olefins using a unique catalyst system.

When producing polymers of olefins (especially propylene), transition metal halides (
It is well known that catalyst systems obtained from organometallic compounds (generally titanium trichloride) and organometallic compounds (generally organoaluminum compounds) are suitable.

However, when producing polymers using these catalysts, the stereoregularity of the resulting polymers is not always satisfactory, and therefore the resulting polymers contain relatively large amounts of non-quality parts and Poor mechanical properties of coalescence, reduced effective utilization of starting olefins, the need for a process to remove amorphous portions at a post-polymerization stage, and low polymerization activity. After the end,
Disadvantages include the need to remove catalyst residue from the produced polymer.

Therefore, many proposals have been made as catalysts for producing polymers with high stereoregularity.

Some of the present inventors have already proposed a catalyst system obtained from titanium trichloride contact-treated with an acyl halide or a eutectic of it and aluminum chloride and an organoaluminum compound (Japanese Patent Laid-Open No. 4726487). .

Although this catalyst system had significantly improved polymerization activity, it was insufficient to eliminate the need to remove catalyst residues from the resulting polymer.

On the other hand, a catalyst system obtained from a solid component in which a titanium compound is supported on magnesium halide and an organoaluminium compound (hereinafter referred to as "A catalyst system") has higher polymerization activity than conventional catalyst systems, and has a high polymerization rate. It is said that there is a possibility that there is no need to remove catalyst residue from the catalyst.

However, the crystallinity of the obtained polymer is relatively low;
If the polymer is used as it is without removing the non-quality polymer present in the polymer, 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 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 system") obtained from a solid component in which titanium tetrahalide is supported on a carrier pretreated with magnesium dihalide with an organic acid ester and a silicon compound and an organoaluminum compound is as follows: When producing a polymer with a low melt flow index (mel 1 flow index), although the stereoregularity of the polymer was improved compared to the above, it was difficult to obtain a practical melt by controlling the molecular weight. When producing a polymer with a flow index, its stereoregularity is greatly reduced, and it is impossible to obtain a product with practical mechanical properties unless the inferior polymer is removed. It cannot be said that this is sufficient to simplify the manufacturing process and reduce manufacturing costs.

For example, using polypropylene (hereinafter referred to as "PP"), a product with a melt flow index (hereinafter referred to as "MFI") of 3 g/10 minutes at a temperature of 230°C and a load of 2.16 kg has a bending rigidity of rate is 11.00
Unless it is 0 kg/cri1 or more, it is difficult to fully demonstrate the inherent advantages of the resin, so it is not practical, but this MFI
When producing PP having PP, the n-heptane extrusion residue (hereinafter referred to as IH) of this PP is used.

R, J) is approximately 94%, and below this H,
In order to make a product showing a value of R, into a practical product, it is necessary to sufficiently remove the low crystallinity PP with an appropriate solvent.

Based on the above, the present inventors aimed to obtain a catalyst system having sufficiently high polymerization activity and sufficiently high stereoregularity of the obtained polymer to the extent that removal of catalyst residues and non-quality polymers is unnecessary. As a result of various studies, we found that (A) (1) Magnesium dihalide pulverized together with acyl halide contains (2) a tetravalent titanium compound having at least one halogen atom (hereinafter referred to as the "titanium compound"). The catalyst system obtained from the solid component obtained by contacting the mixture or addition reaction product of (B) with the trialkylaluminium compound and the (0) organic carboxylic acid ester not only has an extremely high polymerization activity, but also has an extremely high polymerization activity. Surprisingly, unlike conventional olefin polymerization catalysts, H, R, does not decrease at all (see Fig. 1 for details), and therefore, in the MFI region (1 to 21/10 minutes at MFI) with practical formability,
The inventors have discovered that it is possible to obtain a polymer having extremely high stereoregularity, and have arrived at the present invention.

That is, taking polypropylene as an example, as is clear from Fig. 1, conventional catalyst systems, namely, a catalyst system based on titanium trichloride [F in Fig. 1], a catalyst system A [D in Fig. 1]
] and B catalyst system [E in Figure 1], the H, R, of the produced 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-Hepukun selectively extracts the low regularity portions, but the low regularity high molecular weight portions are extracted selectively. Therefore, in polymers with low MFI (high molecular weight), the low regularity portions cannot be completely extracted, whereas as the MFI increases (low molecular weight), the high molecular weight portions are extracted. As a result of the reduction, the MFI is
As the value increases, the amount of residue extracted by n-hebutane decreases, that is, the stereoregularity decreases.

In this way, this phenomenon was thought to be rather natural in the production of polyolefins, but surprisingly, in the polymer obtained by the method of the present invention, MF
This shows a relationship in which even if I is changed in various ways, the H, R, and values do not change at all.

The cause of this phenomenon is currently not clear, but it is thought that 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 an activity that is very different from that of conventional catalysts. It is assumed that it has a point distribution.

Since the polymerization method according to the present invention has the above characteristics, there are various advantages as shown below.

First, when olefins are polymerized using a catalyst system mainly composed of titanium trichloride, A catalyst system, or B catalyst system, although the stereoregularity is high at low MFI, the stereoregularity is low in the practical MFI region. 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 a polymer with excellent moldability and mechanical properties can be obtained. I can do it.

Also, during the production of polymers, especially in the practical MFI range, the soluble content in the polymerization medium is much lower, resulting in process problems such as adhesion, cross-sticking, and agglomeration within equipment such as reactors and flash hoppers. By solving the problems at once and directly evaporating the polymerization solution or polymerization slurry without removing the non-crystalline portion, it is possible to obtain a polymer powder with good fluidity.

Furthermore, even if the low crystallinity portion is somehow removed, the soluble content in the solvent is very low, and therefore,
Since only a small amount is removed by the solvent, the raw material olefin can be used effectively.

Moreover, the polymerization activity of the catalyst system used in the present invention is extremely high, and in particular, the polymerization property 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 produce a polymer that can be used in normal use without any special operation for removing catalyst residue or post-treatment for inactivating catalyst residue.

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.

In the present invention, acyl halide is 1 , I! A compound containing a -C-X group (X is a halogen atom).

As an acyl group, saturated or unsaturated aliphatic carbonyl groups having at most 20 carbon atoms, carbonyl groups containing an alicyclic ring, carbonyl groups containing an aromatic ring, and halogen or alkoxy substituted products thereof are usually used. It is chosen.

Representative examples include acetyl fluoride, acetyl chloride,
Acetyl bromide, acetyl iodide, propionyl chloride, propionyl bromide, butyryl chloride, butyryl bromide, balmitoyl chloride, stearoyl chloride, stearoyl bromide, oleoyl chloride, oleoyl bromide, trichloroacetyl chloride, trichloroacetyl bromide, Oxalyl dichloride, malonyl dichloride, succinyl dichloride, glycaryl dichloride, adipoyl dichloride, acryloyl chloride, acryloyl bromide, fumaroyl dichloride, methacrylic chloride, cinnamoyl chloride, cinnamoyl bromide, β-carbomethoxypropionyl chloride, β - aliphatic carbonyl halides such as carboxyacryloyl chloride and phenoxyacetyl chloride, cyclohexanecarbonyl chloride,
Alicyclic carbonyl halides such as cyclohexanecarbonyl bromide, norbornene dicarbonyl dichloride and furoyl chloride, and benzoyl fluoride, benzoyl chloride, benzoyl iodide, naphthoyl chloride, naphthoyl bromide, toluoyl chloride, toluoyl bromide, phthaloyl dichloride, Examples include aromatic carbonyl halides such as anisoyl chloride and chlorobenzoyl chloride.

Among these acyl halides, aromatic carbonyl halides are preferred, and benzoyl chloride, benzoyl bromide, toluyl chloride, toluyl bromide, and the like are particularly preferred.

In addition, magnesium dihalide is a so-called anhydride that does not contain water of crystallization, and commercially available products generally contain 2
It is desirable to heat and dry at 00 to 600°C.

Typical examples include magnesium chloride, magnesium bromide and magnesium iodide, among others.
Magnesium chloride is preferred.

The treatment of magnesium dihalides with the acyl halides can be obtained 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, cooling may be used for operational convenience. However, it is usually best to do this at around room temperature.

The time required for co-pulverization varies depending on the performance of the pulverizer and so cannot be generally specified, but it is necessary to bring the acyl halide and the magnesium dihalide into intimate contact reaction rather than simple contact.

As an example of the co-pulverization time, a porcelain ball with a diameter of 1 crft is placed in a container with an internal volume of 111 mm and an inner diameter of 10 CrIL, and about 20 g of the material to be crushed is placed in a container with an amplitude of 6 Cr. When co-pulverizing is performed using a vibrating ball mill with a vibration frequency of 30 Hz (Hertz), it takes 30 minutes or more, preferably 1 hour or more.

The co-pulverization ratio of acyl halide to 1 mol of magnesium dihalide is generally 0.01 to 2 mol, particularly preferably 0.04 to 1 mol.

If the co-pulverization ratio of acyl halide to 1 mole of magnesium dihalide is less than 0.01 mole, not only the polymerization activity of the resulting catalyst system is relatively low, but also the effect of improving the stereoregularity of the resulting polymer is hardly noticeable. I can't do it.

On the other hand, if the amount is 2 moles or more, the polymerization activity will be greatly reduced.

The general formula of the titanium-based compound is shown by the following formula.

T i xn (OR:')m(NR2R")l(
OCOR').

In the formula, A number from 1 to 4, m, A? 1 and p are O
A number between 3 and n + m + l! +p is 4
It is.

Typical examples of titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytitanium trichloride, dimethoxytitanium dichloride, trimethoxytitanium chloride, ethoxytitanium trichloride, jetoxytitanium dichloride, and triethoxytitanium. Mention may be made of chloride, propoxytitanium trichloride, butoxytitanium trichloride, diethylaminotitanium trichloride, bis(dimethylamino)titanium dichloride, diethylaminotitanium trichloride, propionate titanium trichloride and benzoate titanium trichloride.

Among these, titanium tetrahalide and titanium alkoxyhalide are preferred, and titanium tetrachloride, methoxytitanium trichloride and ethoxytitanium trichloride are particularly preferred.

Ether compounds include linear or cyclic ethers having at most 40 carbon atoms and having aliphatic, cycloaliphatic, and aromatic hydrocarbon groups (which may be partially substituted with halogen); Typical examples 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 Linear aliphatic ethers of glycol, polypropylene glycol, ethylene glycol dimethyl ether, diethyl cellosolve and benzyl methyl ether; diphenyl ether, JP-)'J 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, and %cc,') ethyl ether, di-n-propyl ether, di-isopropyl ether, di-n-butyl ether, di-isobutyl ether, anisole, ethoxybenzene and diphenyl ether are preferred. .

These titanium compounds and ether compounds are "magnesium dihalide pulverized with acyl halide" (hereinafter referred to as "component (1)") obtained as described above.
It is preferable to contact the component (1) at the same time as the component (1).
) is contacted with a titanium compound, and then the excess is removed by washing with a solvent, and then an ether compound is contacted, or component (1) is contacted with an ether compound, and then the excess is removed with a solvent. A method in which a titanium-based compound is brought into contact with a titanium-based compound after washing and removing it is not desirable because the effects of the present invention cannot be fully exhibited.

Based on the above, component (1) is added to a mixture of a titanium compound and an ether compound, or a mixture of the titanium compound and an ether compound is added to a mixture in which the reaction between the two is completed by a treatment such as heating, or a titanium compound and an ether compound are combined. It is preferable to simultaneously mix component (1) and carry out the contact treatment.

The proportion of the titanium compound used per mol of the titanium compound is generally 0.1 to 50 mol, and 0.2 to 50 mol.
20 mol is preferred.

Particularly suitable is a range of 0.5 to 10 moles that can form a large amount of quantitative complex compound of the ether compound and the titanium compound.

In carrying out the contact treatment, component (1), the titanium compound, and the ether compound may simply be brought into contact with each other, but in order to produce efficiently, the whole should be stirred in an appropriate solvent or a pulverizer should be used. Among them, it is desirable to apply a method such as co-pulverization using the same method as described above.

Solvents used for mixing or reacting titanium compounds with ether compounds and for stirring contact include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene; Although halogenated hydrocarbons such as methylene chloride, trichloroethane, trichloroethylene and chlorobenzene can be used, aliphatic hydrocarbons are particularly preferred.

The concentration of the stirring contact is preferably as high as possible unless there is a problem with the operation, and is usually 0.005 mol-T i /1.
The above 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 good performance. In order to obtain this, 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 if the contact is carried out for more than 10 hours, it is not observed that a better supported material can be obtained.

After the above-mentioned contact, it is desirable to wash with an inert solvent, such as those listed as effective in stirring contact treatment.

Trialkylaluminum compounds have the general formula Al
R1R2R3 (R1, R2 and R3 may be the same or different and are an alkyl group having at most 8 carbon atoms).

Typical examples include trimethylaluminum, triethylaluminum, tri')-n-7'ropylaluminum, triisopropylaluminium, tri-n-butylaluminum, triisobutylaluminum and h')-n-hexylaluminum,
Particularly preferred is triethylaluminum.

Furthermore, organic carboxylic acid esters include aliphatic, alicyclic or aromatic carboxylic acids having at most 20 carbon atoms and aliphatic, alicyclic or aromatic monovalent carboxylic acids having at most 20 carbon atoms. or a carboxylic acid ester derived from a polyhydric alcohol, a part of which 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, vinyl acetate, butyl acetate, ethyl butyrate, phenyl propionate, furfuryl furopionate, diethyl malonate, Aliphatic carboxylic acid esters such as 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-furate Acid esters and methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, phthalate dimethyl acid, diethyl phthalate, diethyl terephthalate,
Aromatic carboxylic acid esters such as ethylene glycol dibenzoate and methyl naphthoate are mentioned.

Among these, aromatic carboxylic acid esters are particularly desirable.

In obtaining the catalyst system used in the present invention, each of the acyl halides, magnesium dihalides, titanium compounds, ether compounds, trialkyl aluminum compounds, and organic carboxylic acid esters may be used alone or in combination. The above may be used in combination.

(4), (B) and (C) Each catalyst component may be introduced separately into the polymerization vessel, but two or three of them (a mixture of component (1) and a titanium compound and an ether compound or Although only one type of addition reaction product may be mixed in advance, it is particularly preferable to mix three types immediately before polymerization.

The ratio of the mixture or addition reaction product (as titanium atoms) and organic carboxylic acid ester to 1 mol of trialkylaluminum compound in the polymerization system is generally 0.001 to 1 mol and 0.0 mol, respectively.
2 to 1 mol, especially o, ooi to 0
．． 2 mol and 0.1 to 0.7 mol are preferred.

The olefins polymerized by the catalyst system obtained as described above are olefins having at most 12 carbon atoms, and representative examples thereof include ethylene propylene, butene-1,4-methylpentene-1, and hexene-1,4-methylpentene-1. 1, octene-1, etc.

In carrying out the present invention, these olefins may be homopolymerized, but two or more 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 180°C, and practically from room temperature to 130°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.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the Examples and Comparative Examples, the heptane index (ie, H, R,) is the amount remaining after extracting the obtained polymer with boiling n-heptane for 6 hours, expressed in %.

The melt flow index (i.e. MFI) is J
Measured according to IS K-6758-1968.

Bending rigidity and tensile yield strength are JISK-6758
ASTM D-747-63 and ASTM D-6, respectively, for pressed pieces obtained according to -1968.
38-64T.

Example 1 [Production of catalyst component (4)] 20 g of anhydrous magnesium chloride obtained by drying a commercially available product at 500° C. for 15 hours in a stream of dry nitrogen and 6.0 g of benzoyl chloride were internally blown with dry nitrogen. Placed in a filled vibratory ball mill container.

This container has a cylindrical shape made of stainless steel, has an internal volume of 11, and is filled with 50% of the apparent volume of magnetic balls having a diameter of 10 mm.

This was attached to a vibrating ball mill with an amplitude of 6 degrees and a frequency of 30 Hz, and co-pulverization was carried out for 8 hours.

Of the obtained homogeneous co-pulverized material, 15 g was placed in a 500 ml flask filled with dry nitrogen and dried (
50Tl11 n-heptane (previously water removed)
A solution of 86.3 g of titanium tetrachloride and 33.7 g of dried diethyl ether mixed and reacted at room temperature was added.

The mixture was stirred and mixed at 65°C for 2 hours.

After the obtained solid components were separated by filtration, they were washed with dry n-hexane until titanium tetrachloride was no longer detected in the filtrate.

After washing, by drying at 40°C under reduced pressure,
A powdered catalyst component (4) was obtained.

Chemical analysis of this catalyst component (A) revealed that it contained 3.3% by weight of titanium atoms.

(Polymerization and physical properties of the produced polymer) Catalyst components (4) prepared by the above method were placed in a stainless steel autoclave of 3, whose interior was filled with dry nitrogen.
58.0 m of 9.0 g of triethylaluminum and 0.22 g of ethyl benzoate were charged, followed immediately by 760 g of propylene and 0.07 g of hydrogen.

The temperature of the autoclave was raised and the internal temperature (polymerization system) was maintained at 70°C.

After 60 minutes, the content gas was released and the polymerization was terminated.

As a result, 386 g of polypropylene powder was obtained.

That is, the polymerization activity was 6,480 g/g-catalyst component (
, A)・hour, 196,000 g/g Ti・hour.

The H and R values of this polypropylene were 96.1%.

Without particularly refining this powder, 100 parts by weight of the powder and 0.15 parts by weight of tetrakis[methylene-3-(3'5'-di-tertiary-jf-4'-
Hydroxyphenyl) Flobionate Tumethane (Ciba・
Manufactured by Geigy, trade name Irganox 1010),
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 extruder with a diameter of 20 mm and an L/D of 40. It was created.

The obtained pellets exhibited whiteness and transparency comparable to those of ordinary commercially available products.

MFI was 5.6 g/10 minutes.

The bending rigidity of the press plate for this pellet is 12,800k.
g/cyyf, and the tensile yield strength is 345 kg/cyyf.
ffl and showed excellent physical properties.

Example 2 Instead of benzoyl chloride Q used in producing the catalyst component (4) in Example 1, 6. (Catalyst component (4) was prepared in the same manner as in Example 1, except that benzoyl bromide of Bi' was used.

This catalyst component contained 2.8% by weight of titanium atoms.

Polymerization of propylene was carried out under the same conditions as in Example 1, except that 57.2 cm of this catalyst component was used in place of catalyst component (4) used in Example 1.

As a result, 389 g of polypropylene powder was obtained.

That is, the polymerization activity was 6800 g/g-catalyst component (A
)・Time, 2430009/j! −T i ·time.

The H and R values of this polypropylene were 96.3%.

Pellets were made from this powder under the same conditions as in Example 1.

The obtained pellets, like the pellets obtained in Example 1, exhibited whiteness and transparency comparable to those of commercially available products.

MFI was 7.3g 710 minutes.

The bending rigidity of the press plate for this pellet is 13,000.9
/-, and the tensile yield strength was 348 kg/i.

Comparative Example 1 Example 1 except that the diethyl ether used in producing catalyst component (4) in Example 1 was not used.
Similarly, the catalyst component (titanium atom content is 2.7% by weight)
was manufactured.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 47.2 cm of this catalyst component was used instead of the catalyst component.

As a result, 259 g of polypropylene powder was obtained.

That is, the polymerization activity is 54,909/9-catalyst component/hour, 203,000 g/g Ti/hour.

The H and R values of this polypropylene powder were 84.7%.

Pellets were made from this powder under the same conditions as in Example 1.

The obtained pellets exhibited whiteness and transparency comparable to those of ordinary commercially available products.

MFI was 6.3 g/10 minutes.

The bending rigidity of the press plate for this pellet is 8400 kg/
-, and the tensile yield strength was 235 kg/i.

Comparative Example 2 A catalyst component (titanium atom content: 2.0% by weight) was produced in the same manner as in Example 1, except that the benzoyl chloride used in producing the catalyst component in Example 1 was not used.

Polymerization of propylene was carried out in the same manner as in Example 1, except that this catalyst component 50.01119 was used instead of catalyst component (4).

As a result, 46. ! 9 polypropylene powder was obtained.

That is, the polymerization activity was 920 fl/g-catalyst component/hour, 46000 g/, 9-Ti/hour.

The H and R values of this polypropylene powder were 83.8%.

Comparative Examples 3 and 4 15 g of a catalyst component containing 2.7% by weight of titanium atoms obtained in the same manner as in Comparative Example 1 was filled with dry nitrogen.
into a 0ml flask.

Further, 507 Ill of dry n-heptane and 0.63 g of dry diethyl ether were added, and the mixture was stirred and mixed at 65° C. for 2 hours.

After filtering off the solid components, washing with dry n-hexane and then drying at 40° C. under reduced pressure,
A catalyst component containing 2.3% by weight of titanium atoms was obtained.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 43.8 cm of this catalyst component was used in place of catalyst component (4).

As a result, 256 g of polypropylene powder was obtained.

That is, the polymerization activity was 5.840 g/g-catalyst component/hr and 254,0009/g Ti/hr.

The H and R values of this polypropylene powder were 85.2%.

Pellets were made from this powder under the same conditions as in Example 1.

The obtained pellets exhibited whiteness and transparency comparable to those of ordinary commercially available products.

Incidentally, the MFI of this pellet was 8.8 g and 710 minutes.

The bending rigidity of the press plate for this pellet is 9,100 kg.
/-, and the tensile yield strength was 254 ky/i (Comparative Example 3).

Note that even when the amount of diethyl ether used was increased to 12 g, the polymerization activity was 3,720 g/fj-catalyst component/hour and 189,000 g/gTi/hour.

Further, H and R were 83.7% (Comparative Example 4).

Comparative Examples 5 and 6 Magnesium chloride and benzoyl chloride were co-pulverized under the same conditions as in the production of the co-pulverized product in Example 1.

15 g of this co-pulverized material was filled with nitrogen at 50 orrt.
into a liter flask.

dry n-hebutane 50- and diethyl ether 0.6-
3 g was added, and the mixture was stirred and mixed at 65° C. for 2 hours.

After the obtained solid component was filtered off, it was washed with dry n-hexane.

This solid component was then filled with nitrogen at 50 ort.
i! in a flask with 50 rr of dry n-hebutane.
Add Ll and 86.3.9 titanium tetrachloride and heat to 65°C.
The mixture was stirred and mixed for 2 hours.

After the solid components were filtered off, they were washed with dry n-hexane and then dried at 40° C. under reduced pressure to obtain a powdered catalyst component (titanium atom content: 2.5% by weight).

Polymerization of propylene was carried out under the same conditions as in Example 1, except that 46.7 m9 of this catalyst component was used instead of catalyst component (4).

As a result, 329 g of polypropylene powder was obtained.

That is, the polymerization activity was 70,409 g/g-catalyst component/hour and 282,000 g/g-Ti/hour.

The H and R values of this polypropylene powder were 89.8%.

Pellets were made from this powder under the same conditions as in Example 1.

The obtained pellets exhibited whiteness and transparency comparable to those of ordinary commercially available products.

Note that the MFI of this pellet was 7.3 g/10 minutes.

The bending rigidity of the pressed plate of this pellet is 10.000
kg/cr? t, and the tensile yield strength is 282 kg
/ffl (Comparative Example 5).

In addition, even when the amount of diethyl ether used was increased to 12 g, the polymerization activity was 7370 g/g - catalyst component / time,
It was 263,000 g/g Ti/hour.

Further, H and R were 89.6% (Comparative Example 6).

Comparative Examples 7-10 Unground magnesium chloride 15g, benzoyl chloride 4.
5g and 40rrLl of dry n-hebutane were placed in a 300111 flask filled with nitrogen, and stirred at 65°C for 8 hours (300 revolutions/min with a rod-like stirrer, then the solid components were filtered out and washed with n-hebutane. did.

The solid component thus obtained was contacted with titanium tetrachloride and ether in the same manner as in Example 1 to obtain a powdered catalyst component (Comparative Example 7).

A catalyst component was prepared in the same manner as in Example 1, except that 63.9 g of benzoyl chloride was used instead of diethyl ether, and dry toluene was used instead of n-hebutane and n-hexane (comparison). Example 8).

A catalyst component was prepared in the same manner as in Example 1, except that 6.0 g of dibutyl ether was used instead of benzoyl chloride (Comparative Example 9).

In place of the magnesium chloride used in Example 1, magnesium oxide (same amount as in Example 1) was added under the same conditions.
A catalyst component was prepared in the same manner as in Example 1, except that the following was used (Comparative Example 10).

Polymerization of propylene was carried out in the same manner as in Example 1, except that the respective catalyst components obtained as described above were used in the amounts shown in Table 1.

The results are shown in Table 1.

Comparative Example 11 A co-milled product was prepared under the same conditions as in Example 1, except that 20 g of magnesium chloride, 6.0 g of benzoyl chloride and 1.1 g of dried diethyl ether were used. .

86. :l titanium tetrachloride treatment only was carried out with 50 ml of n-hebutane.

The resulting catalyst component (titanium atomic weight content: 2.9% by weight)
) Polymerization of propylene was carried out in the same manner as in Example 1, except that 52.4 m9 was used.

As a result, 273 g of polypropylene powder was obtained.

That is, the polymerization activity is 5210 g/g-catalyst component/hour and 178000 g/g-Ti/hour.

In addition, the H, R, of this polypropylene powder is 87.6%
Met.

This powder was pelletized (MFI) under the same conditions as in Example 1.
3.8 g/10 minutes).

Furthermore, the bending rigidity of the press plate for this pellet is 9.1.
00 kg/i, and the tensile yield strength is 256 kg/i.
- (Comparative Example 11).

Further, a catalyst component was prepared in the same manner as in Comparative Example 11, except that the amount of diethyl ether used in Comparative Example 11 was changed to 3.2 g.

Propylene polymerization was carried out in the same manner as in Comparative Example 11, except that this catalyst component was used, and pellets were produced.

Polymerization activity is 3.810 g/g-catalyst component/time, 12
It was 3.000 g/g-Ti/hour.

The H, R, of the obtained polypropylene powder was 91.2%, and the MFI of the pellet was 3.4 g 710 minutes.

The bending rigidity of the press plate for this pellet is 10,300k.
g/i, and the tensile yield strength was 281 kg/i (Comparative Example 12).

Comparative Example 13 The catalyst component (4) used in Example 1 was 21.3
Further, propylene polymerization was carried out in the same manner as in Example 1 except that ethyl benzoate was not used.

As a result, 233 g of polypropylene powder was obtained.

In other words, the polymerization activity is 10,900 g/g-catalyst component (
4)・Time, 331,000g/,! ? Ti・time.

Further, the H and R values of this powder were as low as 55.7%.

Comparative Example 14, 15 Solution 5.3a obtained by mixing and reacting n-hebutane 5omma1 titanium tetrachloride 86.3g and dried diethyl ether 33.7fl at room temperature and magnesium chloride 21 dried under the same conditions as Example 1. A catalyst component was prepared by co-pulverizing under the same conditions as in Example 1 (titanium atom content: 3.3% by weight).

Polymerization of propylene was carried out under the same conditions as in Example 1, except that 52.9 cm of this catalyst component was used in place of catalyst component (4).

As a result, 395 g of polypropylene powder was obtained.

That is, the polymerization activity is 7,4709 g/g-catalyst component/hour and 226,000 g/g-Ti/hour.

H, R of this powder. was 83.2%.

Pellets were made from this powder in the same manner as in Example 1.

The obtained pellets had whiteness and transparency comparable to those of ordinary commercially available products.

The bending rigidity of the press plate of this pellet is 10.00 o
kg/yellow, and the tensile yield strength was 257 kg/-, indicating poor mechanical properties (Comparative Example 14).

Comparative Example 14 was also used, except that the material to be co-pulverized with magnesium chloride in Comparative Example 14 was changed to a solution 5.4a prepared by mixing, stirring, and reacting toluene 157IL11 titanium tetrachloride 8.6 g and 6.4 g of benzoyl chloride. Polymerization of propylene was carried out in the same manner.

Polymerization activity is 4,020 E/9-catalyst component/time, 13
It was 0.000 gl&-Ti·hr.

Moreover, H and R of the obtained polypropylene powder are 85.
It was 3% (Comparative Example 15).

Example 3 A catalyst component (titanium atom content: 4.0% by weight) was prepared in the same manner as in Example 1, except that 49.2 g of anisole was used instead of diethyl ether used in Example 1.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 52.7 cm of this catalyst component was used in place of catalyst component (4).

As a result, 392 g of polypropylene powder (H, R, 97.0%) was obtained.

That is, the polymerization activity is 7.440 g/j; 1-catalyst component/hr, 186,000 g/g-Ti/hr.

Pellets were made from the obtained powder under the same conditions as in Example 1.

The pellets had whiteness and transparency comparable to those of ordinary commercially available products.

The MFI of this pellet was 7.3 g/10 minutes.

The bending rigidity of the press plate for this pellet is 13,300 kg.
/crA, and the tensile yield strength is 354kg/crA.
It showed excellent mechanical properties.

Example 4 The same catalyst components as in Example 1 were used (the titanium atom content was 2.5 g) except that 59.2 g of di-n-butyl ether was used instead of the diethyl ether used in Example 1.
6% by weight).

Polymerization of propylene was carried out in the same manner as in Example 1, except that 49.7 cm of this catalyst component was used in place of catalyst component (4).

As a result, 270 g of polypropylene powder (H, R, 95.8%) was obtained.

That is, the polymerization activity is 5,430 El/g-catalyst component/hour and 209.000 g/g Ti/hour.

Pellets were made from the obtained powder under the same conditions as in Example 1.

The pellets had whiteness and transparency comparable to those of ordinary commercially available products.

The MF I of this pellet was 5.6 g/l 0 min.

The bending rigidity of the press plate for this pellet is 12,200 kg.
/i, and the tensile yield strength is 321 kg/C11￥
, and showed excellent mechanical properties.

Example 5 Instead of diethyl ether used in Example 1, 77.4f! In addition to using diphenyl ether,
As in Example 1, the catalyst component (titanium atom content is 3.1
% by weight) was created.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 52.7 cm of this catalyst component was used in place of catalyst component (4).

As a result, 221 g of polypropylene powder (H, R, 94.3%) was obtained.

That is, the polymerization activity is 4900 g/g-catalyst component.hr and 158.000 g/g-Ti.hr.

Pellets were made from the obtained powder under the same conditions as in Example 1.

The pellets had whiteness and transparency comparable to those of ordinary commercially available products.

The MFI of this pellet was 6.2!9/10 minutes.

The bending rigidity of the press plate for this pellet is 12,100 kg.
/art, and the tensile yield strength was 317 kg/-, showing excellent mechanical and bending properties.

Examples 6 to 8, Comparative Examples 16 to 25 Instead of benzoyl chloride used in Example 1,
Acetyl chloride [hereinafter referred to as “compound (4)”], trichloroacetyl chloride [hereinafter referred to as “compound (B)”], P-chlorobenzoyl chloride [hereinafter referred to as “compound (C)J]”, benzaldehyde [hereinafter referred to as “compound (C)J”] Compounds (D), J], acetofesson [hereinafter referred to as "compound (odor)]", ethyl benzoate [hereinafter referred to as "compound (O)]", N,N-dimethylbenzamide [hereinafter referred to as "compound (Glj)]" or benzoyl alcohol [hereinafter referred to as "Compound 0"]
A catalyst component was prepared in the same manner as in Example 1 using real rice, except that .

Polymerization of propylene was carried out in the same manner as in Example 1, except that the catalyst component obtained as described above was used instead of catalyst component (4).

The results are shown in Table 2. In addition, pellets were created from the polypropylene powders obtained in Examples 6 to 8 under the same conditions as in Example 1.

The physical properties of each pellet are shown in Table 2 (Example) 6-8, Comparative Examples 16-20).

In addition, in the production in Comparative Examples 16 to 20 above, except that diethyl ether was not used, the catalyst components were produced in the same manner, and each catalyst component was used.
Polymerization of propylene was carried out in the same manner.

The results are shown in Table 2 (Comparative Examples 21 to 25).

Example 9 A catalyst component (titanium atom content: 31% by weight) was prepared in the same manner as in Example 1, except that 90.71 ethoxytitanium trichloride was used instead of titanium tetrachloride.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 50.2 cm of this catalyst component was used in place of catalyst component (4).

As a result, 264 g of polypropylene powder was obtained.

That is, the polymerization activity is 5,2609/g-catalyst component/time, 170,000! ! / g-T i · hours.

The H and R values of this polypropylene powder were 95.6%.

Pellets were prepared from this powder E,% under the same conditions as in Example 1.

The obtained pellets exhibited whiteness 1J, strength, and transparency comparable to those of ordinary commercially available products.

Note that the MFI of this pellet was 5.7 g/10 minutes.

The bending rigidity of the press plate for this pellet is 12.70 o
kg/-, and the tensile yield strength was 325 kg/i, showing excellent physical property values.

Example 10 A co-pulverized product was prepared in the same manner as in Example 1, and then a solution 5. 5. 311 Ll was added to the above co-milled material and co-milling was continued for an additional hour.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 44.5 cm of the thus obtained powdered catalyst component (titanium atom content: 3.1% by weight) was used instead of catalyst component (4). I did this.

As a result, 180 g of polypropylene powder (H, R, 94.5%) was obtained.

That is, the polymerization activity is 4,0409/g-catalyst component/hour and 130,000 glfl-Ti/hour.

The obtained polypropylene was pelletized in the same manner as in Example 1 (
MFI was 3.8 g/10 minutes).

These pellets had a whiteness comparable to that of ordinary commercially available products.

The bending rigidity of the pressed plate of the obtained pellets was 11.40.
0kg/crrL, tensile yield strength is 310kg
It showed excellent physical property values of /-.

Comparative Example 26, 27 6.0.9 instead of benzoyl chloride during co-grinding
A catalyst component was prepared in the same manner as in Example 1, except that ethyl benzoate and 4.6 g of silicon tetrachloride were used, and diethyl ether 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 content: 2.8% by weight) was used instead of catalyst component (4).

As a result, 178 g of polypropylene powder (H, R, 92.7%) was obtained.

That is, the polymerization activity is 3,520 j9/g-catalyst component/hour and 126,000 fl/fl-Ti/hour.

Pellets (MFI: 5.2 g, 710 minutes) were prepared from the obtained polypropylene powder in the same manner as in Example 1.

The pellets had the same level of whiteness and transparency as ordinary commercially available products.

The bending rigidity of the pressed plate of the obtained pellets was 10.80.
0 kg/crj, and the tensile yield strength was 285 to 9/ffl, showing insufficient mechanical properties (Comparative Example 26).

Further, polymerization was carried out in the same manner as in Comparative Example 26, except that ethyl benzoate was not used when polymerizing propylene.

Polymerization activity is 7,5501/j! -Catalyst components/time, 13
H, R of the obtained polypropylene powder.

was very low at 43.7% (Comparative Example 27).

Example 11 Except that the amount of catalyst component (4) used in polymerizing propylene in Example 1 was changed to 44.9μ, and 0.33F ethyl anisate was used instead of ethyl benzoate. , Polymerization of propylene was carried out in the same manner as in Example 1.

As a result, 304 g of polypropylene powder (H, R, 96.4%) was obtained.

That is, the polymerization activity is 6,7709/g-catalyst component concentration.
hours, 205,000 gl & -T i hours.

Pellets were prepared from the obtained polypropylene powder in the same manner as in Example 1.

These pellets (MFI: 6.4 g/10 min) had whiteness and transparency comparable to those of ordinary commercially available products.

The bending rigidity of the pressed plate of the obtained pellets was 12.80.
0kg/CrIt, tensile yield strength is 330kg
/i, showing excellent physical property values.

Example 12 The same conditions as in Example 1 were used, except that the amount of catalyst component (4) used in polymerizing propylene in Example 1 was changed to 48.3 cm, and 12 g of ethylene was allowed to coexist during polymerization. Copolymerization of ethylene and propylene was carried out.

As a result, 321. ! copolymer of li' (as a result of infrared absorption spectrum analysis, the ethylene unit content is 3.4% by weight)
) powder was obtained.

That is, the polymerization activity is 6.650g/g-catalyst component (4
)・hour, 201,000 glg-T i・hour.

This powder has good fluidity (the powder is not sticky, but free flowing), and the grease-like component extracted by boiling n-butyl alcohol is 1.7%.
Met.

Example 13 Catalyst component (A) used in Example 1 50.811
19, triethylaluminum 0.339 and 0.0
2 g of ethyl benzoate was placed in a 3, OA' stainless steel autoclave whose interior was filled with dry nitrogen, followed immediately by 1 kg of isobutane and 0.19 g of hydrogen.

The temperature of the autoclave was raised, and when the internal temperature reached 86°C, ethylene was added so that its partial pressure became 10 atm (gauge pressure), and from then on, polymerization was carried out while maintaining the temperature and ethylene partial pressure at these values. Ta.

After 60 minutes, the content gas was released to terminate the polymerization.

As a result, 356 g of polyethylene powder was obtained.

That is, the polymerization activity is 701g/g-catalyst component (4).
Time and atmospheric pressure, 21,200g/! ? -Ti, time, and atmospheric pressure.

The obtained polyethylene was made into pellets in the same manner as in Example 1.

This pellet has a whiteness comparable to that of regular commercially available products.
The melt index (according to JIS K-6760) is 0.51.9/10 minutes, and the density is 0.9559.
/crtl (according to JIS K-6760)
.

Example 1, Example 3, Example 5, Comparative Example 14, Comparative Example 26, and Reference Example (0.20 g of AA type cyclic titanium chloride) except that the amount of hydrogen used was changed as shown in Table 3. 0.5
Polymerization of propylene was carried out under the same conditions as in Example 1 (B) using a catalyst system obtained from diethylaluminum chloride (Diethylaluminum chloride in Example 8.9).

H and R of each obtained polypropylene powder.

Table 3 shows the MFI of pellets made from each polypropylene powder under the same conditions as in Example 1.

FIG. 1 shows the relationship between H and R of each polypropylene powder obtained using each catalyst system in Table 3 and the MFI of the pellet.

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 H and R values of the pellets hardly change. If propylene is polymerized using the catalyst system used, increasing the MFI of the resulting polypropylene will increase the H, R of the pellets.
It is clear that , is significantly reduced.

[Brief explanation of drawings]

FIG. 1 shows the H, R,
(Subordinate axis, unit: ratio) and pellet MFI (horizontal axis, unit: g/10 min).

Claims (1)

[Claims] 1 (A) (1) A mixture or addition reaction of (2) a tetravalent titanium compound having at least one halogen atom and an ether compound to a magnesium dihalide that has been pulverized with an acyl halide. The solid component obtained by contacting the product with (B))I
A method for producing an olefin polymer, which comprises polymerizing an olefin in the presence of a catalyst system obtained from a J-deal aluminum compound and (C) an organic carboxylic acid ester.