JPS5840566B2 - Improved method for producing olefin polymers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to an improved process for making olefin polymers.

More specifically, the present invention relates to a method for producing an olefin polymer having extremely high polymerization activity and excellent mechanical properties and moldability using a novel catalyst.

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 titanium trichloride and aluminum chloride, and an organoaluminum compound (JP-A-47-26487 issue).

Although this catalyst system had significantly improved stereoregularity as well as 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, although the stereoregularity of the polymer was improved compared to the above-mentioned one, a practical melt flow index was obtained by adjusting the molecular weight. When producing a polymer with It cannot be said that this is sufficient to simplify the process and reduce manufacturing costs.

For example, if we take polypropylene (hereinafter referred to as rPPJ) as an example, a product with a melt flow index (hereinafter referred to as rMFIJ) at a temperature of 230°C and a load of 2.16 kg of: lll/10 minutes has a flexural rigidity of 11 ，
If it is less than 9/crL in 000, it is difficult to fully demonstrate the inherent advantages of the resin, so it is not practical, but this MFI
When producing PP with PP, the n-heptane extraction residue (hereinafter referred to as rH,R,J) of this PP is approximately 94%, and products with H,R, values lower than this are not practical products. In order to achieve this, it is necessary to sufficiently remove low-crystalline 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, (A) (1) Magnesium dihalide that has been pulverized together with acyl halide contains (2) "tetravalent titanium compound having at least one halogen atom" (hereinafter referred to as "titanium-based compound"). and an organic compound having an rsi-0 bond (hereinafter referred to as a "silicon compound"), or a solid component obtained by contacting an addition reaction product with (B) a trialkylaluminum compound and (C) an organic carbon. The catalyst system obtained from the acid ester not only has extremely high polymerization activity, but surprisingly, it is completely different from conventional olefin polymerization catalysts and uses hydrogen etc. during polymerization to adjust the molecular weight of the resulting polymer. Even when producing a polymer with high melt flow, H and R do not decrease at all (see Figure 1 for details). g/l 0 min), it was discovered that a polymer having extremely high stereoregularity could be obtained, and the present invention was achieved.

That is, taking polypropylene as an example, as is clear from Fig. 1, conventional catalyst systems, namely, a catalyst system based on titanium trichloride [E in Fig. 1], a catalyst system A [C in Fig. 1]
] and B catalyst system [D 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 as well as polymers of various stereoregularities, and extraction with boiling n-hebutane selectively extracts the low regularity portions, but the low regularity polymers Therefore, in a polymer with a low MFI (high molecular weight), even the low regularity parts cannot be completely extracted, whereas as the MFI increases (low molecular weight), the high molecular weight parts As a result of the reduction in extraction, the MFI
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, in the practical M-F I region, the stereoregularity is As a result of the reduced regularity, when compared as a practical product, the product obtained by the method of the present invention has much better stereoregularity, and therefore is a polymer with excellent moldability and mechanical properties. can be obtained.

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 evaporating the polymerization solution or polymerization slurry as it is without removing the non-crystalline part, it is possible to obtain a polymer powder with good fluidity (free flowing). Obtainable.

Furthermore, even if the low crystallinity portion is somehow removed, the soluble content in the solvent is very low, and therefore,
When removing the olefin using a solvent, which is generally carried out, only a very small amount is removed by the solvent, so the raw olefin can be effectively utilized.

Moreover, 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 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 portions and catalyst residues from the resulting polymer and inactivation of the catalyst residues, and has 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.

A compound containing an X group (X is a halogen atom), and examples of the acyl group include a saturated or unsaturated aliphatic carbonyl group having at most 20 carbon atoms, a carbonyl group containing an alicyclic ring, and a carbonyl group containing an aromatic ring and their halogen or alkoxy substituents.

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, trichloracetyl bromide , oxalyl dichloride, malonyl dichloride, succinyl dichloride, glycaryl dichloride, adipoyl dichloride, acryloyl chloride, acryloyl bromide, fumaroyl dichloride, methacrylic chloride, cinnamoyl chloride, cinnamoyl bromide, β-carboxypropionyl chloride, β - Aliphatic carbonyl halides such as carboxyacryloyl chloride and phenoxyacetyl chloride, alicyclic carbonyl halides such as cyclohexanecarbonyl chloride, cyclohexanecarbonyl bromide, norbornene dicarbonyl dichloride and furoyl chloride, and benzoyl fluoride, benzoyl chloride, iodide. Aromatic carbonyl halides such as benzoyl, naphthoyl chloride, naphthoyl bromide, toluoyl chloride, toluoyl bromide, phthaloyl dichloride, anisoyl chloride and chlorobenzoyl chloride, and the like.

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, 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 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 cfrL is put into a container with an internal volume of 111 cm and an inner diameter of 10 cm with an apparent volume of 50%, about 20 g of the material to be crushed is put therein, and the amplitude is set for 6 minutes. When co-milling 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.

- 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.

TiXn(OR”)m(NR2R3)l(OCOR')
In formula p, X is a chlorine atom, bromine atom or iodine atom, R1, R2, R3 and R4 are aliphatic, alicyclic or aromatic hydrocarbon groups having at most 12 carbon atoms, and n is It is a number from 1 to 4, ml and p are numbers from O to 3, and n+m+7+p is 4.

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 titanium chloride, propoxytitanium trichloride, butoxytitanium trichloride, dimethylaminotitanium trichloride, bis(dimethylamino)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.

A silicon-based compound is an organic compound having a 5i-0 bond, and the typical general formula among them is shown by the following formula.

S i (OR”) mR old (I) R3 (R4SiO) lSiR treasure (II) (Ren5i
O)p (In) In the formula, R1, R
2 and R6 may be the same or different, and may be an alkyl group, a cycloalkyl group, or an aryl group having at most 20 carbon atoms.
aryl ) group and aralkyl group (which may be unsaturated or substituted with a halogen atom or an alkoxide group having at most 20 carbon atoms), and R2 is a hydrogen atom or is a halogen atom, R3, R4 and R5 may be the same or different, and are the above hydrocarbon group (which may be unsaturated or substituted) or a halogen atom, m+n is 4 (however, m\\ 0), l is an integer from 1 to 1000, and p is an integer from 2 to 1000.

Representative silicon compounds represented by formula (I) include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, and jetoxydiethylsilane.

Ethoxytriethylsilane, tetrapropoxysilane,
Dipropoxydipropylsilane, tetra-isopropoxysilane, di-isopropoxy-di-isopropylsilane, dimethoxydiethylsilane jetoxydibutylsilane tetra-n-butoxysilane, di-n-butoxy-di-n-butylsilane, tetra- Secondary-butoxysilane, tetrahexoxysilane, tetraoctoxysilane.

Trimethoxychlorosilane, dimethoxydichlorosilane, dimethoxydibromosilane, triethoxychlorosilane, jetoxydibromosilane, dibutoxydichlorosilane dicyclopentoxydiethylsilane, jetoxydiphenylsilane, 3゜5-dimethylphenoxytrimethylsilane, methylphenyl-bis (2-chloroethoxy)silane, dimethoxydibenzylsilane, tri-n-
propylallyloxysilane, allyl
Tris(2-chloroethoxy)silane and trimethoxy-3-ethoxypropylsilane are mentioned.

Further, typical silicon-based compounds represented by formula (II) include hexamethyldisiloxane, decamethyltrisiloxane, tetracosamethylundecasiloxane, 3-hydrohebutamethyltrisiloxane, and hexaphenyldisiloxane. , hexacyclohexyldisiloxane, 1,3-dimethyldisiloxane, hexaethyldisiloxane, octaethyltrisiloxane, hexapropyldisiloxane 13-dichlorotetramethyldisiloxane, 1,3-bis(n-phenoxyphenyl)- 1,3
-dimethyl-1,3-diphenyldicycloxane, l,
3-diallyl (al lyl ) tetramethyldisiloxane, 1,3-dibenzyltetramethyldisiloxane,
2,2,4,4-tetraphenyl-2,4-disylar 1
-Oxacyclopentane 1133-Tetramethyldisiloxane and hexachlorodisiloxane are mentioned.

Furthermore, typical silicon-based compounds represented by formula (1) include 1,3.5-trimethylcyclotrisiloxane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane.

Pentamethylchlorocyclocyclotrisiloxane.

1.3.5-trictyltriphenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,3,
Mention may be made of 5-tribenzyltrimethylcyclotrisiloxane and 1,3,5-1-allyl)limethylcyclotrisiloxane.

Preferred among these silicon-based compounds are alkoxycune and low viscosity methyl and ethyl polysiloxanes, especially tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyljethoxysilane, methoxytrimethylsilane, trimethoxysilane, etc. Methylsilane, hexamethyldisiloxane,
These include octamethyltrisiloxane and dimethylpolysiloxane.

These titanium-based compounds and silicon-based compounds are "magnesium dihalide pulverized with acyl halide" (hereinafter referred to as "component (1)") obtained as described above.
It is preferable to simultaneously contact the components (1) and 1.
) with a titanium-based compound, then remove the excess by washing with a solvent, and then contact, or contact component (1) with a silicon-based compound, then wash off the excess with a solvent. A method in which a titanium-based compound is contacted after removal 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 a silicon compound, or a mixture of the titanium compound and a silicon compound is added to a mixture in which the reaction between the two is completed by a treatment such as heating, or a mixture of a titanium compound and a silicon compound is added. It is preferable to simultaneously mix and carry out the contact treatment with component (1).

The ratio of the titanium compound to 1 mol of the silicon 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, which can form a large amount of quantitative complex compound of the silicon compound and the titanium compound.

In carrying out the contact treatment, it is sufficient to simply bring component (1), the titanium-based compound, and the silicon-based compound into contact with each other, but for efficient production, the whole must be stirred in an appropriate solvent or a pulverizer may be used. Among them, it is preferable to apply a method such as co-pulverization using the same method as described above.

As a solvent used for mixing or reacting a titanium compound and a silicon compound and a solvent for stirring contact,
Aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene and halogenated hydrocarbons such as methylene chloride, trichloroethane, trichloroethylene and chlorobenzene may be used, but Aromatic hydrocarbons are particularly preferred.

The concentration of the stirring contact is preferably as high as possible as long as there is no operational problem, and usually 0.005 mol-Ti/1 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;
At high temperatures, the stereoregularity of the resulting polymer is low, so in order to obtain a polymer with very good performance, it is necessary to
℃ is preferable.

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 contact treatment, it is preferable to wash using an inert solvent (for example, an aliphatic hydrocarbon and an aromatic hydrocarbon used as a solvent in the stirring contact treatment).

Trialkylaluminum compounds have the general formula Al
R1R2R3 (RI 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-propylaluminum,
Tri-isopropyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum and tri-n-hexyl aluminum are mentioned, and triethyl aluminum is particularly preferred.

Furthermore, organic carboxylic acid esters include aliphatic, alicyclic or aromatic carboxylic acids having at most 20 carbon atoms and monovalent or aliphatic, alicyclic or aromatic carboxylic acids having at most 20 carbon atoms. It is a carboxylic acid ester derived from a polyhydric alcohol, and a portion thereof may be substituted with a halogen atom or an alkoxy group.

Representative examples of the organic carboxylic acid ester include methyl formate, ethyl formate, methyl acetate, ethyl acetate, amyl acetate, cyclohexyl acetate, vinyl acetate, butyl acetate, ethyl butyrate, phenyl propionate, furfuryl propionate, 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-furoate. Acid esters and methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, butyl benzoate, octyl benzoate,
Cyclohexyl benzoate, phenyl benzoate, methyl toluate.

Mention may be made of aromatic carboxylic acid esters such as ethyl toluate, methyl anisate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, ethylene glycone dibenzoate and methyl naphthoate.

Among these, aromatic carboxylic acid esters are particularly desirable.

"Acyl halides, magnesium dihalides, titanium compounds, silicon compounds, trialkyl aluminum compounds, and organic carboxylic acid esters" (hereinafter referred to as "each catalyst component") are used to obtain the catalyst system used in the present invention. ) may be used alone or in combination of two or more.

Each catalyst component may be introduced separately into the polymerization vessel, but two or three of them (the mixture or addition reaction product of component (1) and a titanium compound and a silicon compound is one type). Although they may be mixed in advance, it is particularly preferred to mix the 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 0.001 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, hexene-1,
Examples include octene-1.

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 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 force 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 (i.e., H, R,) is the amount remaining after extracting the obtained polymer with boiling n-hebutane for 6 hours, expressed as a cloud.

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

Bending rigidity and tensile yield strength are JIS K-675
8-1968, ASTM D-747-63 and ASTM D-
638-64T.

In each Example and Comparative Example, all the compounds (organic solvents, olefins, titanium compounds, organic carboxylic acid esters, silicon compounds, etc.) used in the production and polymerization of catalyst components were essentially water-free. In addition, the preparation and polymerization of the catalyst components were essentially moisture-free and conducted under a nitrogen atmosphere.

Example 1 Preparation of Catalyst Component Preparation 20 g of anhydrous magnesium chloride (obtained by heating and drying a commercially available product at about 500° C. for 15 hours in a stream of dry nitrogen) and 6.0 g of benzoyl chloride were milled in a vibrating ball mill. Container (stainless steel, cylindrical, internal volume: 111) A porcelain ball with a diameter of 10 and an apparent volume of 5
0 coefficient filling), and the amplitude is 6 and the frequency is 30H.
It was attached to a Z vibration ball mill and co-pulverized for 8 hours.

Of the obtained homogeneous co-pulverized material, 15g was placed in a 500-liter flask, and 125 grams of toluene and 86 grams of toluene were added. A solution of :1 titanium tetrachloride and 12.4 g dimethyldimethoxysilane mixed at room temperature was added.

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

The obtained solid component was separated by F and then dried.

Washing was performed using toluene until titanium tetrachloride was no longer detected in the p solution.

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 2.36 weight percent titanium atoms.

(8) Polymerization and physical properties of the produced polymer 56.4 m of catalyst component (4) produced by the above method was placed in a 3.07 stainless steel autoclave.
1(7)l-IJ ethylaluminum 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, 277 g of polypropylene powder was obtained.

That is, the polymerization activity was 4,911 g/El-0 hour for the catalyst component and 208 kg/F-Ti-hour.

This polypropylene had H, R, and 96.

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-tert-butyl-4'-
Hydroxyphenyl) propionate comethane (Ciba)
Manufactured by Geigy, product name: Irganox 1010)
, 0.20 parts by weight of distearyl thiodipropionate and 0.10 parts by weight of calcium stearate were kneaded at 210° C. under a nitrogen atmosphere using an extruder with a diameter of 20 m and TIL1L/D of 40 to create pellets. did.

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

MFI was 7.3 g/10 minutes. The flexural rigidity of the pressed plate of this pellet was 12,900/9/cTL, and the tensile yield strength was 342 ky/-, showing excellent physical properties.

Comparative Example 1 The catalyst component (titanium atom content (2.4% by weight) was prepared.

Polymerization of propylene was carried out in the same manner as in Example 1 (B) except that 46.8 cm of this catalyst component was used instead of the catalyst component (blade).

As a result, 252 g of polypropylene powder (H, R, 85.2%) was obtained.

That is, the polymerization activity was 5,384 g1&-catalyst component/hour, 224 kg/9-Ti/hour.

Pellets (MFI: 5.8.!li'/10 minutes) were prepared from the obtained polypropylene powder in the same manner as in Example 1 (8).

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

The bending rigidity of the pressed plate of this pellet is 8.500 k
g/cyri, and the tensile yield strength is 232! iiiI
/Cl7L and exhibited poor mechanical properties.

Examples 2 to 12, Comparative Examples 2 and 3 Tetra Ethoxysilane [
Tetramethoxysilane (hereinafter referred to as "compound (0)"), hexamethyldisiloxane (hereinafter referred to as "compounder"), dimethylpolysiloxane (25°C, 350 centistokes) 1,3-dichlorotetramethyldisiloxane (hereinafter referred to as "compound ω)"), 3-hydroheptamethyltrisiloxane (hereinafter referred to as "compound 0")
Methylhydrophorisiloxane (25°C, 40 centistokes) [hereinafter referred to as “Compound 0”], triethoxychlorosilane [hereinafter referred to as “Compound (J)”], hexamethylcyclotrisiloxane [hereinafter referred to as “Compound ■”] say〕
, tetrachlorosilane [hereinafter referred to as "compound (L)"]
Alternatively, a catalyst component was prepared in the same manner as in Example 1 except that dimethyldichlorosilane (hereinafter referred to as "compound book") was used.

In place of the catalyst component, propylene was polymerized in the same manner as in Example 1 (B).

Then, pellets were made from each of the obtained polypropylene powders under the same conditions as in Example 1 (8).

Polymerization activity, H, R of polypropylene powder, M of pellets
Table 1 shows the flexural rigidity and tensile yield strength of the FI and pellet press plates.

Examples 13 to 17, Comparative Examples 4 to 9 Benzoyl chloride used in producing the co-pulverized product in (A) of Example 1 [hereinafter referred to as "compound (1)"]
Instead, compound (1), benzoyl bromide [hereinafter referred to as “compound (2)”], trichloroacetyl chloride [hereinafter referred to as “compound (3)”], p-chlorobenzoyl chloride [hereinafter referred to as “compound (4)”] ”)
p-methoxybenzoyl chloride [hereinafter referred to as "compound (5)"
)”], benzaldehyde [hereinafter referred to as “compound (6)
], acetophenone [hereinafter referred to as "compound (7)"], methyl benzoate [hereinafter referred to as "compound (8)"], N,N-dimethylbenzamide [hereinafter referred to as "compound (9)"],
)" or benzyl alcohol (hereinafter referred to as "Compound (10) J") in the amounts shown in Table 2.
A catalyst component was prepared in the same manner as in Example 1 (A).

Example 1 (B) except that each catalyst component was used.
Polymerization of propylene was carried out under the same conditions.

Then, pellets were created from each of the obtained polypropylene powders under the same conditions as in Example 1.

Table 2 shows the polymerization activity, H, R, of the polypropylene powder, MFI of the pellets, and physical properties of the press plate of the pellets.

Example 18 In (4) of Example 1, a reaction product of titanium tetrachloride and dimethyldimethoxysilane was added to 13 g of the co-pulverized product of magnesium chloride and benzoyl chloride used in producing the catalyst component (4). Then, co-pulverization treatment was carried out for 1 hour (the content of titanium atoms in the obtained co-pulverized product was 2.36 wt.).

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

Polymerization activity is 3,461g/g-catalyst component/time, 147
It was on 9/9 Ti・hours.

The H, R, of the obtained polypropylene powder is 94.3o7
It was 0.

This polypropylene was made into pellets under the same conditions as in Example 1) (
MFI was 6.8 g/10 minutes).

The bending rigidity of the press plate for this pellet is 12,00 o
k! 97crA, tensile yield strength is 316kg/c
It was 11 tons.

Comparative Example 10 The same amounts of the four components as in Example 17, namely 10 g of magnesium chloride, 3! ! benzoyl chloride, 1.3
1 g of titanium tetrachloride and 0.44 g of dimethyldimethoxysilane were added in this order to the vibratory ball mill container used in Example 1 (4), and pulverized for 8 hours.

Polymerization of propylene was carried out under the same conditions as in Example 1 (CB), except that the obtained co-pulverized product (catalyst component) was used instead of the catalyst component (A).

Polymerization activity is 512g/g-catalyst component/time, 22kg/g
g-Ti·hours.

The H, R, of the obtained polypropylene powder was 8 g and 6%.

This polypropylene was made into pellets under the same conditions as in Example 1) (
MFI was 6.8g, 710 minutes).

The bending rigidity of the pressed plate of this pellet is 10.000
kg/cyrt, and the tensile yield strength is 276 kg/i
Met.

Comparative Example 11 Polymerization of propylene was carried out under the same conditions as in (B) of Example 1, except that ethyl benzoate used in [F]) of Example 1 was not used.

The polymerization activity was 12.430 g/g-catalyst component/hour.

The H and R values of the obtained polypropylene powder were 56.1%.

Example 19 Except that 0.339 ethyl anisate was used instead of ethyl benzoate used in Example 1 (B),
Polymerization of propylene was carried out under the same conditions as in Example 1 (B).

The polymerization activity was 3,881/g-catalyst component/hour.

The H and R values of the obtained polypropylene powder were 95.2%.

This polypropylene was pelletized under the same conditions as in Example 1 (
MFI was created (6.7.9/10 minutes).

The bending rigidity of the pressed plate of this pellet is 12,400k
It was p/-.

Example 20 The catalyst component (4) obtained in Example 1 (4) was
0.61n9, 0.33g of triethylaluminum and o,ol of ethyl benzoate were placed in a 34 stainless steel autoclave, followed immediately by 1kg of isobutane and 0.19g of hydrogen.

The temperature of the autoclave was raised, ethylene was supplied, and polymerization was carried out for 60 minutes at 85° C. while maintaining the partial pressure at 10 atm (gauge pressure).

The polymerization was terminated by releasing the contained gas.

As a result, 327 g of polyethylene powder was obtained.

That is, the polymerization activity is 805 g/g - catalyst component (4)
・Time/pressure, 34.120. ! 9/, 9-Ti, time, and pressure.

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

These pellets have a whiteness comparable to that of regular commercially available products, a melt index (according to JIS K-6760) of 0152g710min, and a density of 0.956.
g/i (according to JISK-6760).

Comparative Example 12 Except for using 6,0g of ethyl benzoate and 4.6g of silicon tetrachloride instead of benzoyl chloride during co-grinding, and not using dimethyldimethoxysilane when preparing the catalyst component, A catalyst component was prepared in the same manner as in Example 1.

(B) of Example 1 except that the above catalyst component (titanium content 2.8 weight range) was used instead of catalyst component (A)
) Polymerization of propylene was carried out in the same manner.

As a result, 178 g of polypropylene powder (H, R, is 9
A score of 2.7 excellent was obtained.

In other words, the polymerization activity is 3.520 g/f! -Catalyst components/time, 126! 9/g-Ti·hour.

Pellets (MFI: 5.2 g/10 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/cft, and the tensile yield strength is 285 to 9
/crIL and showed poor mechanical properties.

Example 21 A catalyst component was prepared in the same manner as in Example 1 (4), except that 90.7 g of ethoxytitanium trichloride was used instead of the titanium tetrachloride used in Example 1 (A).

Polymerization of propylene was carried out under the same conditions as in Example 1 [F]), except that the obtained catalyst component was used in place of catalyst component (4).

Polymerization activity is 4,22397g-catalyst component/time, 212
kg/g-Ti/hour.

The H and R values of the obtained polypropylene powder were 95.7%.

The MFI of pellets made from this polypropylene powder under the same conditions as in Example 1 was 5.6 g/10 minutes.

Example 22 Ethylene and 1-butene were combined in the same manner as in Example 20, except that 46°7cm of the catalyst component used in Example 6 was used, and 15.6 g of 1-butene was allowed to coexist during polymerization. Polymerization was carried out.

As a result, 322 g of polymer powder (number of ethyl groups per 1000 carbons: 4.6) was obtained.

In other words, the polymerization activity is 690g/g-catalyst component・time・
Atmospheric pressure, 27,900 g/ji - T i · time · atmospheric pressure.

The MI of pellets of this polymer is 0.46 g/10 min (J
IS K6760) and the density is 0.939
It was 8 g/c/l (according to JIS K6760).

Example 23 Catalyst component (4)-4 obtained in Example 1-(4)
Polymerization was carried out in the same manner as in Example 1, 03), except that 9.8rv was used and 109 ethylene was allowed to coexist during the polymerization.

As a result, 247 g of ethylene-propylene copolymer (
A powder with an ethylene content of 3.8 weight range) was obtained.

That is, the polymerization activity is 4.960 g/g-catalyst component (
4)・hour, 210 kg/, 9-Ti・hour.

The boiling n-butyl alcohol extraction residue of this copolymer was 97
．． It was 91%.

Example 1, Example 7, Comparative Example 4, Comparative Example 12, and Reference Example (
Polymerization of propylene was carried out under the same conditions as in Example 1 using a catalyst system obtained from 0.209 AA type ring titanium chloride (0.58 g of diethylaluminum chloride).

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

1) Example 1 2) Example 7 3) Comparative example 4 4) Comparative example 12 Table 3 shows the relationship between H, R, and MFI of the pellets of each polypropylene powder obtained using each catalyst system. Shown in Figure 1.

Figure 1 shows that when propylene is polymerized using the catalyst system used in the present invention, H and R hardly change even if the MFI of the resulting polypropylene is increased. If propylene is polymerized using a catalyst system, the MFI of the resulting polypropylene can be increased, and the H, R of the polypropylene powder can be increased.
It is clear that , is significantly reduced.

[Brief explanation of drawings]

Figure 1 shows the H, R, (vertical axis units are fb) and pellet MFI (horizontal axis unit is g/10 min).

Claims (1)

[Scope of Claims] 1 (A) (1) Milled Sareta magnesium dihalide together with acyl halide (2) A mixture of a northwest titanium compound having at least one halogen atom and an organic compound having a 5i-0 bond Or an olefin polymer characterized by polymerizing an olefin in the presence of a solid component obtained by contacting an addition reaction product with (B) a trialkylminium compound and a catalyst system obtained from an organic carboxylic acid ester. improved manufacturing method.