JPH1192518A - Catalyst component for polymerization of propylene polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the rigidity, surface hardness, heat resistance, transparency, surface gloss, steam barrier properties, etc., by polymerizing propylene in the presence of a catalyst containing a solid polymerization catalyst component having a specified composition, an organoaluminum compound and an electron donating compound. SOLUTION: A magnesium compound, a titanium compound, a halogen compound and a first electron donating compound are brought into contact with each other at -30 to 150 deg.C so as to provide a molar ratio of the electron donating compound to titanium atoms (D/T) of 1 or greater, giving a solid polymerization catalyst component. This component is combined with an organoaluminum compound and a second electron donating compound to give a polymerization catalyst. Propylene and, if necessary, an α-olefin of the formula: R-CH=CH2 (wherein R is H, or a 1-20C hydrocarbon residue which may be a branched group) are (co)polymerized in the presence of the polymerization catalyst under atmospheric pressure to 100 kg/cm<3> , preferably 3-50 kg/cm<3> , at -50 to 200 deg.C, preferably 20-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to rigidity, surface hardness,
The present invention relates to a catalyst component for polymerization of a propylene-based polymer which is excellent in physical properties such as heat resistance and steam barrier properties and is suitable for automobiles, home electric appliances and packaging materials, and a method for producing the same.

[0002]

2. Description of the Related Art Propylene polymers are generally inexpensive, and their characteristics are transparency, mechanical strength, heat resistance, and the like.
Utilizing properties such as surface gloss, chemical resistance, oil resistance, rigidity, and bending fatigue resistance, it is used in a wide range of fields such as industrial materials, food packaging materials, cosmetic packaging materials, and chemical packaging materials.

[0003] The propylene-based polymer is, as described above,
Utilizing features such as rigidity and impact resistance,
Widely used in various industries such as sundries. Recently, it has been studied to increase the surface hardness in order to reduce the weight or cost of the product, to reduce the thickness of the product, and to prevent the surface of the product from being damaged. That is, a propylene-based polymer is required to have high rigidity, high surface hardness, and excellent impact resistance. In addition, demands for physical properties and workability are also becoming higher and higher. In particular, there is a strong demand for improvements in rigidity and strength at high temperatures, durability, and moldability of large molded products.

Conventionally, high rigidity and transparency improvement of the propylene-based polymer, with respect to surface gloss improvement, I _a and II _a group metal salts (e.g., sodium benzoate) monocarboxylic acids, dicarboxylic acids (adipic acid) A method of using a filler such as a salt of a group III-IV metal of an aliphatic dicarboxylic acid (for example, aluminum adipate), a dibenzylidene sorbitol derivative, or talc as a nucleating agent (Japanese Patent Publication No. 399-1).
809, JP-A-60-139731, etc.)
And a method for broadening the molecular weight distribution of a propylene-based polymer (JP-A-56-2307, JP-A-59-1725).
No. 07, JP-A-62-195007, etc.) are well known.

[0005] However, when these nucleating agents are used, the effect of improving the above-mentioned properties is obtained, but it is not always sufficient depending on the use. Therefore, by reducing the mechanical strength such as impact resistance and rigidity, and the surface hardness and heat resistance, the propylene polymer and the fillers such as talc and the like, which are suitable for automobiles, home appliances, and packaging materials, have a high product density. Therefore, it is desired to reduce the thickness of the product.

In addition, the tacticity (isotacticity) of the propylene-based polymer is improved, or the molecular weight distribution is widened to increase the strength and durability depending on the high molecular weight component.
Efforts have been made to improve the formability such as extrusion molding and hollow molding. Among them, the development of a catalyst having particularly high activity and high stereoregularity has been energetically studied in recent years. Each of them is a catalyst system comprising a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound as essential components, an organoaluminum, and an electron donating compound. JP-A-32604, JP-A-58-83006, JP-A-59-206408, JP-A-59-219311, JP-A-60-130607, JP-A-61-209207,
JP-A-61-21309, JP-A-62-72702,
JP-A-62-104811, JP-A-62-1705,
JP-A-63-197703, JP-A-63-26460
9, JP-A-1-126306, JP-A-1-31110
6, JP-A-3-62805, JP-A-3-70710, JP-A-4-103604, JP-A-4-11409, and JP-A-4-202505 are disclosed.

Further, the inventors have recently disclosed in Japanese Patent Application Laid-Open No. 4-43.
407, JP-A-4-149217, JP-A-4-1784
06, JP-A-4-180903, JP-A-4-18561
3, JP-A-4-198202, JP-A-4-19820
4, which have been disclosed in JP-A-5-9209 and JP-A-5-287019. In the propylene-based polymers disclosed in these prior art documents, the xylene-extractable insoluble portion is less than 99%, and a ¹³ C nuclear magnetic resonance spectrum (hereinafter, ¹³ C-NM)
R), the isotactic pentad fraction (mmmm) of the methyl group of the polypropylene measured at 93 to 98 at most
%, And there is a limit in improving various physical properties such as rigidity and heat resistance.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a propylene-based polymer having excellent rigidity, surface hardness, heat resistance, transparency, surface gloss, water vapor barrier properties, etc. without impairing the inherent properties of the propylene-based polymer. An object of the present invention is to provide a polymerization catalyst component of a propylene-based polymer suitable for automobiles, home electric appliances, and packaging materials, and a method for producing the same.

[0009]

The present inventors have studied various methods for solving the above-mentioned problems. As a result, (1) the xylene-extracted insoluble portion (XI) is 99.0% by weight or more, and (2) ¹³ C Isotactic pentad fraction (IP) by nuclear magnetic resonance spectrum of 98.0% or more, (3) average isotactic chain length (N) of 500 or more, and (4) column separation method of xylene-insoluble portion A new polymerization catalyst component which makes it possible to produce a propylene-based polymer in which the total chain length (N _f ) of the fractions according to the above is not less than 800 and the total of the fractions is not less than 10% by weight,
The present invention has been completed.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the characteristics of the propylene-based polymer provided by the present invention will be specifically described. (1) The xylene-extracted insoluble portion (XI) is the weight% of the polymer insoluble in xylene at 25 ° C. Specifically, 135 ° C
% Of the polymer once dissolved in ortho-xylene and precipitated at 25 ° C. X of the propylene polymer of the present invention
I is at least 99.0%, preferably at least 99.5%, more preferably at least 99.7%. XI is 9
If it is less than 9.0%, desired stiffness, heat resistance, surface hardness, surface gloss, transparency, water vapor barrier property and the like are insufficient.

(2) The isotactic pentad fraction (hereinafter, sometimes abbreviated as IP) in a polypropylene molecular chain by ¹³ C nuclear magnetic resonance spectrum is described in A.I. Za
mbelli, Macromolecules, 6 , 9
25 (1973). That is, it refers to an isotactic fraction in pentad units in a propylene-based polymer molecular chain measured using a nuclear magnetic resonance spectrum ( ¹³ C-NMR) of isotope carbon. The IP of the present invention is a measured value of polypropylene itself obtained by polymerization, not a measured value of polypropylene after the above-mentioned xylene extraction, other extraction, fractionation, and the like.

The assignment of the peaks was determined by Macromoleccu.
Based on a revised version of the above document described in Les, 8 , 687 (1975), IP was measured based on the intensity fraction of the mmmm peak in all the absorption peaks in the methyl carbon region of the ¹³ C-NMR spectrum. The IP in the propylene-based polymer measured in this way must be 98.0% or more, and if it is lower than this value, the desired rigidity, heat resistance, surface hardness, surface gloss, transparency, and steam barrier property are obtained. Etc. are insufficient. Preferably, the IP in the propylene-based polymer is 98.
5% or more is good. Particularly preferred is a propylene polymer having an IP of 99.0% or more.

(3) Isotactic average chain length (N)
Is the isotactic average chain length of the methyl group in the polypropylene molecule. C. The method reported by Randall (Polymer Sequen)
ce Distribution, Academic
Press, New York 1977, chapter
er2).

Specifically, polypropylene is 1,2,4-
The polymer is dissolved in a mixed solvent of trichlorobenzene and heavy benzene by heating to a temperature of 130 ° C. so that the polymer concentration becomes 10% by weight. This solution is placed in a glass sample tube having an inner diameter of 10 mmφ, and ¹³ C-NMR is measured under the same measurement conditions as the above isotactic pentad fraction (IP).

"Shan-Nong ZHU. Xiao"
-Zhen YANG, Riichiro CHUJ
O; Polymer Journal, vol. 15,
No. 12, p859-868 (1983), that is, it is assumed that there are two types of active sites during polymerization. One of them is a catalyst controlled polymerization, and the other is a terminal controlled polymerization.
(The details of the catalyst-controlled polymerization and the terminal-controlled polymerization are described in detail in Junji Furukawa; Essence of Polymers and Topics 2, “Polymer Synthesis”, p73, issued by Kagaku Dojin (1986).) The two-site model is as follows: α: catalyst-controlled polymerization (enantiomorphic process) Probability that D-form and L-form are added to the polymerization terminal, that is, an index of the degree of disturbance in the isotactic component σ: terminal-controlled polymerization (Bernoulli process) Probability of forming a meso-form to which the same one as the polymerization terminal is added can be summarized as ω: ratio of α-site.

In the homopolypropylene, the methyl group is split into 10 peaks in pentad units due to stereoregularity.
So that the actual measurement and the calculated intensity (area) match
α, σ, ω are obtained by the least square method, and then the quantities A _{1 to} A ₁₀ of each pentad unit are obtained by the following equation.

[0017]

[Table 1]

Next, the above-mentioned J.I. C. The definition of the average chain length (N) described in Randall's document is applied to each of the pentad units of A _{1 to} A ₇ determined above, where N = the number of chains in the meso form / the number of units in the meso form.

[0019]

(Equation 1)

[0020] The N value in the present invention is a measured value of the polypropylene itself obtained by polymerization, not a measured value of the polypropylene after the above-mentioned xylene extraction, other extraction, fractionation and the like. N of the highly stereoregular propylene polymer of the present invention
Is 500 or more, preferably 700 or more, and more preferably 800 or more. When N is less than 500, desired rigidity and heat resistance are insufficient.

Generally, the ¹³ C-NMR signal of polypropylene has three main peaks of methylene, methine and methyl. When the peak in the methyl region is enlarged, data as shown in FIG. 1 is obtained... Mmmmrmmmm..., Mmmmmm
You can see the shape of the irregular connection such as rrmmmmm. The average crystallizable isotactic chain length may be considered to be inversely related to the number of asymmetric bonds.

The larger the number of asymmetric bonds, that is, the larger the number of racemic structures cutting the mm mm structure, the shorter the average chain length (N). Average chain length (N) obtained in this way
Represents the length of the sequence of the isotactic structure that can be crystallized as described above. Therefore, the longer the length (ie, the smaller the number of asymmetric bonds), the higher the rigidity and heat resistance of the propylene-based polymer and the steam barrier. It is considered that physical properties such as properties are improved.

(4) The method of column separation of xylene-insoluble parts
Average chain length of each fraction (N _f) Means (1)
The obtained xylene-extracted insoluble polypropylene is
Dissolve in Siren at a temperature of 130 ° C, add celite and add 10
At a cooling rate of ℃ / hour to a temperature of 30 ℃, Celite
Attached and packed into a column, temperature 70-130
Heat to 2.5 ° C every 2.5 ° C and fractionate by fraction
And average chain length (N) for each fraction collected
Are calculated by the above method, and these are averaged for each fraction.
Chain length (N_f).

In the propylene polymer of the present invention,
The fractions having an average chain length (N _f ) of 800 or more for each fraction are preferably 10% by weight or more based on the whole. Preferably, 3
The content is preferably 0% by weight or more, particularly preferably 50% by weight or more. _If the total of those having an average chain length (N _f ) of 800 or more is 10% by weight or less, the effects of improving rigidity, surface hardness, heat resistance, and water vapor barrier properties are poor, which is not preferable.

Next, a method for producing a propylene polymer according to the present invention will be described. The propylene-based polymer of the present invention comprises (A) a first electron-donating compound supported on a solid catalyst component for polymerization containing a magnesium compound, a titanium compound, a halogen-containing compound and a first electron-donating compound as essential components. The compound / titanium atom content molar ratio (D / T) is D /
A solid catalyst component for polymerization, wherein T ≧ 1;
It can be produced by polymerizing propylene using a polymerization catalyst comprising (B) an organic aluminum compound and (C) a second electron donating compound.

Here, the magnesium compound includes magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide; and alkoxy compounds such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium and diphenoxymagnesium. Magnesium; carboxylic acid salts such as magnesium laurate, magnesium stearate, and magnesium acetate; and alkylmagnesium such as dimethylmagnesium, diethylmagnesium, and butylethylmagnesium. These various magnesium compounds can be used alone or in combination of two or more. Preferably, magnesium halide or alkoxymagnesium is used, or magnesium halide is formed during catalyst formation.
Particularly preferably, the halogen is chlorine.

Titanium compounds include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide; tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetraphenoxytitanium Examples thereof include alkoxytitanium such as titanium; and alkoxytitanium halides such as ethoxytitanium chloride, butoxytitanium chloride, phenoxytitanium chloride, dibutoxytitanium dichloride, and tributoxytitanium chloride. These various titanium compounds can be used alone or in combination of two or more. Preferably, a tetravalent titanium compound containing halogen,
Particularly preferred is titanium tetrachloride.

Halogen containing compounds are those wherein the halogen is fluorine, chlorine, bromine or iodine, preferably chlorine;
Specific compounds actually exemplified depend on the catalyst component preparation method, but titanium halides such as titanium tetrachloride and titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, and phosphorus trichloride. And halogenated phosphorus such as phosphorus pentachloride, but halogenated hydrocarbons, halogen molecules and hydrohalic acid may be used depending on the method of preparing the catalyst component.

The first electron donating compound generally includes an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, a sulfur-containing compound and the like. As the oxygen-containing compound, for example,
Examples include alcohols, ethers, esters, acid halides, and acid anhydrides. More specifically, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, 2-ethyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol Alcohols such as phenol, cresol, ethylphenol, naphthol; ethers and diethers such as methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran, anisole, diphenyl ether; ethyl acetate;
Ethyl chloroacetate, ethyl propionate, ethyl butyrate,
Ethyl acrylate, ethyl crotonate, ethyl oleate, ethyl stearate, ethyl phenylacetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, propyl toluate, toluic acid Butyl, methyl ethyl benzoate, methyl anisate, ethyl anisate, methyl ethoxy benzoate, ethyl ethoxy benzoate, ethyl cinnamate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, phthalate Esters such as diisobutyl acid, dihexyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone, ethylene carbonate; acid chlorides such as acetyl chloride, benzoyl chloride, toluic acid chloride, phthalic chloride; maleic anhydride Acid anhydrides such as formic acid and phthalic anhydride are exemplified.

Further, these first electron donating compounds can be used alone or in combination of two or more. Esters are preferred, and phthalates are particularly preferred.
Of course, one compound of the magnesium compound, the titanium compound, the halogen compound, and the first electron donating compound can also serve as two or more of these four types of compounds.

The use amount of each component is arbitrary as long as the effect is recognized in the present invention, but the following range is generally preferable. The amount of the titanium compound used is 0.000 in molar ratio with respect to the amount of the magnesium compound used.
It is good to be in the range of 1 to 1000, preferably 0.01 to 1
00 is within the range. Although halogen compounds are used as necessary, when a halogen compound is used, the amount of the titanium compound or the magnesium compound may or may not include halogen, regardless of whether or not the halogen compound is used. On the other hand, the molar ratio is preferably in the range of 0.01 to 1000, and more preferably in the range of 0.1 to 100. The amount of the first electron donating compound used is 0.001 to 10 in a molar ratio to the amount of the magnesium compound used.
Is good, and it is preferably in the range of 0.01 to 5.

The method for preparing the solid catalyst component used in the present invention is a method in which a magnesium compound, a titanium compound, a first electron-donating compound and, if necessary, an auxiliary such as a halogen-containing compound are temporarily or stepwise mixed. A conventionally known method for preparing a solid catalyst component obtained by contacting with and reacting with a catalyst can be used. Specific examples of known methods include the following preparation methods.

(1) A method in which a magnesium halide is brought into contact with a first electron-donating compound and, if necessary, a titanium compound. (2) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a tetraalkoxytitanium and a specific polymer silicon compound.

(3) dissolving the magnesium compound with tetraalkoxytitanium and the first electron-donating compound,
A method in which a titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halide compound. (4) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, a first electron-donating compound, and a titanium halide compound are brought into contact therewith.

(5) A method in which a Grignard reagent typified by an organomagnesium compound is allowed to act on a reducing agent, a halogenating agent, or the like, and then the first electron-donating compound is brought into contact with a titanium compound. (6) A method in which a halogenating agent and / or a titanium compound is brought into contact with an alkoxymagnesium compound in the presence or absence of a first electron-donating compound.

(7) A method in which a magnesium compound is dissolved in tetraalkoxytitanium, treated with a polymer silicon compound, and then treated with a silicon halide and an organometallic compound. (8) A method of treating a spherical magnesium compound / alcohol complex with a first electron-donating compound, a titanium halide compound and the like.

In order to produce the propylene-based polymer of the present invention, any of the above-described methods for preparing a solid catalyst component may be employed. However, at least the first electron-donating compound supported on the solid catalyst component may be used. / Titanium atom content molar ratio (D
/ T) is required to use a solid catalyst component for polymerization such that D / T ≧ 1. In this case, it is more preferable that D / T ≧ 1.5.

When D / T <1, it is difficult to obtain the highly stereoregular propylene polymer of the present invention. As described above, according to the present invention, the solid catalyst component having the magnesium compound, the titanium compound, the halogen compound and the first electron-donating compound as essential components, and the first catalyst component supported on the solid catalyst component.
Molar ratio of the electron donating compound (D) to titanium (T) (D
(T) wherein D / T ≧ 1 is provided. Although this solid catalyst component was developed for the production of polypropylene having a high stereoregularity, the solid catalyst component for general polymerization of propylene-based polymers or α-olefins other than propylene-based polymers for general polymerization was used. It is also useful. Especially high stereoregularity,
In order to obtain a propylene polymer requiring rigidity and heat resistance, it is preferable that D / T ≧ 1.5.

In the conventional preparation method, the above condition (D
Even if the solid catalyst component does not satisfy the condition (/ T ≧ 1), the solid catalyst component may satisfy the above conditions by further performing the following treatment, and more preferably. In this case, the first in the solid catalyst component before improvement
Of the electron donor compound / Ti atom content (D /
T) _i and the first electron donating compound / T in the improved catalyst component
The molar ratio (D / T) _{m of the} i-atom content is (D / T) _m /
(D / T) _i > 1 needs to be satisfied, and (D / T) _i
/ T) _m / (D / T) _i ≧ 2 is more preferable.

For example, a solid catalyst component containing magnesium, titanium, a halogen and a first electron-donating compound as essential components, prepared by various known methods as described above, is further added to a first electron-donating compound. And / or by treating with a halogen-containing compound, the D / T can be made larger than before treatment to improve the catalyst. The order and number of the treatment with the first electron donating compound and the treatment with the halogen compound are not particularly limited, but as a general treatment method for the solid catalyst component, the solid catalyst component is supported by being treated with the first electron donating compound. After that, it is treated with a halogen-containing compound, washed, and further washed with a hydrocarbon.

The first electron donating compound used for improving the catalyst component may be the same as or different from the one used at the time of preparing the solid catalyst component before the improvement. The first electron donating compound can be used alone or in combination of two or more. Preferred are esters, particularly preferred are phthalates.

The amount of the first electron-donating compound used is 0.001 to 500 with respect to titanium atoms in the solid catalyst component.
The molar ratio is preferably in the range of 0.01 to 50, and preferably in the range of 0.01 to 50. If the amount of the first electron donating compound used is extremely small, it is difficult to satisfy the relationship of (D / T) _m / (D / T) _i > 1, and conversely, the amount of the first electron donating compound used Is extremely large, it is not preferable because the polymerization activity decreases.

The halogen-containing compound used for improving the catalyst includes:
It may be the same as or different from that used during the preparation of the solid catalyst component before the improvement. Among them, titanium halide, silicon halide and halogenated hydrocarbon are preferred. The halogen-containing compounds can be used alone or in combination of two or more.
The amount of the halogen-containing compound used is in the range of 0.1 to 10000 mol ratio, preferably in the range of 1 to 3000 mol ratio, based on titanium atoms in the solid catalyst component,
Particularly preferably, the molar ratio is in the range of 5 to 500. When the amount of the halogen-containing compound is extremely small, it is difficult to satisfy the relationship of (D / T) _m / (D / T) _i > 1, and when the amount of the halogen-containing compound is extremely large, This is not preferred because the polymerization activity is reduced and the amount of waste liquid is increased.

The temperature at which the solid catalyst component is treated with the first electron donating compound for improvement is in the range of -30 to 150 ° C, preferably 0 to 100 ° C. The temperature at which the solid catalyst component is treated with the halogen-containing compound is 0 to 200.
° C, preferably in the range of 50 to 150 ° C. Temperature conditions other than these are not preferred because the polymerization activity is reduced.

A first electron-donating compound of the solid catalyst component,
The improvement treatment with a halogen-containing compound can be usually performed in a hydrocarbon solvent. As the hydrocarbon used at this time, an inert hydrocarbon such as an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, and decane; and an aromatic hydrocarbon such as benzene, toluene, and xylene are preferable. Further, these hydrocarbons can be used as a washing solvent for the solid catalyst component after the treatment with the first electron-donating compound and the halogen-containing compound of the solid catalyst component.

The temperature at which the solid catalyst component before improvement is treated with the first electron-donating compound and the catalyst for improved olefin polymerization after washing with the halogen-containing compound is washed with the hydrocarbon is in the range of 0 to 100 ° C. Yes, preferably 60-
140 ° C. If the cleaning temperature is extremely low, it is difficult to satisfy the relationship of (D / T) _m / (D / T) _i > 1, and if the cleaning temperature is extremely high, (D / T) _m
The relationship of / (D / T) _i > 1 is not preferable because the polymerization activity decreases.

When the solid catalyst component is treated with the first electron-donating compound, treatment with the halogen-containing compound (washing)
If not carried out, the polymerization activity is extremely reduced and the effect of the present invention is not exhibited. The number of times of treatment (washing) with a halogen-containing compound is not particularly limited, but is preferably 2 to 4 times in order to sufficiently exert the effects of the present invention.
Once, the effect of the present invention is not sufficiently exhibited, and if it is repeated too many times, the polymerization activity is undesirably reduced.

[0048] As the first electron-donating compound in the present invention, the general formula TiX _a · Y _b (wherein, X is Cl, B
a titanium atom represented by r or I, a is 3 or 4, Y is an electron donating compound (1), and 0 <b ≦ 3), and after treating with and supporting the same, By washing with a compound and further washing with a hydrocarbon, the solid catalyst component can be improved to a solid catalyst component in which D / T ≧ 1. Thus, when the solid catalyst component is treated with the first electron-donating compound, the number of treatments (washing) with the halogen-containing compound of the present invention is generally required to be at least twice as described above. when using _a · Y _b, the effect of the present invention by treatment with a halogen-containing compound (washed) number 1 to 2 times is expressed sufficiently. Further, since the amount of the halogen-containing compound used can be reduced as described later, the amount of waste liquid discharged when the improved solid catalyst component is washed with hydrocarbons can be greatly reduced.

TiX _a (where X is a halogen atom of Cl, Br, I, a is 3 or 4) is described, for example, in R. S.
P. Coutts, P .; C. Ways, Adva
n. Organometal. Chem. , 9 , 135
(1970), 4th Edition New Experimental Chemistry Course 17 Inorganic Complexes / Chelate Complexes The Chemical Society of Japan Maruzen (1991) p. 3
5, H. K. Kakkoen, J. et al. Pursiaine
n, T. A. Pkkanen, M .; Ahlgren,
E. FIG. Iiskola, J .; Organomet. Che
m. , 453 , 175 (1993) and the like, it is generally known that a complex easily forms with an electron donating compound.

X in TiX _a · Y _b is a halogen atom of Cl, Br and I, and of these, Cl is preferred.
a is 3 or 4, but preferably 4. Y
The (first electron donating compound) can be selected from those described above, and may be the same as or different from the one used at the time of preparing the solid catalyst component before improvement. When preparing TiX _a and Y _b , the first electron donating compound can be used alone or in combination of two or more. Among Y, preferred are organic acid esters, and particularly preferred are phthalic esters.
Y is a b, the molar ratio TiX _a in Y in preparing TiX _a · Y _b as 0 <b ≦ 2 when of 0 <b ≦ 3, a case of the aforementioned a is 3 4 , Y and the valence of Ti. Most preferably, a is 4,
This is the case where b is 1.

[0051] The amount of TiX _a · Y _b, relative to the titanium atom in the solid catalyst component prior to improvement, from 0.001 to 500
The molar ratio is preferably in the range, preferably in the range of 0.01 to 50 molar ratio, and particularly preferably in the range of 0.1 to 10 molar ratio. Moreover, when the extremely small amount of the TiX _a · Y _{b is, (D / T) m /} (D / T) i> 1 of the difficulties in establishing the relationship, extremes usage TiX _a · Y _b in the opposite If the amount is too high, the polymerization activity is undesirably reduced.

The amount of the halogen-containing compound used is in the range of 0.1 to 1000 mole ratio, preferably in the range of 1 to 500 mole ratio, particularly preferably 5 to 500 mole ratio with respect to titanium atom in the solid catalyst. It is in the range of １００100 molar ratio.
The selection of the halogen-containing compound can be the same as described above. Further, the temperature for processing the solid catalyst component TiX _a · Y _b, the first thing it is similar to the processing temperature of the electron donor compound, also to wash the solid catalyst component with a halogen-containing compound temperature Can be the same as described above.

The treatment of the solid catalyst component with TiX _a and Y _b and the washing with the halogen-containing compound may be the same as the treatment with the first electron-donating compound and the washing with the halogen-containing compound. TiX _a · Y _b by the processing number,
No particular limitation is imposed on the number of washes with a halogen-containing compound, as described above, after processing TiX _a · Y _b,
Washing once or twice with a halogen-containing compound sufficiently exerts the effects of the present invention. Without washing with a halogen-containing compound, the high performance obtained in the present invention cannot be obtained. Prepolymerization The improved solid catalyst component prepared by the above method is used for the polymerization of propylene by a combination with an organoaluminum compound described below and a second electron-donating compound.
It is possible to prepolymerize a small amount of the monomer before the polymerization. Usually, 1 g of the prepared improved solid catalyst component
About 0.01 g to about 1000 g, and the temperature of the prepolymerization is -30 to 80 ° C., although it is optional. The pre-polymerization is usually performed in the coexistence of an organic aluminum compound and a second electron donating compound used in the polymerization described later.
The prepolymerization can be generally carried out in an inert hydrocarbon solvent, but can also be carried out in a liquid monomer or a gas phase monomer.

The monomers used in the prepolymerization include:
In addition to propylene, for example, ethylene, 1-butene, 3
-Methyl-1-butene, 3-methyl-1-pentene, 4
Α-olefins such as -methyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane and vinylcyclohexane; styrene derivatives such as styrene and α-methylstyrene; and diene such as butadiene and 1,9-decadiene. And allyltrialkylsilanes may be used. In addition, these monomers can be used not only in one kind but also in two or more kinds stepwise or as a mixture. In addition, hydrogen can also be used as a molecular weight regulator at the time of prepolymerization. Propylene Polymerization The above-mentioned improved solid catalyst component can polymerize a propylene polymer in the presence of an organic aluminum compound and a second electron donating compound.

The organoaluminum compound used in the present invention is typically a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum; dimethylaluminum hydride; Alkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; alkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride; alkyl aluminum such as diethyl aluminum ethoxide and diethyl aluminum phenoxide Alkoki De; methyl aluminoxane, ethyl aluminoxane, can be exemplified aluminoxanes such as methyl aluminoxane. These organoaluminum compounds may be used alone or in combination of two or more. Preferably, it is a trialkylaluminum.

The second electron-donating compound used in the present invention may be the same as or different from the first electron-donating compound, but is typically an aromatic carboxylic acid ester compound,
Examples thereof include a silicon compound having an Si—O—C or Si—N—C bond, an acetal compound, a germanium compound having a Ge—O—C bond, and a nitrogen or oxygen heterocyclic compound having an alkyl substituent.

Specific examples of these compounds include aromatic carboxylic acid esters such as ethyl benzoate, ethyl p-toluate and ethyl p-anisate; phenyltrimethoxysilane, diphenylmethoxysilane, di-n-propyl. Dimethoxysilane, di-i-propyldimethoxysilane, di-t-butyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, t-butyltrimethoxysilane, cyclohexyltrimethoxysilane, texyltrimethoxysilane Silicon compounds such as, tetramethoxysilane, tetraethoxysilane;
Acetal compounds such as benzophenone dimethoxyacetal, benzophenonediethoxyacetal, acetophenonedimethoxyacetal, acetophenonediethoxydiethoxyacetal; germanium compounds such as diphenyldimethoxygermane and phenyltriethoxygermane; 2,2,6,6-tetramethylpiperidine And heterocyclic compounds such as 2,2,6,6-tetramethylpyran.

These electron donating compounds can be used alone or in combination of two or more. Preferred are silicon compounds and acetal compounds, and particularly preferred are silicon compounds having a Si—O—C bond. The polymerization method in the production method of the present invention is not particularly limited, and a known method can be used. The polymerization method can be applied to a gas phase polymerization method in addition to a liquid phase polymerization method such as a slurry polymerization and a park polymerization. Further, the present invention can be applied not only to patch polymerization but also to a method of performing continuous polymerization or batch polymerization. As a polymerization solvent in the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptanecyclohexane, and toluene is used. Further, the polymerization method in the production method of the present invention can be used for multistage polymerization of two or more polymerization reactors.

The polymerization temperature is about -50 to 200 ° C., preferably 20 to 150 ° C., and the polymerization pressure is between atmospheric pressure and 1
00 kg / cm ² G, preferably 3 to 50 kg / cm ² G. In addition, the molecular weight can be adjusted by adding an appropriate amount of hydrogen during the polymerization. In addition to homopolymerization of propylene in the production method of the present invention, generally propylene formula R-CH = CH ₂ (R is a hydrogen atom, or a C 1 -C 20
Which may be a branched group). Specifically, ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane, vinyl Cyclohexane and the like are exemplified. Further styrene, styrene derivatives such as α-methylstyrene,
Examples thereof include dienes such as butadiene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene, and allyltrialkylsilanes. These monomers can be used alone or in combination of two or more.

Incidentally, among the propylene polymers of the present invention, the propylene-ethylene block copolymer can be produced by multi-stage polymerization of two or more polymerization reactors, and in particular, the homo-polypropylene is produced in the first stage. Is preferred. In this case, if the homopolypropylene extracted after the completion of the first-stage polymerization satisfies the constitutional requirements of the present invention, the finally obtained copolymer also solves the problems of the present invention and was obtained. It can have physical properties.

The propylene polymer obtained in the present invention can be made into a resin composition further improved in crystallinity and high-speed moldability by adding a known nucleating agent. Examples of nucleating agents include the monocarboxylic acids _Ia and II
_a group metal salts (e.g., sodium benzoate), a dicarboxylic acid (adipic acid), III to IV group metal salts of aliphatic dicarboxylic acids (e.g. p-t-butylbenzoic acid aluminum salt), dibenzylidene sorbitol derivatives, talc And the like.

Particularly preferred are 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, and 1,3,2,4-di- (p- Ethylbenzylidene) sorbitol, 1,3
2,4-di- (p-chlorobenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, sodium-bis (4
-T-butylphenyl) phosphate, sodium-
2,2-methylene-bis- (4,4-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, and the like, and And inorganic fillers such as talc and calcium carbonate.

When the nucleating agent is added to the propylene polymer in an amount of at least 0.05 to 15% by weight, the effect of the present invention is remarkably preferable. Preferably from 0.08 to 0.8% by weight, particularly preferably
It is preferable to add 0.1 to 0.5% by weight. However,
An inorganic compound such as talc has a smaller nucleating agent effect than the nucleating agent exemplified above, and thus is preferably added at 1 to 15% by weight. Preferably from 2 to 13% by weight, particularly preferably from 5 to
10% by weight.

The propylene-based polymer or resin composition of the present invention may contain other additives (eg, antioxidants, weathering stabilizers, antistatic agents, lubricants, antiblocking agents) commonly used in thermoplastic resins. , An anti-fogging agent, a dye, a pigment, an oil, a wax, etc.) can be appropriately compounded as long as the object of the present invention is not impaired. For example, examples of such additives include 2,5-di-t-butylhydroquinone as an antioxidant,
2,6-di-t-butyl-p-cresol, 4,4-thiobis- (6-t-butylphenol), 2,2-methylene-bis (4-methyl-6-t-butylphenol), octadecyl-3 -(3 ', 5'-di-tert-butyl-1'-hydroxyphenyl) propionate, 4,
4'-thiobis (6-butylphenol); as an ultraviolet absorber, ethyl-2-cyano-3,3-diphenylacrylate, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxy-4 -Octoxybenzophenone, dimethyl phthalate, diethyl phthalate, wax, liquid paraffin, phosphate ester as a plasticizer, monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide, carbon dioxide as an antistatic agent Waxes, lubricants such as ethylene bisstearamide, butyl stearate, etc., coloring agents, such as carbon black, phthalocyanine, quinacridone, indoline, azo pigments, titanium oxide, red iron oxide, etc., and fillers, glass fiber,
Asbestos, mica, parastonite, calcium silicate, aluminum silicate and the like. Many other high molecular compounds can also be blended to such an extent that the effects of the present invention are not impaired.

The melting index (MFR to JIS-7210, Table 1, condition 14) of the propylene-based polymer of the present invention is not particularly limited and is selected depending on the molding method and application, but is usually 0.1 to 500 g. A range of / 10 minutes is appropriate. The propylene-based polymer of the present invention can be obtained by injection molding, film, sheet,
It can be molded into tubes, bottles, etc., and can be used alone or when laminated with other materials.

For example, as such a laminating method, a dry laminating adhesive such as a polyurethane-based or polyester-based adhesive is used, and another thermoplastic resin layer is added to a single-layer product of the propylene-based polymer or the resin composition of the present invention. Lamination is performed by a so-called dry lamination molding method or sandwich lamination method, or a coextrusion lamination method, a coextrusion method (feed block method, multi-manifold method), a coinjection molding method, or a coextrusion pipe molding method.

The multilayer laminate thus obtained is then reheated and stretched using a vacuum forming machine, a press forming machine, a stretch blow molding machine or the like, or the multilayer laminate or a single molded product is obtained. Can be subjected to a heat stretching operation using a uniaxial or biaxial stretching machine. Hereinafter, the present invention will be described in more detail by way of examples.

[0068]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method and an apparatus for measuring each physical property value in the present invention will be described below. (1) Xylene-insoluble portion (XI) 2.5 g of the polymer was added to ortho-xylene (25
0ml) and precipitated at 25 ° C (wt%)
Was defined as a xylene-insoluble portion (XI).

(2) Isotactic pentad fraction
(Mmmm) The mmmm fraction is calculated based on the methyl group in the propylene polymer molecular chain.
Isotactic fraction in pentad units. Measurement
Is JNM-GSX400 (manufactured by JEOL Ltd.) ¹³C nuclear
(100 MHz). Each
Gunnar states that Macromol from Zambelli et al.
ecules,13, 267, (1980)
Was. The measurement conditions are shown below.

Measurement mode: Proton decoupling method Pulse width: 8.0 μs Pulse repetition time: 3.0 μs Number of integrations: 20000 Solvent: Mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene (75/25 volume) %) Internal standard: hexamethyldisiloxane Sample concentration: 300 mg / 3.0 ml Solvent Measurement temperature: 120 ° C. (3) Average isotactic chain length (N) C. Rad
all reported method (Polymer
Sequence Distribution, Aca
demic Press, New York 197
7, Chapter 2). Specifically, polypropylene is mixed with 1,2,4-trichlorobenzene / deuterated benzene in a mixed solvent having a polymer concentration of 1%.
The mixture is heated to a temperature of 130 ° C. so as to be 0% by weight and dissolved.

This solution was placed in a glass sample tube having an inner diameter of 10 mmφ, and the isotactic pentad fraction (IP)
< ¹³ > C-NMR is measured under the same measurement conditions as described above. Next, as described above, the average chain length (N) can be determined by the following definition from the number of chains of the meso body and the number of units of the meso body. N = the number of chains of the meso form / the number of units of the meso form (4) Column fractionation method The propylene-based polymer in the xylene-insoluble portion was dissolved in para-xylene at a temperature of 130 ° C., and celite was added. The temperature is lowered to 30 ° C. and adhered to Celite. This deposit is packed in a column and the temperature is reduced from 70 ° C. to 13
The temperature is raised to 0 ° C. every 2.5 ° C. and fractionated by fraction.

(5) Injection molding IS-170FII manufactured by Toshiba Machine Co., Ltd. (theoretical injection capacity 25
0cm ³ ), molding temperature 220 ° C, mold cooling temperature 50
℃, Izod impact test specimen, flexural modulus test specimen, deflection temperature under load test specimen, specimen for surface gloss (thickness 2mm × 15
cm × 11 cm flat plate). Next, after being left in a constant temperature room at a humidity of 50% and a temperature of 23 ° C. for two days and nights, their physical properties were measured.

(6) Izod impact strength (with notch) This was carried out in accordance with JIS K7110. The apparatus used was a U-F impact tester manufactured by Kamishima Seisakusho Co., Ltd. (7) Flexural modulus It was performed in accordance with JIS K7203.

(8) Ethylene content J. ¹³ C- reported by Carman et al.
NMR method (Macromolecules, 1
0 , 537 (1977)). (9) MFR (melt flow rate) This was carried out in accordance with JIS K7210 Table 1 Condition 14.
The apparatus used was a melt indexer manufactured by Takara Co., Ltd.

(10) Deflection temperature under load Based on JIS K7207B table, the deflection temperature was measured using an HDTεVSPT tester manufactured by Toyo Seiki Seisaku-sho, Ltd. (10) Rockwell Surface Hardness A sample for measurement was prepared using a press molding machine at a temperature of 230 ° C., and the measurement was performed according to JIS K7202 using an AR-10 type Rockwell hardness tester manufactured by Toyo Seiki Seisaku-sho, Ltd.

(12) Film Forming A film having a thickness of 60 μm was prepared using a 40 mmφT die film forming machine manufactured by Yoshii Iron Works Co., Ltd. under the conditions of a die temperature of 230 ° C., a cooling temperature of 30 ° C., and a take-up speed of 10 m / min. The transmission amount, haze, and surface glossiness were measured. (13) HG manufactured by Suga Test Machine Co., Ltd. in accordance with Haze JIS K7105
The measurement was performed using an Haze meter of the M-2D type.

(14) Surface glossiness The glossiness was measured using a VG-1D type gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K7105. (15) Amount of water vapor permeated According to ASTM-E96, MODERN CONTR
Using OLS INC's PERMATRAN W,
The measurement was performed under the conditions of a temperature of 37.8 ° C. and a relative humidity of 90%.

(16) Catalyst Analysis The solid catalyst component before improvement and the solid catalyst component for improved olefin polymerization were decomposed with dilute sulfuric acid, and organic substances were extracted with heptane.
The amount of Ti in the aqueous layer was quantified by using an atomic absorption type AA610S manufactured by Shimadzu Corporation. Heptane layer is manufactured by Hitachi, Ltd.
The electron donating compound was quantified by gas chromatography 263-50. Example 1 (1) Preparation of solid catalyst component before improvement (conventional method) 56.8 g (597 mmol ) of anhydrous magnesium chloride, 100 g (174 mmol) of anhydrous ethanol, and Idemitsu Kosan Co., Ltd.
Vaseline oil CP15N manufactured by Shin-Etsu Silicone Co., Ltd. and 500 ml of silicone oil KF96 manufactured by Shin-Etsu Silicone Co., Ltd.
It was completely dissolved at 120 ° C. under a nitrogen atmosphere. This mixture was stirred at 120 ° C. and 3000 rpm for 3 minutes using a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. With stirring maintained, it was transferred into 2 liters of anhydrous heptane not to exceed 0 ° C. The obtained white solid was sufficiently washed with anhydrous heptane and dried under vacuum at room temperature.

The obtained MgCl ₂ .2.5C ₂ H ₅ OH
Was suspended in 200 ml of anhydrous heptane. While stirring at 0 ° C., 500 ml of titanium tetrachloride (4.
5 mol) was added dropwise over 1 hour. Next, when heating was started and the temperature reached 40 ° C., diisobutyl phthalate 4.9 was added.
6 g (17.8 mmol) was added, and the temperature was raised to 100 ° C. in about 1 hour. After reacting at 100 ° C. for 2 hours, a solid portion was collected by hot filtration. Thereafter, 500 ml (4.5 mol) of titanium tetrachloride was suspended in the reaction product, and
The reaction was performed at 0 ° C. for 1 hour. After the completion of the reaction, the solid portion was collected again by filtration under hot conditions, and washed with 1.0 liter of hexane at 60 ° C. seven times and three times with 1.0 liter of hexane at room temperature. When the titanium content in the obtained solid catalyst component was measured, it was 2.25% by weight. Further, the electron donating compound (1) was contained at 7.81% by weight.

(2) Preparation of Improved Solid Catalyst Component 20 g of the solid catalyst component obtained above was added to 300 ml of toluene.
And 2.78 g of diisobutyl phthalate at 25 ° C.
(10 mmol) for 1 hour. After completion of the reaction, 100 ml (900 mmol) of titanium tetrachloride was added and reacted at 90 ° C. for 1 hour. After completion of the reaction, a solid portion was collected by hot filtration, and then 300 ml of toluene and 100 ml (900 mmol) of titanium tetrachloride were suspended in the reaction product.
Allowed to react for hours. After the completion of the reaction, the solid portion was collected again by filtration under hot conditions, and washed seven times with 500 ml of 90 ° C. toluene and three times with 500 ml of hexane at room temperature. When the titanium content in the obtained solid catalyst component was measured, it was 1.01% by weight. The first electron donating compound is 12.0
% By weight. Table 1 shows a comparison of the analysis results of the catalyst components before and after the improvement.

(3) Prepolymerization In an autoclave having a content volume of 3 liters under a nitrogen atmosphere, 500 ml of n-heptane, 6.0 g (53 mmol) of triethylaluminum, 3.9 g (17 mmol) of dicyclopentyldimethoxysilane, and 10 g of the improved olefin polymerization catalyst component obtained in the above (2) was charged, and 0 to 5
The mixture was stirred for 5 minutes in a temperature range of ° C. Next, propylene was fed into the autoclave so that 10 g of propylene was polymerized per 1 g of the improved olefin polymerization catalyst component.
Prepolymerization was performed for 1 hour in a temperature range of ° C. The obtained prepolymerized solid catalyst component was washed three times with 500 ml of n-heptane and used for the production of the following propylene-based polymer.

(4) In a main polymerization nitrogen atmosphere, 2.0 g of the prepolymerized solid catalyst component prepared as described above and 11.4 g of triethylaluminum (10 g) were placed in a 60-liter autoclave equipped with a stirrer.
0 mmol), 6.84 dicyclopentyldimethoxysilane.
g (30 mmol) was added, hydrogen was then charged so as to be 18 kg of propylene, and 13000 mol ppm based on propylene, and the temperature was raised to 70 ° C., and polymerization was performed for 1 hour. 1
After an hour, unreacted propylene was removed to terminate the polymerization. As a result, 6.56 kg of polypropylene was obtained, and the polymerization activity was 32.8 kg / g-solid catalyst component, MF of the polymer.
R was 33.0 g / 10 minutes. Table 2 shows the evaluation results of the physical properties of the polymer. Example 2 (1) Preparation of solid catalyst component before improvement Same as Example 1.

(2) TiCl ₄ [C ₆ H ₄ (COO ⁱ C
Preparation of ₄ H ₉ ) ₂ ] Hexane containing 19 g (100 mmol) of titanium tetrachloride.
In 0 liter of solution, diisobutyl phthalate: C ₆ H ₄
(COO ⁱ C ₄ H ₉ ) ₂ 27.8 g (100 mmol)
The solution was added dropwise over about 30 minutes while maintaining 0 ° C. After completion of the dropwise addition, the temperature was raised to 40 ° C., and the reaction was performed for 30 minutes. After the reaction,
The solid portion was collected and washed three times with 500 ml of hexane to obtain the desired product.

(3) Preparation of Improved Olefin Polymerization Catalyst Component 20 g of the solid catalyst component obtained in the above (1) was dissolved in toluene 3
In 25 ml of TiCl ₄ [C ₆ H ₄ (C
OO ⁱ C ₄ H ₉ ) ₂ ] was treated with 5.2 g (11 mmol) for 1 hour to be supported. After the loading was completed, a solid portion was collected by hot filtration, and 300 ml of toluene and 10 ml of titanium tetrachloride (9
0 mmol), washed by stirring at 90 ° C. for 1 hour, and collecting a solid portion by hot filtration.
5 times with 500 ml of toluene at 0 ° C and 500 ml of hexane at room temperature.
Washed three times with ml. When the titanium content in the obtained solid catalyst component was measured, it was 0.91% by weight. The first electron donating compound was contained at 10.6% by weight. Table 1 shows a comparison of catalyst analysis results before and after the improvement.

(4) Prepolymerization In an autoclave having an internal volume of 3 liters under a nitrogen atmosphere, 500 ml of n-heptane, 6.0 g (53 mmol) of triethylaluminum, 3.9 g (17 mmol) of dicyclopentyldimethoxysilane, and 10 g of the improved olefin polymerization catalyst component obtained in the above (3) was charged, and 0 to 5
The mixture was stirred for 5 minutes in a temperature range of ° C. Next, propylene was fed into the autoclave so that 10 g of propylene was polymerized per 1 g of the improved olefin polymerization catalyst component.
Prepolymerization was performed for 1 hour in a temperature range of ° C. The obtained prepolymerized solid catalyst component was washed three times with 500 ml of n-heptane and used for the production of the following propylene-based polymer.

(5) Under an atmosphere of main polymerization nitrogen, 2.0 g of the prepolymerized solid catalyst component prepared in the above manner and 11.4 g of triethylaluminum (10 g) were placed in a 60-liter autoclave equipped with a stirrer.
0 mmol), 6.84 dicyclopentyldimethoxysilane.
g (30 mmol) was added, hydrogen was then charged so as to be 18 kg of propylene, and 13000 mol ppm based on propylene, and the temperature was raised to 70 ° C., and polymerization was performed for 1 hour. 1
After an hour, unreacted propylene was removed to terminate the polymerization. As a result, 6.64 kg of polypropylene was obtained, the polymerization activity was 34 kg / g-solid catalyst component, and the MFR of the polymer was 34.2 g / 10 minutes. Table 2 shows the evaluation results of the physical properties of the polymer. Comparative Example 1 In a nitrogen atmosphere, a Tosoh. 6.0 g of AA type titanium trichloride and 23.5 g (195 mmol) of diethyl aluminum chloride manufactured by Akzo Co., Ltd.
Then propylene 18 kg, 8000 to propylene
Hydrogen was charged so as to be mol ppm, the temperature was raised to 70 ° C., and polymerization was performed for 1 hour. One hour later, unreacted propylene was removed to terminate the polymerization. As a result, 6.23 kg of polypropylene was obtained, and the MFR of the polymer was 32.2 g.
/ 10 minutes. Table 2 shows the evaluation results of the physical properties of the polymer. Comparative Example 2 The solid catalyst component before improvement prepared in (1) of Example 1 was used, and the charged amount of hydrogen during propylene polymerization was 93.
Preliminary polymerization and propylene polymerization were carried out in the same manner and under the same conditions as in Example 2 except that the amount was changed to 00 mol ppm. As a result, 6.88 kg of polypropylene was obtained, and the MFR of the polymer was 33.0 g / 10 minutes. Table 2 shows the evaluation results of the physical properties of the polymer. Examples 3 to 5 The MFR of the resulting polypropylene was 10.
All methods and conditions were the same as in Example 2 except that the amount of hydrogen charged during the production of the propylene-based polymer was adjusted so as to be 5 g / 10 min, 2.7 g / 10 min, and 0.7 g / 10 min. To produce polypropylene. Table 2 shows the physical property evaluation results of the obtained polymer. Comparative Example 3 The MFR of the resulting propylene-based polymer was 3.2 g / 1.
A propylene-based polymer was produced in the same manner and under the same conditions as in Comparative Example 1, except that the amount of hydrogen charged during the production of the propylene-based polymer was adjusted so as to be 0 minutes. Table 2 shows the physical property evaluation results of the obtained polymer. Example 6 (1) Preparation of solid catalyst component before improvement 47.6 g (50%) of anhydrous magnesium chloride under a nitrogen atmosphere
0 mmol), 250 ml of decane and 234 ml (1.5 mol) of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to form a homogeneous solution. After that, 11.1 g (75 mmol) of phthalic anhydride was added to the solution. Stirring was further performed at 1 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution. After cooling the obtained homogeneous solution to room temperature,
2.0 liters of titanium tetrachloride (1
8 mol) over 1 hour. After completion of the dropwise addition, the temperature of the mixed solution was raised to 110 ° C. over 4 hours,
When the temperature reaches 110 ° C., diisobutyl phthalate 2
6.8 ml (125 mmol) were added, and the mixture was stirred and reacted at 110 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected by hot filtration. After that, 2.0 liters (18 mol) of titanium tetrachloride was suspended in the reaction product, and reacted at 110 ° C. for 2 hours. After completion of the reaction, the solid portion was collected again by filtration under hot conditions, and washed seven times with 2.0 liters of decane at 110 ° C. and three times with 2.0 liters of hexane at room temperature to obtain a solid catalyst component. Table 1 shows the results of the catalyst analysis.

(2) TiCl ₄ [C ₆ H ₄ (COO ⁱ C
Preparation of ₄ H ₉ ) ₂ ] Same as (2) of Example 2. (3) Preparation of improved olefin polymerization catalyst component 40 g of the solid catalyst component obtained in the above (1) was dissolved in toluene 6
Of the Ti obtained in the above (2) at 90 ° C.
10.3 g of Cl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ]
(22 mmol) for 1 hour. After the loading was completed, the solid portion was collected by hot filtration, and toluene (600 ml) was collected.
And 20 ml (180 mmol) of titanium tetrachloride.
The mixture was washed with stirring at 0 ° C. for 1 hour, and a solid portion was collected by hot filtration. Thereafter, the reaction product was washed 5 times with 1.0 liter of toluene at 90 ° C. and 3 times with 1.0 liter of hexane at room temperature. Thus, an improved olefin polymerization catalyst component was obtained. Table 1 shows the results of the catalyst analysis.

(4) Preliminary polymerization Under a nitrogen atmosphere, 500 ml of n-heptane, 6.0 g (0.053 mmol) of triethylaluminum, and 4.15 g (0.017 mmol) of diphenyldimethoxysilane were placed in an autoclave having a content volume of 3 liters. And Example 2 above
10 g of the improved olefin polymerization catalyst component obtained in (3)
And stirred for 5 minutes in a temperature range of 0 to 5 ° C. Next, propylene was fed into the autoclave so that 10 g of propylene was polymerized per 1 g of the improved olefin polymerization catalyst component, and prepolymerized for 1 hour in a temperature range of 0 to 5 ° C. The obtained pre-polymerized solid catalyst component was composed of n-heptane 5
Washing was performed three times with 00 ml, and used for the production of the following propylene-based polymer.

(5) Polymerization of propylene Under a nitrogen atmosphere, 2.0 g of the prepolymerized solid catalyst component prepared in the above manner and 11.4 g of triethylaluminum (10 g) were placed in a 60-liter autoclave with a stirrer.
0 mmol), 7.32 g of diphenyldimethoxysilane (3
0 mmol), and then hydrogen was charged to 18 kg of propylene and 5300 mol ppm based on propylene.
The temperature was raised to 0 ° C., and polymerization was performed for 1 hour. One hour later,
Unreacted propylene was removed to terminate the polymerization. The polymerization activity was 22.0 kg / g-solid catalyst component. The MFR of the obtained polypropylene was 14.5 g / 10 minutes. Table 2 shows the evaluation results of the physical properties of the polymer. Example 7 (1) Preparation of solid catalyst component before improvement 50.0 g (440 mmol) of diethoxymagnesium and 15.3 g (55 mmol) of di-n-butyl phthalate were refluxed in 250 ml of methylene chloride under a nitrogen atmosphere for 1 hour. Stirred. The obtained suspension was mixed with 2.0 liters of titanium tetrachloride (1 liter).
8 mol), heated to 110 ° C. and reacted for 2 hours. After completion of the reaction, the precipitated solid was treated with titanium tetrachloride 2.0
The reaction was carried out at 110 ° C. for 2 hours with liter (18 mol).
After completion of the reaction, 2.0 liters of n-decane at 110 ° C.
It was washed twice and washed with 2.0 liters of n-hexane at room temperature until no chloride ion was detected. Drying under reduced pressure at 40 ° C. gave the desired solid catalyst component. Table 1 shows the results of the catalyst analysis.

(2) TiCl ₄ [C ₆ H ₄ (COO ⁱ C
Preparation of ₄ H ₉ ) ₂ ] Same as (2) of Example 2. (3) Preparation of improved olefin polymerization catalyst component 40 g of the solid catalyst component obtained in (1) above
Of the Ti obtained in the above (2) at 90 ° C.
10.3 g of Cl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ]
(22 mmol) for 1 hour. After the loading was completed, the solid portion was collected by hot filtration, and toluene (600 ml) was collected.
And 20 ml (180 mmol) of titanium tetrachloride.
The mixture was washed with stirring at 0 ° C. for 1 hour, and a solid portion was collected by hot filtration. Thereafter, the reaction product was washed 5 times with 1.0 liter of toluene at 90 ° C. and 3 times with 1.0 liter of hexane at room temperature. . Table I shows the results of the catalyst analysis.

[0091]

[Table 2]

The prepolymerization and propylene polymerization were all carried out in the same manner and under the same conditions as in Example 6. As a result, the polymerization activity was 21.1 kg / g-solid catalyst component. The MFR of the obtained polypropylene was 16.3 g / 10 minutes. Table II shows the results of evaluating the physical properties of the polymer.

[0093]

[Table 3]

[0094]

[Table 4]

Example 8 In the same manner as in Example 2, propylene was polymerized in an autoclave having an internal volume of 60 liters and equipped with a stirrer (first stage), and then liquid propylene was removed.
Copolymerization was conducted for 40 minutes at a supply rate of 0/60 (molar ratio) of a mixed gas of 2.2 Nm ³ / hour and hydrogen of 20 NL / hour (second stage). After 40 minutes, the unreacted gas was removed to terminate the polymerization. As a result, 8.0 kg of a propylene-ethylene-block copolymer was obtained. ^The ethylene content by ＣC-NMR was 9.7% by weight and the MFR was 17.8 g / 10 minutes. The results of evaluation of the physical properties of the polymer are shown in Table III. In addition,
XI, IP and N in Table III are those of homopolypropylene extracted after the completion of the first-stage polymerization. Comparative Example 4 Propylene was polymerized in a 60-liter autoclave equipped with a stirrer in the same manner as in Comparative Example 1, and then liquid propylene was removed. Ethylene / propylene = 40/60 at 65 ° C.
(Molar ratio) mixed gas 2.2 Nm ³ / hour, hydrogen 20 NL /
Feeding was performed for 40 minutes at a feed rate of time. After 40 minutes, the unreacted gas was removed to terminate the polymerization. As a result, 7.7kg
Of propylene-ethylene-block copolymer was obtained. ^The ethylene content by ＣC-NMR was 9.6% by weight, and the MFR was 18.3 g / 10 minutes. The results of evaluation of the physical properties of the polymer are shown in Table III. XI, I in Table III
P and N are those of homopolypropylene extracted after the completion of the first-stage polymerization.

[0096]

[Table 5]

[0097]

[Table 6]

Examples 9 and 10 and Comparative Example 5 As an example of the propylene polymer composition, 0.05% by weight of di-t-butyl-p-cresol, pentaerythrityl -0.15% by weight of tetrakis [3- (3,5-dibutyl-4-hydroxyphenyl)] propionate and 0.10% by weight of calcium stearate were blended into a mixture of 20
The mixture was compounded using a 1 liter super mixer (SMV20 type), and pelletized using a 30 mmφ twin screw extruder AS30 manufactured by Nakatani Machinery Co., Ltd. In addition, the following were used as nucleating agents, and the compounding amounts were appropriately changed. (Types of nucleating agent) Nucleating agent A: aluminum pt-butyl benzoate Nucleating agent B: 2,2-methylenebis (4,6-di-phosphate)
tert-Butylphenyl) sodium A composition obtained by mixing the above nucleating agent and the like with the polypropylene obtained in Example 2 (Examples 9 and 10) and a composition obtained by mixing the nucleating agent with the polypropylene obtained in Comparative Example 1 Table 4 shows the physical property evaluation results of the product (Comparative Example 5). Example 11 and Comparative Example 6 Table IV shows the physical property evaluation results of the composition obtained by blending the propylene-ethylene-block copolymer obtained in Example 8 and Comparative Example 4 with a nucleating agent in the same manner as in Example 9. Shown in

[0099]

[Table 7]

[0100]

[Table 8]

[0101]

According to the present invention, a propylene-based polymer and composition suitable for automobiles, home electric appliances, and packaging, which are more excellent in physical properties such as rigidity, surface hardness, heat resistance, and steam barrier property than conventional ones, can be obtained. Because it can be manufactured, it has industrially sufficient value.

[Brief description of the drawings]

FIG. 1 shows ¹³ C in the methyl region of homopolypropylene.
It is an example of a -NMR spectrum figure.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hirotoshi Takahashi Oita Prefecture, Oita City, Nakanosu No. 2 Showa Denko Co., Ltd. Oita Research Laboratories (72) Inventor Kazuharu Ito Oita City, Oita City Oita No. 2 Showa Denko Oita Research Laboratories

Claims (9)

[Claims] 1. A solid catalyst component for polymerization comprising (i) a magnesium compound, a titanium compound, a halogen compound and a first electron-donating compound as essential components, and a first electron donor supported on the solid catalyst component. A solid catalyst component for polymerization wherein the molar ratio (D / T) of the reactive compound (D) to titanium (T) is D / T ≧ 1, (ii) an organoaluminum compound, and (iii) a second electron donating compound A method for producing a propylene-based polymer, comprising a step of polymerizing propylene using a polymerization catalyst containing: 2. The method according to claim 1, wherein the solid catalyst component satisfying D / T ≧ 1.5 is used. 3. An insoluble part of xylene extracted at 25 ° C. (X
(I) is 99.0% by weight or more, (2) isotactic pentad fraction (IP) by ¹³ C nuclear magnetic resonance spectrum
98.0% or more, (3) average isotactic chain length (N) is 500 or more, and (4) average chain length (N _f ) of each fraction by column fractionation of xylene-insoluble portion.
2. A propylene-based polymer having a total of 10% by weight or more of the total of fractions having a value of 800 or more is produced.
The manufacturing method as described. 4. A method according to claim 1, wherein a magnesium compound, a titanium compound, a halogen compound and a first electron-donating compound are essential components, and the first electron-donating compound (D) and titanium (T) supported on a solid catalyst component are mixed. When the molar ratio (D / T) is D / T ≧
1. A solid catalyst component for propylene polymerization which is 1. 5. The solid catalyst component according to claim 4, wherein D / T ≧ 1.5. 6. A solid catalyst component for polymerization comprising a magnesium compound, a titanium compound, a halogen compound and a first electron donating compound as essential components, wherein the supported first electron donating compound (D) and titanium ( T) is (D /
T) forming a solid catalyst component for polymerization which is _i , treating the solid catalyst component for polymerization, and the supported first electron-donating compound (D: titanium (T) has a molar ratio of (D /
T) _m was improved to a solid catalyst component for polymerization.
/ T) _m / (D / T) _i > 1, a process for producing a solid catalyst component for propylene polymerization, comprising the step of: 7. The method of claim 6, wherein (D / T) _m / (D / T) _i ≧ 2. 8. The method of claim 6, wherein the treatment of the solid catalyst component comprises a step of treating the solid catalyst component with a first electron-donating compound, supporting the solid catalyst component, treating the solid catalyst component with a halogen-containing compound, cleaning, and further washing with a hydrocarbon. the method of. 9. The treatment of the solid catalyst component comprises the step of converting the solid catalyst component into a compound represented by the general formula TiX _a · Y _b (where X is Cl, Br
And / or I represents a halogen atom, a represents 3 or 4, Y represents a first electron donating compound, and 0 <b ≦ 3. 7. The method according to claim 6, further comprising a step of washing with a halogen-containing compound after treating with a titanium compound represented by the formula (1), and further washing with a hydrocarbon.