JPH059225A - Polypropylene resin and its compositon - Google Patents

Abstract

PURPOSE:To provide a polypropylene resin which has high rigidity and heat resistance and can be used as such as an industrial material for automobile parts, household electric appliances, etc. CONSTITUTION:A polypropylene resin comprising a propylene homopolymer having an mmmm fraction of 96.0% or above in a pentad fraction as determined by <13>C NMR, a main elution peak in climbing temperature fractionation positioned at 118 deg.C or above, a half-width (sigma) of below 3.4 deg., and a melt index of 0.01g/10min-200g/10min.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin having high rigidity and high heat resistance, which can be used in various fields such as automobiles and home electric appliances.

[0002]

BACKGROUND OF THE INVENTION Polypropylene resin alone has insufficient rigidity and heat resistance. Therefore, as a fiber reinforced polypropylene resin filled with glass fiber or the like, or a filler filled with polypropylene resin, As a polypropylene resin with heat resistance, it is used in industrial materials such as various automobile parts (including interior materials) and home electric appliances.

On the other hand, in order to improve the rigidity and heat resistance of the polypropylene resin, a technique for improving the pentad fraction (mmmm fraction) by NMR has been proposed (Japanese Patent Publication No. 2-33047), but NMR measurement has been proposed. By mm
The mm fraction is merely an indication of continuous 5 isotactic fractions, and is a rough guideline for achieving high rigidity, but the effect of such improvement is insufficient. In addition, this technique is expected to have some effect if it is limited to a process capable of separating atactic components, such as solvent polymerization, but in the case where all-produced polymers such as gas-phase polymerization become products. Is meaningless, and in fact its effect was not observed. Further, the improvement of only the pentad fraction by NMR is possible by, for example, radically changing the polymerization temperature or adding an additional electron donor, but it cannot be said to be advantageous in terms of cost because it significantly reduces the productivity.

As described above, in order to improve the rigidity and heat resistance of polypropylene, the pentad fraction in NMR has been conventionally improved, but the rigidity can be improved only by improving the pentad fraction. Further, the effect of improving heat resistance is insufficient, and means for further improving these properties have been desired. The present invention has been made in view of the above circumstances, and an object thereof is to provide a polypropylene resin which has extremely high rigidity and heat resistance and can be used as it is as an industrial material for various automobile parts, home electric appliances and the like.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that the position of the main elution peak and the half-value width of the peak in the temperature-raising fractionation method are the same as those of polypropylene resin. It was found that it affects rigidity and heat resistance. And, the pentad fraction, the value of the main elution peak position and half-value width in the temperature rising fractionation method, the polypropylene resin in which each value of the melt index is within a certain range, the crystallinity and melting temperature is high, extremely high rigidity and The present invention has been accomplished by finding that it has heat resistance.

Accordingly, the present invention provides a polypropylene resin comprising a propylene homopolymer having the following characteristics and: Mm in pentad fraction measured by ¹³ C-NMR
The mm fraction is 96.0% or more, and the position (Tmax) of the main elution peak in the temperature rising fractionation method is 1
18.0 ° C. or higher, and the peak half width (σ) is less than 3.4 degrees. Melt index is 0.01 g / 10 min or more, 20
0 g / 10 minutes or more Further, the present invention provides a polypropylene resin composition containing at least the above-mentioned propylene resin, and optionally other resins such as EPR, EPDM and polyethylene.

The present invention will be described in more detail below.
First, each characteristic will be described in detail. Pentad Fraction (mmmm Fraction) The mmmm fraction referred to in the present invention is a value obtained by measurement by ¹³ C-NMR. The polypropylene of the present invention has a pentad fraction measured by ¹³ C-NMR of 96.0.
% Or more, preferably 97.0% or more, more preferably,
It is 97.5% or more. The value of the pentad fraction is 96.0
If it is less than%, the rigidity and heat resistance are insufficient.

Main elution peak position and half-value width of peak by the temperature rising fractionation method. These values are obtained by introducing the sample solution into the column, adsorbing the sample to the packing material, and then increasing the temperature of the column. ,
It can be measured by detecting the concentration of polymer eluted at each temperature. Here, the main elution peak position (Tm
The ax) and the peak half width (σ) are values defined by the analysis chart shown in FIG. 1. That is, Tmax
Is the peak position (temperature) when the largest peak appears, and σ is the peak width at a position half the height of the peak. Since the stereoregularity of the polymer depends on the elution temperature, the stereoregularity distribution of the polymer can be known by determining the relationship between the elution temperature and the polymer concentration by the temperature rising fractionation method.

The polypropylene of the present invention has a main elution peak (Tmax) measured by the temperature rising fractionation method of 118.0 ° C. or higher, preferably 118.5 ° C. or higher, more preferably 11
It is 9.0 ° C or higher. The full width at half maximum (σ) of the main elution peak is less than 3.4 degrees, preferably less than 3.1 degrees, and more preferably less than 3.0 degrees. If the position of the main elution peak (Tmax) is less than 118.0 ° C, the crystallinity decreases, and the rigidity and heat resistance decrease. Further, if the full width at half maximum (σ) of the main elution peak is 3.4 degrees or more, the rigidity and heat resistance are also insufficient.

Melt Index (MI) The melt index referred to in the present invention is JIS K721.
It is a value measured according to 0. The polypropylene of the present invention has a melt index of 0.01 to 200 g / 1.
It is 0 minutes, preferably 0.1 to 200 g / 10 minutes, and more preferably 1.0 to 150 g / 10 minutes. If the melt index is less than 0.01 g / 10 min, the rigidity and heat resistance will be low, and if it exceeds 200 g / 10 min, low molecular weight components will be produced, which is not preferable.

The method for producing the propylene resin of the present invention having the above characteristics is not particularly limited, but it is preferable to use a polymerization catalyst capable of exhibiting high polymerization activity and stereoregularity. Examples of such a polymerization catalyst and a method for producing a polyolefin using the polymerization catalyst include a polymerization catalyst and a production method disclosed in Japanese Patent Application No. 2-413883 previously filed by the applicant of the present application. . The catalyst for polymerization disclosed in Japanese Patent Application No. 2-413883 is characterized by using a solid product (a) obtained by reacting magnesium metal, alcohol and a specific amount of halogen as a carrier. And such a solid product (a) and a titanium compound (b),
Polymerization is carried out using a solid catalyst component (A) obtained by using an electron donating compound (c), an organometallic compound (B), and optionally an electron donating compound (C). .

The solid product (a) is obtained from magnesium metal, alcohol, halogen and / or halogen-containing compound. In this case, the shape of metallic magnesium is not particularly limited. Therefore, it is possible to use metallic magnesium having an arbitrary particle diameter, for example, granular, ribbon-shaped or powdered metallic magnesium. The surface state of the metallic magnesium is not particularly limited, but it is preferable that the surface of the metallic magnesium is not coated with magnesium oxide.

Although any alcohol can be used, it is preferable to use a lower alcohol having 1 to 6 carbon atoms. In particular, the use of ethanol is preferable because a solid product that significantly improves the expression of catalytic performance can be obtained. The purity and the water content of the alcohol are not limited, but when an alcohol having a high water content is used, magnesium hydroxide [Mg (OH) ₂ ] is produced on the surface of magnesium metal, so that the water content is 1% or less, particularly 2000 ppm.
It is preferable to use the following alcohols. Furthermore, in order to obtain a solid product (a) having a better morphology, the smaller the water content, the more preferable, and generally 200 ppm or less is desirable.

The type of halogen is not particularly limited, but chlorine, bromine or iodine, especially iodine is preferably used. The kind of the halogen-containing compound is not limited, and any compound containing a halogen atom in its chemical formula can be used. In this case, the type of halogen atom is not particularly limited, but chlorine, bromine or iodine is preferable. Further, among the halogen-containing compounds, halogen-containing metal compounds are particularly preferable. As the halogen-containing compound, specifically, MgCl ₂ , MgI ₂ , M
g (OEt) Cl, Mg (OEt) I, MgBr ₂ , C
ACl ₂ , NaCl, KBr, etc. can be preferably used. Of these, MgCl ₂ and MgI ₂ are particularly preferable. These states, shapes, particle sizes and the like are not particularly limited and may be arbitrary, and for example, they can be used in the form of a solution in an alcohol solvent (for example, ethanol).

The amount of alcohol is not limited, but it is preferably 2 to 100 mol, and particularly preferably 5 to 50 mol per mol of magnesium metal. If the amount of alcohol is too large, the yield of the solid product (a) having a good morphology may decrease, and if it is too small, stirring in the reaction tank may not be smoothly performed. However, the molar ratio is not limited.

The amount of halogen used is 1 magnesium metal.
The amount of gram atom is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, and more preferably 0.001 gram atom or more. The halogen-containing compound has a halogen atom in the halogen-containing compound of 0.0001 gram atom or more, preferably 0.0005 gram atom or more, based on 1 gram atom of metallic magnesium.
More preferably, it is used in an amount of 0.001 gram atom or more. If the amount is less than 0.0001 gram atom, there is no great difference from the amount of halogen used as the reaction initiator, and the pulverizing and classifying treatment of the solid product is indispensable to obtain the desired particle size.

Each of the halogen and the halogen-containing compound may be used alone or in combination of two or more. Further, halogen and a halogen-containing compound may be used in combination. When halogen and a halogen-containing compound are used in combination, the total amount of halogen atoms is 0.0001 gram atom or more per 1 gram atom of metallic magnesium.
The amount is preferably 0.0005 gram atom or more, and more preferably 0.001 gram atom or more. The upper limit of the amount of halogen and / or halogen-containing compound used is not particularly limited and may be appropriately selected within a range in which the desired solid product is obtained. Generally, the amount of all halogen atoms is 1 g of magnesium metal. It is preferably less than 0.06 gram atom per atom. In this case, halogen and /
Alternatively, the particle size of the solid product can be freely controlled by appropriately selecting the amount of the halogen-containing compound used.

The reaction itself between the magnesium metal, the alcohol, the halogen and / or the halogen-containing compound can be carried out in the same manner as a known method. For example, metallic magnesium, an alcohol, a halogen and / or a halogen-containing compound are reacted under reflux (about 79 ° C.) until generation of hydrogen gas is no longer recognized (usually about 20 to 30 hours) to produce a solid. It is a way to get things. Specifically, for example, when iodine is used as the halogen, a method in which solid iodine is introduced into metallic magnesium and alcohol, and then heated and refluxed, metallic alcohol is added after the alcohol solution of iodine is dropped into the alcohol and heated. And the like, and a method of dropping an alcohol solution of iodine while heating the magnesium metal or alcohol solution. Both methods are preferably carried out under an inert gas (for example, nitrogen gas or argon gas) atmosphere, optionally using an inert organic solvent (for example, saturated hydrocarbon such as n-hexane).

Regarding the addition of magnesium metal, alcohol, halogen and / or halogen-containing compound, it is not necessary to add the whole amount to the reaction tank from the beginning, and it may be added in a divided manner. A particularly preferable form is a method in which the entire amount of alcohol is charged from the beginning, and metallic magnesium is charged in several times. If you do this,
It is possible to prevent the generation of a large amount of hydrogen gas temporarily, which is highly desirable from the viewpoint of safety. Also, the reaction tank can be downsized. Further, it becomes possible to prevent the entrainment of alcohol, halogen and / or halogen-containing compound caused by the temporary large generation of hydrogen gas. The number of divisions may be determined in consideration of the scale of the reaction tank,
Although not particularly limited, it is usually 5 to 10 in consideration of complexity of operation.
Times are preferred.

It goes without saying that the reaction itself may be either batch type or continuous type. Furthermore, as a modified method, a small amount of metallic magnesium is first added to the alcohol that has been entirely added from the beginning, the product produced by the reaction is separated and removed in another tank, and then a small amount of metallic magnesium is added again. It is also possible to repeat. When the solid product (a) thus obtained is used for the next synthesis of the solid catalyst component, a dried product may be used, or a product washed with an inert solvent such as heptane after filtration may be used. Good. In any case, the obtained solid product (a) can be used in the following steps without pulverization or classification operation for adjusting the particle size distribution.

Further, the solid product (a) is close to spherical and has a sharp particle size distribution. Furthermore, even if each particle is taken, the variation in sphericity is very small.
In this case, the sphericity (S) represented by the following formula (1) is less than 1.60, particularly less than 1.40, and the particle size distribution index (P) represented by the following formula (2) is 5.0. It is preferably less than 4.0, particularly less than 4.0. S = (E1 / E2) ² (1) (where E1 is the contour length of the projected particle and E2 is the circumference of a circle equal to the projected area of the particle.) P = D90 / D10 ... (2) (Here, D90 means a particle size corresponding to a weight cumulative fraction of 90%. That is, the weight sum of the particle groups smaller than the particle size represented by D90 is 90% of the total weight of all particles. (The same applies to D10.)

Examples of the titanium compound (b) in the solid catalyst component (A) include, for example, the general formula TiX ¹ n (OR ¹ ) _4-n (wherein, X ¹ is a halogen atom, particularly a chlorine atom, and R ¹
Is a hydrocarbon group having 1 to 10 carbon atoms, in particular a linear or branched alkyl group, and when a plurality of groups R ¹ are present, they may be the same or different from each other. n is 0-4
Is an integer. ) And titanium compounds. Specifically, Ti (O-i-C 3 H 7) 4, Ti (O
_{-C 4 H 9) 4, TiCl} (O-C 2 H 5) 3, TiCl (O
_{-I-C 3 H 7) 3} , TiCl (O-C 4 H 9) 3, TiCl
_{2 (O-C 4 H 9} ) 2, TiCl 2 (O-i-C 3 H 7) 2, T
Examples thereof include iCl ₄ .

In the solid catalyst component (A), any electron donating compound (c) can be used, if necessary. The electron donating compound (c) is usually an organic compound containing oxygen, nitrogen, phosphorus or sulfur. Specifically, amines, amides, ketones, nitriles, phosphines, phosmylamides, esters, ethers, thioethers, alcohols, thioesters, acid anhydrides, acid halides, aldehydes, Examples thereof include organic acids and organic silicon compounds having a Si—O—C bond, and more specific examples include the following.

Aromatic carboxylic acids such as benzoic acid, p
-Oxybenzoic acid; acid anhydrides such as succinic anhydride,
Benzoic anhydride, p-toluic anhydride; C3 to C1
5 ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone; aldehydes having 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, benzalded, naphthaldehyde; 2 carbon atoms ~ 18 esters, for example:
Methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, Ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluyl. Methyl acid, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate;

Aromatic dicarboxylic acid mono- and diesters such as phthalic acid monoesters and diesters are preferred, for example monomethyl phthalate, dimethyl phthalate, monomethyl terephthalate, dimethyl terephthalate, monoethyl phthalate, diethyl phthalate,
Monoethyl terephthalate, diethyl terephthalate,
Monopropyl phthalate, dipropyl phthalate, monopropyl terephthalate, dipropyl terephthalate,
Monobutyl phthalate, dibutyl phthalate, monobutyl terephthalate, dibutyl terephthalate, monoisobutyl phthalate, diisobutyl phthalate, monoamyl phthalate, diamyl phthalate, monoisoamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate, ethyl propyl phthalate;

Acid halides having 2 to 20 carbon atoms,
The acid portion (acyl group portion) of the acid halide is an aliphatic (including those having a ring such as alicyclic) carbon atoms of about 2 to 20, monobasic, dibasic or tribasic. A monovalent to trivalent acyl acid obtained by removing each hydroxyl group from an acid, or an aromatic (alkali-containing) having about 7 to 20 carbon atoms.
Also includes le-type and aralkyl-type. ) Monovalent to trivalent acyl groups obtained by removing each hydroxyl group from a monobasic, dibasic or tribasic acid of the system are preferred. The halogen atom in the acid halide is preferably a chlorine atom, a bromine atom, etc., and particularly preferably a chlorine atom.

Acid halides that can be preferably used include, for example, acetyl chloride, acetyl bromide, propionyl chloride, butyryl chloride, isobutyryl chloride, 2-methylpropionyl chloride,
Valeryl chloride, isovaleryl chloride, hexanoyl chloride, methylhexanoyl chloride, 2-ethylhexanoyl chloride, octanoyl chloride, decanoyl chloride, undecanoyl chloride, hexadecanoyl chloride, octadecanoyl chloride, benzylcarbonyl Chloride, cyclohexane carbonyl chloride, malonyl dichloride, succinyl dichloride, pentane dioil dichloride, hexane dioil dichloride, cyclohexane dicarbonyl dichloride, benzoyl chloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride. , Benzene-1,2,4-
Tricarbonyl trichloride etc. can be mentioned. Among these, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride and the like are preferable, and phthaloyl chloride is particularly preferable. These acid halides may be used alone or in combination of two or more.

Ethers having 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether; acid amides such as acetic acid amide, benzoic acid Acid amide, toluic acid amide; amines such as tributylamine, N, N′-dimethylpiperazine, tribenzylamine, aniline, pyridine,
Pyroline, tetramethylethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolunitrile; Tetramethylurea, nitrobenzene, lithium butyrate;

Organosilicon compounds having a Si--O--C bond, such as trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, phenyltri. Methoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl Triisopropoxysilane,
Vinyltributoxysilane, isopropylcyclohexyldimethoxysilane, isobutylcyclohexyldimethoxysilane, tert-butylcyclohexyldimethoxysilane, isopropylcyclohexyldiethoxysilane,
Isobutylcyclohexyldiethoxysilane, tert-butylcyclohexyldiethoxysilane, methylcyclohexyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane , Dimethyltetraethoxydisiloxane, and the like. Among these, preferred are esters, ethers, ketones, acid anhydrides and the like.

The solid catalyst component (A) can be prepared by a known method using (a) a solid product, (b) a titanium compound and, if necessary, (c) an electron donating compound. . For example, it is preferable to contact the solid product (a) with the electron-donating compound (c) and then contact with the titanium compound (b). The conditions for bringing the electron donating compound (c) into contact with the solid product (a) are not particularly limited and may be appropriately determined depending on various circumstances. Usually, 0.01 to 10 moles of the electron-donating compound (c), preferably 0.1 to 1 mole of the solid product (a) in terms of magnesium atom.
05 to 5 moles may be added, and the catalytic reaction may be performed at 0 to 200 ° C. for 5 minutes to 10 hours, preferably at 30 to 150 ° C. for 30 minutes to 3 hours. Incidentally, an inert hydrocarbon such as pentane, hexane, heptane or octane can be added to this reaction system as a solvent.

The titanium compound (b) is added to the solid product (a) or the contact product of the solid product (a) and the electron-donating compound (c).
There are no particular restrictions on the conditions for contacting, but usually 1 to 50 mol, preferably 2 to 20 mol of the titanium compound (b) is added to 1 mol of magnesium in the product. The reaction is performed at ˜200 ° C. for 5 minutes to 10 hours, preferably at 30 to 150 ° C. for 30 minutes to 5 hours. The liquid titanium compound (for example, titanium tetrachloride) is used alone for the contact with the titanium compound (b), and the titanium compound other than the above is used for any inert hydrocarbon solvent (for example, hexane,
It can be carried out in a state of being dissolved in heptane, kerosene). In addition, prior to the contact between the solid product (a) and the titanium compound (b), and optionally the electron donating compound (c), for example, a halogenated hydrocarbon, a halogen-containing silicon compound, It is also possible to bring halogen gas, hydrogen chloride, hydrogen iodide, or the like into contact with the solid product (a).
After the reaction, it is preferable to wash the product with an inert hydrocarbon (for example, n-hexane or n-heptane).

As the organometallic compound (B), any organic compound containing a metal of Groups 1 to 3 of the periodic table can be preferably used. Examples of the metals of Groups 1 to 3 of the periodic table include lithium, sodium, potassium, zinc, cadmium, aluminum and the like, and aluminum is particularly preferable. Specific examples of the organometallic compound (B) include alkyllithium, for example,
Methyl lithium, ethyl lithium, propyl lithium or butyl lithium; dialkyl zincs such as dimethyl zinc, diethyl zinc, dipropyl zinc or dibutyl zinc.

As the organoaluminum compound,
In the general formula ^{_{AlR 2 m X 2 3-m}} ( wherein, R ² is an alkyl group, a cycloalkyl group or an aryl group having 1 to 10 carbon atoms, m is an integer of 1 to 3, X ² is a halogen Compounds represented by atoms such as chlorine or bromine are widely used. Specifically, trialkyl aluminum compounds such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum or trioctyl aluminum; or dialkyl aluminum monohalide compounds such as diethyl aluminum monochloride and dipropyl aluminum monochloride. Alternatively, dioctylaluminum monochloride and the like can be mentioned.

The electron donating compound (C) can be used in combination, if necessary. In this case, as the electron donating compound (C), the same one as the electron donating compound (c) used in the preparation of the solid catalyst component (A) can be used. At this time, the electron donating compound (C) is
It may be the same as or different from the electron-donating compound (c) used in the preparation of the solid catalyst component (A).

The polypropylene of the present invention can be produced using the above catalyst. The polymerization conditions are not particularly limited, and the same conditions as known methods can be used, for example, under a partial pressure of propylene higher than atmospheric pressure, at −80 ° C.
It can be carried out in the liquid phase or in the gas phase at a temperature of ˜ + 150 ° C., optionally in the presence of an inert hydrocarbon diluent. The polypropylene powder thus obtained is nearly spherical and has a sharp particle size distribution. That is,
The sphericity (S) is less than 1.60 and the particle size distribution index (P) is less than 5.0.

The polypropylene resin composition of the present invention contains at least the above polypropylene of the present invention, and may contain EPR, EPDM, polyethylene, EBR, polybutene-1 and the like, if necessary. Further, additives such as various stabilizers, pigments, dispersants and nucleating agents may be added to the polypropylene resin composition of the present invention as required.

[0037]

EXAMPLES Next, the present invention will be specifically shown by Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the following reagents were used in the following Examples and Comparative Examples. Metallic magnesium: Granular (average particle size 350 μm) Ethanol: Wako Pure Chemical Industries, Ltd., reagent special grade Iodine: Wako Pure Chemical Industries, Ltd., reagent special grade

Example 1 (1) Preparation of solid product (a) A glass reactor equipped with a stirrer (internal volume of about 6 liters) was sufficiently replaced with nitrogen gas, and about 2430 g of ethanol, 16 g of iodine and 160 g of magnesium metal were obtained. Was added, and the mixture was reacted with heating under reflux until the generation of hydrogen gas disappeared from the inside of the system under stirring, to obtain a solid reaction product. The reaction liquid containing this solid product was dried under reduced pressure to obtain a solid product (a). The resulting solid product (a) had a sphericity (S) of 1.20 and a particle size distribution index (P) of 1.8.

(2) Preparation of solid catalyst component (A) In a glass three-necked flask (internal volume of 500 ml) sufficiently replaced with nitrogen gas, 16 g of the solid product (a) (not crushed) and purified heptane 80 ml, 2.4 ml of silicon tetrachloride and 2.3 ml of diethyl phthalate were added. Maintaining the system temperature at 90 ° C, stirring titanium tetrachloride 7
After adding 7 ml and reacting at 110 ° C. for 2 hours, solid components were separated and washed with purified heptane at 80 ° C. Further, 122 ml of titanium tetrachloride was added, and the mixture was reacted at 110 ° C. for 2 hours and then thoroughly washed with purified heptane to obtain a solid catalyst component (A).

(3) Polymerization of Propylene 30 g of polypropylene powder was placed in an autoclave made of styrene steel (internal volume of about 5 liters), the system was sufficiently replaced with nitrogen gas, and then 2.0 mmol of triethylaluminum and diphenyldimethoxysilane were added. 0.5 mmol and 0.01 mmol of the solid catalyst component (A) in terms of titanium atom were added, and further hydrogen was 0.7 kg / cm.
² G and propylene 27.3 Kg / cm ² G were introduced, and polymerization was carried out at a total pressure of 28.0 Kg / cm ² G and 70 ° C. for 2 hours. A propylene homopolymer was obtained.

Example 2 (3) Polymerization was carried out in the same manner as in Example 1 except that 0.3 mmol of cyclohexylmethyldimethoxysilane was used instead of diphenyldimethoxysilane in the polymerization of propylene to obtain a propylene homopolymer. Obtained.

Example 3 (3) In the polymerization of propylene, the amount of hydrogen added was 2.0.
Polymerization was carried out in the same manner as in Example 1 except that the temperature was increased to Kg / cm ² G and the polymerization temperature was changed to 80 ° C. to obtain a propylene homopolymer.

Comparative Example 1 (1) Preparation of solid catalyst component In a glass reactor equipped with a stirrer, which was sufficiently replaced with nitrogen gas, 600 ml of purified n-heptane, 0.5 mol of diethylaluminum chloride and 1.2 mol of diisoamyl ether were added. It was charged and reacted at room temperature for 5 minutes. Titanium tetrachloride (4.0 mol) was placed in a separately prepared reactor,
Next, the above reaction solution was added dropwise over 180 minutes, reacted at room temperature for 80 minutes, further heated to 75 ° C., and then heated and stirred for 1 hour. After thoroughly washing the obtained solid product with purified heptane, 3 liters of n-heptane, 160 g of diisoamyl ether and 350 g of titanium tetrachloride were added, and the mixture was reacted at 65 ° C. for 1 hour, and further thoroughly washed with heptane, A solid catalyst component was obtained by drying under reduced pressure.

(2) Preparation of prepolymerization catalyst A stainless steel autoclave (internal volume: 10 liters) was charged with 5 liters of n-heptane, 14 g of diethylaluminum chloride and 10 g of the above solid catalyst component, and the total pressure of hydrogen was 3 Kg / cm ^2. After introducing so as to have G, propylene was introduced so as to have a total pressure of 8 Kg / cm ² and reacted for 5 minutes. Then, the system was degassed, the solid product in the reaction solution was filtered off, and dried under reduced pressure to obtain a prepolymerized catalyst.

(3) Polymerization of Propylene In a stainless steel polymerization vessel with an internal volume of 10 liters, which was replaced with nitrogen gas, with a turbine type stirring blade, 4.0 liters of n-hexane, then 0.4 g of diethylaluminum monochloride, the above prepolymerization was carried out. 0.4 g of a catalyst and 0.44 g of methyl p-toluate were charged, and 4.0 Nl of hydrogen was further added. Next, after raising the temperature to 70 ° C., propylene was supplied and the total pressure was raised to 10 Kg / cm ² G. 70
After continuing the polymerization for 4 hours while maintaining the temperature at 10 ° C and 10 Kg / cm ² G, 1.0 liter of methanol was supplied and the temperature was raised to 80 ° C. After 30 minutes, add 4.0 g of 20% caustic soda water and stir for 20 minutes.
After adding liter, residual propylene was discharged. After the water layer was extracted, 2.0 liters of pure water was added, and the mixture was washed with stirring water for 10 minutes. Extract the water layer and add polypropylene-
After extracting the n-hexane slurry, it was filtered and dried to obtain a polypropylene powder.

Comparative Example 2 (3) In the polymerization of propylene, the amount of hydrogen added was 4.4.
Polymerization was performed in the same manner as in Comparative Example 1 except that the content was increased to Nl to obtain polypropylene powder.

Comparative Example 3 (1) Preparation of solid catalyst component 30 g anhydrous magnesium chloride, 150 ml n-heptane
Further, 6 times mol of ethanol with respect to magnesium chloride was introduced into a glass reactor equipped with a stirrer, which was sufficiently replaced with nitrogen gas, and the mixture was heated and stirred for 2 hours under reflux conditions. Then, this reaction liquid was cooled to -20 ° C, and titanium tetrachloride 1500 m
It was fed under pressure to a glass reactor equipped with a stirrer and heated to room temperature with stirring, and then dibutyl phthalate 160 was added.
ml was added and the mixture was heated with stirring at 110 ° C. for 2 hours. The produced solid component was separated, further heated and stirred in 150 ml of titanium tetrachloride at 110 ° C. for 2 hours, and then sufficiently washed with purified n-heptane to obtain a solid catalyst component. (2) Polymerization of propylene Polymerization was carried out in the same manner as in Example 1 using the obtained solid catalyst component to obtain propylene powder.

Comparative Example 4 (2) Polymerization was carried out in the same manner as in Comparative Example 3 except that the polymerization temperature was changed to 60 ° C. in the polymerization of propylene to obtain polypropylene powder.

Pentad fraction (mmmm) of the polypropylene resins obtained in Examples 1 to 3 and Comparative Examples 1 to 4 above.
%), Main elution peak position (Tmax) by the temperature-raising fractionation method
(° C.), full width at half maximum (σ) (degree) of main elution peak, and melt index (MI) (g / 10 minutes) were determined based on the following measurement methods and measurement conditions, respectively. The results are shown in Table 1.
Shown in.

As a pentad fraction measuring instrument, JNM-EX400 ( ¹³
It was measured under the following conditions using a C nuclear resonance frequency of 100 MHz. Measurement mode: Scalar decoupling method Pulse width: 9.0 μs (45 °) Pulse repetition time: 4 s Accumulation number: 10,000 times Solvent: 1,2,4-Trichlorobenzene / deuterated benzene mixed solvent (90/10% by volume) Sample concentration: 200 mg / 3.0 ml Solvent measurement temperature: 130 ° C. In this case, the pentad fraction was determined by measuring the split peak in the methyl group region of the ¹³ C-NMR spectrum.
In addition, the attribution of the peak of the methyl group region is "Macromolecul
es, 13 (2), 267 (1980) (A. Zambelli et al.) ”.

Tmax and σ were measured under the following conditions. Solvent: Orthodichlorobenzene Flow rate: 2 ml / min Temperature rising rate: 20 ° C./hr Detector: Infrared detector for liquid chromatography Measured wave number: 3.41 μm Column: 1.07 cmφ × 30 cm Filler: Chromosolve P concentration: 7 0.5 mg / 20 ml Injection volume: 2 ml Column temperature distribution: Within ± 0.2 ° C In this case, the sample solution was introduced into the column under the conditions of 135 ° C and then cooled at 2 ° C / hr to use the polymer as the packing material. After adsorption and cooling to room temperature, the column temperature was raised under the above conditions, and the concentration of polymer eluted at each temperature was detected by an infrared detector. It was measured according to MI JIS K 7210.

Further, 0.1% of a phenolic antioxidant and 0.1% of calcium stearate were added to the obtained resin and pelletized by a 20 mm uniaxial granulator, followed by press plate molding to obtain physical properties. A sample for measurement was prepared and the physical properties were measured. The physical properties are measured by the tensile modulus (Kg /
cm ² ), yield stress (Kg / cm ² ), crystallization temperature (° C.) and melting temperature (° C.) by differential calorimetry thermometer (DSC)
And heat distortion temperature (deflection temperature under load) (HDT) (° C)
About. The results are shown in Table 1. The evaluation of each physical property was performed by the following methods.

Tensile elastic modulus was measured according to JIS-K7113. Yield point stress Measured according to JIS-K7113. Crystallization temperature After holding the pressed test piece at 220 ° C for 3 minutes, 10 ° C /
The crystallization peak when the temperature was lowered at min was examined. Melting temperature The melting peak when the temperature of the pressed test piece was raised from 50 ° C at 10 ° C / min was examined. It was measured according to HDT JIS-K7207. The measurement sample was used without annealing, and the bending stress applied to the sample was 4.6 Kg / cm @ 2.

[0054]

[Table 1]

[0055]

As described above, the polypropylene resin of the present invention and the composition thereof have high rigidity and heat resistance.

[Brief description of drawings]

FIG. 1 Main elution peak position (Tma
x) and the half-value width (σ) of the peak.

[Explanation of symbols]

Tmax ... Main elution peak position σ ... half width of peak

Claims (2)

[Claims] 1. A polypropylene resin comprising a propylene homopolymer having the following characteristics: Mm in pentad fraction measured by ¹³ C-NMR
The mm fraction is 96.0% or more, and the position (Tmax) of the main elution peak in the temperature rising fractionation method is 1
18.0 ° C. or higher, and the peak half width (σ) is less than 3.4 degrees. Melt index is 0.01 g / 10 min or more, 20
0g / 10 minutes or less 2. A polypropylene-based resin composition comprising the polypropylene resin according to claim 1.