JPH059226A - Polypropylene resin and its composition - Google Patents

Abstract

PURPOSE:To provide a polypropylene resin having high rigidity, heat resistance and melt tension and being inexpensive and usable as the material of plastic sheets or films. CONSTITUTION:A polyproplene 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 peak in climbing fractionation positioned at 117.0 deg.C or above (Tmax) of 0.01-3.0g/10min and satisfying the relationship: T>=-5.2 log MI+3.0 (wherein T is the melt tension at 230 deg.C, and MI is the melt index).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inexpensive polypropylene resin having high rigidity, high heat resistance and high melt tension, and a composition thereof.

[0002]

2. Description of the Related Art Conventionally, polypropylene resins, especially melt index (M
Polypropylene resin having a low I) is used as a plastic material such as a sheet and a film. Here, in the field of extrusion molding of low-MI grade polypropylene resin sheets and films, means for improving the rigidity and heat resistance of polypropylene resins have been desired. Also,
Conventionally, multistage polymerization has been indispensable in order to obtain sufficient melt tension in the low MI grade region, and improvement in productivity and cost has been desired.

On the other hand, it has been proposed to improve the pentad fraction and boiling heptane extraction rate (II) by NMR measurement in order to improve the rigidity and heat resistance of polypropylene resin (Japanese Patent Publication No. 30605/1993). No.), these pentad fractions and boiling heptane extraction rate (II) can be used as an approximate guideline for high rigidity and high heat resistance, but the effect alone is not sufficient.

Further, the prior arts (Japanese Patent Laid-Open Nos. 63-284252 and 63-317505), which are premised on multi-stage polymerization, are not only restricted in terms of process and cost, but also under different conditions. The combination of the polymerizations in 1) has the disadvantage of broadening the stereoregularity and the distribution of the molecular weight. In other words,
Stereoregularity as an average value, even if the molecular weight is good,
A small amount of low stereoregularity and low molecular weight components had to be incorporated, resulting in quality problems (especially in the gas phase polymerization method). The present invention has been made in view of the above circumstances, and an object thereof is to provide an inexpensive polypropylene resin having extremely high rigidity, heat resistance, and melt tension.

[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. Then, the pentad fraction, the value of the main elution peak position and the half width in the temperature rising fractionation method, the melt index, the polypropylene resin in which each value of the relationship between the melt tension and the melt index is within a certain range,
The present invention has been accomplished by finding that it has extremely high rigidity and heat resistance, and is also excellent in moldability and drawdown resistance.

Therefore, the present invention has the following characteristics:
Provided is a polypropylene resin comprising a propylene homopolymer having 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
The temperature at 17.0 ° C. or higher and the half width (σ) of the peak is less than 4.0 degrees. The melt index is 0.01 g / 10 minutes or more, 3.
The relationship between the melt tension (T) and MI measured at 230 ° C. for 0 g / 10 minutes or less is T ≧ −5.2 logMI + 3.0, and the present invention includes at least the above-mentioned propylene resin, and if necessary, EPR, EPDM. Provided is a polypropylene resin composition containing other resin such as 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 117.0 ° C. or higher, preferably 117.5 ° C. or higher, more preferably 11
The temperature is 8.0 ° C or higher. The full width at half maximum (σ) of the main elution peak is less than 4.0 degrees, preferably less than 3.8 degrees, and more preferably less than 3.4 degrees. If the position (Tmax) of the main elution peak is less than 117.0 ° 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 4.0 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 3.0 g / 1.
It is 0 minutes, preferably 0.1 to 3.0 g / 10 minutes. If the melt index is less than 0.01 g / 10 minutes, the rigidity and heat resistance will be low, and if it exceeds 3.0 g / 10 minutes, the melt tension will be decreased, such being undesirable.

Melt Tension In the polypropylene resin of the present invention, it is necessary that the value of melt tension (T) measured at 230 ° C. and the value of MI have the relationship represented by the following formula. T ≧ −5.2 log MI + 3.0 If the value of melt tension (T) is smaller than −5.2 log MI + 3.0, drawdown becomes large at the time of molding a sheet or blown product, 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 present applicant. . The polymerization catalyst 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 1 mol of metal magnesium. 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 metallic magnesium 1
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 of 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 above solid catalyst component (A) include, for example, the general formula TiX ¹ n (OR ¹ ) _4-n (wherein X ¹ is a halogen atom, especially 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 above 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 organic metal 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. In this case, the polypropylene of the present invention is preferably produced by substantially one-step polymerization, whereby good quality can be obtained and the production can be performed at low cost. The polypropylene powder thus obtained is nearly spherical and has a sharp particle size distribution. That is, the above-mentioned 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-mentioned polypropylene of the present invention, and may optionally contain EPR, EPDM, polyethylene, EBR, polybutene-1 and the like. 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.

[0038]

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: 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: 500 ml) sufficiently replaced with nitrogen gas, 16 g of the above 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 of propylene was carried out in the same manner as in Example 1 except that 0.3 mmol of cyclohexylmethyldimethoxysilane was used in place 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 performed in the same manner as in Example 1 except that the content was increased to Kg / cm ² G to obtain a propylene homopolymer.

Comparative Example 1 5 liters of purified heptane was put into a stainless steel autoclave (internal volume 10 liters), 5 ml of diethylaluminum chloride (DEAC) and 0.7 g of TiCl ₃ catalyst (Type 01 made by Solvay Co., Ltd.) were successively put in.
After introducing a predetermined amount of hydrogen and propylene and polymerizing at 70 ° C. and a total pressure of 8.0 Kg / cm ² for 90 minutes, the reaction gas is purged from the system. Then, n-butyl alcohol 50
After adding ml and heating and stirring at the same temperature for 30 minutes, the solid product was separated by filtration and dried under reduced pressure to obtain a propylene homopolymer.

Comparative Example 2 (1) Preparation of solid catalyst component Anhydrous magnesium chloride 30 g, n-heptane 150 ml
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, and again 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 (3) using the obtained solid catalyst component to obtain propylene powder.

Comparative Example 3 (1) Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Comparative Example 2. (2) Polymerization of propylene Preparative polymerization was carried out in the same manner as in Example 1, except that first, the polymerization was carried out with a hydrogen / propylene composition such that the intrinsic viscosity [η] = 5.0, and then all the reaction gases in the system were After purging, and then adjusting the reaction gas composition such that [η] = 1.0 so that the reaction amount ratio of the first stage / the second stage is 55% / 45%, polymerization is carried out again, and the final propylene homopolymer is obtained. Got

Comparative Example 4 (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 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 4 liters of purified heptane was placed in a stainless steel autoclave (internal volume: 10 liters), 0.4 g of diethylaluminum chloride (DEAC), 0.4 g of the prepolymerized catalyst, and 0.4 g of methyl P-toluate. After adding 44 g (manufactured by Inoue Fragrance Co., Ltd.), as in Comparative Example 3, the intrinsic viscosities [η] = 5.0 and [η] = 1.0 were 55% and 4 respectively.
Polymerization was carried out in two steps so that the concentration became 5%. 50 ml of n-butyl alcohol in the obtained polypropylene slurry
Was added, and the mixture was heated and stirred at 70 ° C. for 30 minutes, filtered,
It was dried under reduced pressure to obtain a propylene homopolymer.

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, melt index (MI) (g / 10 minutes), and melt tension were determined based on the following measurement methods and measurement conditions, respectively.
The results are shown in Table 1.

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 in 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. Melt tension Using a melt tension tester (manufactured by Toyo Seiki Co., Ltd.), the sample is melted at a melting temperature of 230 ° C. and a nozzle (pore diameter:
2.10mm, Length: 8.00mm, Cylinder inner diameter 9.55mm) From constant speed (Piston descending speed: 10
mm / min), and the stress generated when the molten strand extruded through the load cell is taken up by a roller (outer diameter: 5.0 cm) rotating at a constant speed (20 rpm) to measure the melt tension ( g) was determined.

Further, 0.1% of phenolic antioxidant and 0.1% of calcium stearate were added to the obtained resin and pelletized with 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 ) and heat distortion temperature (deflection temperature under load) (HDT)
(° C). 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. 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 .

[0056]

[Table 1]

[0057]

As described above, the polypropylene resin of the present invention and the composition thereof have extremely high rigidity, heat resistance and melt tension, and are advantageous in terms of cost.

[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 (3)

[Claims] 1. 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
The temperature at 17.0 ° C. or higher and the half width (σ) of the peak is less than 4.0 degrees. The melt index is 0.01 g / 10 minutes or more, 3.
The relationship between the melt tension (T) and MI measured at 230 ° C. for 0 g / 10 minutes or less is T ≧ −5.2 logMI + 3.0. 2. The polypropylene resin according to claim 1, wherein the polymerization of the propylene homopolymer is carried out in substantially one step. 3. A polypropylene-based resin composition comprising the polypropylene resin according to claim 1 or 2.