JPH09165421A - Crystalline polypropylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crystalline polypropylene having excellent heat resistance by regulating the residual amount after extraction with boiling n-heptane to a specified value or higher, and bringing a specified relationship between the frequency determined from dynamic melt viscoelasticity and the melt flow rate. SOLUTION: A solid component obtained from metallic magnesium, a halohydrocarbon and an alkoxy compound is reacted with a halogen-containing alcohol, an electron-donating compound and a titanium compound to obtain a magnesium- containing solid. Next, an organoaluminum compound such as trialkylaluminum is mixed with an organosilicon compound such as t-butoxymethyldiethoxysilane in a solvent, the resultant mixture is fed into a reactor, and a hydrogen gas and propylene are injected into the reactor. The magnesium-containing solid is then fed into the reactor, and the reaction mixture is subjected to polymerization under heating. After the reaction, a crystalline PP having a melt flow rate(MFR) of below 5 as determined according to ASTM-D1238 and a content of the residue after extraction with boiling n-heptane of 90% or above and satisfying the relationship: log(ωp )<0.966.log(MFR)-0.436 (wherein ωp is the frequency determined from a dynamic melt viscoelasticity at 200 deg.C) is taken out from the reaction mixture.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crystalline polypropylene, and more particularly to a crystalline polypropylene having an excellent balance of rigidity, heat resistance and moldability, and particularly suitable for extrusion, sheet, blow molding and the like.

[0002]

TECHNICAL FIELD Polypropylene has excellent heat resistance, chemical resistance, and electrical properties, and further has good rigidity, tensile strength, optical characteristics, and processability. It is injection molded, film molded, sheet molded, blown, or blown. Used for molding, etc.
Polypropylene has a light specific gravity and is widely used in fields such as containers and packaging materials. However, depending on the application, these properties are not sufficiently satisfied, and the use is limited.

Among the above-mentioned performances, polypropylene is polystyrene, AB
It is inferior to S resin. Therefore, polypropylene cannot be used as a material for producing a molded product requiring rigidity and heat resistance, and the above-mentioned polystyrene or AB is used as a material for a molded product requiring rigidity and heat resistance.
When polypropylene is intentionally used instead of the S resin, a thick molded product must be formed in order to satisfy the above properties, which prevents the molded product from being thin and increases the cost of the molded product. That is, the application of polypropylene or polypropylene composition cannot be expanded. If polypropylene has excellent rigidity, chemical resistance, moldability, heat resistance, hardness, etc., such polypropylene can be used as an alternative to polystyrene or ABS resin, and its application can be expanded. . In addition, since it is possible to finish a thin molded product, resource saving and cost reduction can be expected. As a known technique for improving the melt tension, which is one of the indicators of the moldability of crystalline polypropylene, there is a method of mixing polyethylene, but this method has a drawback that the original transparency and rigidity of polypropylene are lowered.

As a known technique for improving the rigidity of crystalline polypropylene, an organic nucleating agent such as paratertiarybutyl benzoic acid aluminum salt or 1,3-2,4-dibenzylidene sorbitol is added. Although there is a method of molding, it has a drawback that the cost is high and it is not economical, and that the addition thereof greatly reduces gloss, impact strength, tensile elongation and the like. As another means of improving rigidity, talc,
There is a method of using various inorganic fillers such as calcium carbonate, mica, sulphate valueum, asbestos and calcium silicate, but in addition to impairing the lightness and transparency which are the characteristics of polypropylene, impact strength, gloss, tensile elongation, There are drawbacks such as reduced workability and insufficient improvement of melt tension. Therefore, in order to improve the rigidity, moldability, and heat resistance of polypropylene, it is necessary to develop polypropylene with high crystallinity, and attempts have been made to develop crystalline polypropylene by devising the polymerization catalyst and polymerization method. Although somewhat improved, it is still insufficient and moldability and heat resistance have not reached a satisfactory level.

[0005]

DISCLOSURE OF THE INVENTION The present invention has improved rigidity, heat resistance, and high hardness due to improved crystallinity, and has fatigue characteristics, wear resistance, dimensional stability, chemical resistance, and molding. Provided is a novel propylene polymer excellent in balance of properties and the like.

[0006]

As a result of intensive studies, the inventors of the present invention have found that the melt flow rate (MFR) of crystalline polypropylene and the frequency (ω _p ) obtained from the dynamic melt viscoelasticity at 200 ° C. Is a specific relationship, that is, the expression log (ω _p ) <0.996 · log (MFR) −0.
It was found that when the relation of 436 is satisfied, the balance of rigidity, heat resistance and moldability of the crystalline polypropylene becomes extremely good, and the first invention of the present application was completed. Further, although the crystalline polypropylene can be produced by various polymerization catalysts and polymerization means, the crystalline polypropylene can be easily produced by using the specific stereoregular polymerization catalyst previously invented by the present inventors. This led to the completion of the second invention of the present application.

SUMMARY OF THE INVENTION That is, the gist of the present invention is that the melt flow rate (MFR) measured according to ASTM-D1238 is MFR ≦.
5 and the residual amount (HI, wt%) after extraction with boiling n-heptane exceeds 90, and 20
Frequency ω _p and MFR obtained from dynamic melt viscoelasticity at 0 ℃
And log (ω _p ) <0.966 · log (MFR) −0.
436, which is a crystalline polypropylene, which satisfies the relationship of 436.

A polypropylene obtained by polymerizing propylene in the presence of a catalyst consisting of the following components (A) and (B), which is prepolymerized and / or
Alternatively, the crystalline polypropylene according to claim 1, which is obtained by using the following component (C) in combination during the main polymerization or during the main polymerization when the preliminary polymerization is not performed. (A) Solid component containing magnesium, titanium, halogen and an electron donating compound as essential components (B) Organoaluminum compound (C) Organosilicon compound represented by the following general formula (1) R ¹ Si (OR ² ) _x ( OR ³ ) _y (1) (wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are the same at the same time. It is not a substituent. X is 1 or 2, y is 1 or 2, and x + y = 3.)

The polypropylene used in the present invention is ASTM-
Melt flow rate (MF measured according to D1238
R) is in the range of MFR ≦ 5, preferably MFR ≦ 4, more preferably MFR ≦ 3. When the melt flow rate (MFR) exceeds 5, the melt tension improving effect is insufficient, which is not preferable. Further, the polypropylene in the present invention,
Remaining amount (HI, wt%) after extraction with boiling n-heptane
Is more than 90, preferably more than 92, and more preferably more than 94. If the residual amount (HI,% by weight) after extraction with boiling n-heptane is 90 or less, the rigidity decreases, which is not preferable.

Further, 20 of the polypropylene of the present invention is used.
The frequency ω _p obtained from the dynamic melt viscoelasticity at 0 ° C. has a log (ω _p ) of 0.966 · log (MFR) -0.
Less than 436, preferably 0.966 · log (MFR)
Less than −0.448, more preferably 0.966 · log
(MFR) -less than 0.474, and the value is 0.966.
-Log (MFR) -0.436 or more is not preferable because the balance between the rigidity and the melt tension of polypropylene is lowered. Here, the frequency ω _p obtained from the dynamic melt viscoelasticity means the complex viscosity η ^* (= η′−i · η ″) at 200 ° C. by the dynamic melt viscoelasticity measuring device, and the imaginary number of the value. The response of the part η ″ to the frequency ω is obtained. FIG. 1 shows an example of an η ″ -ω curve in which η ″ is plotted on the vertical axis and ω is plotted on the horizontal axis.

From the obtained η ″ -ω curve, ω is 0.01
(1.00E-02) [rad / sec] to 100
Η ″ in the range of (1.00E + 02) [rad / sec]
The value of ω at which is the maximum is defined as ω _p . The polypropylene in the present invention includes not only a propylene homopolymer but also a polypropylene resin obtained by copolymerizing propylene with a small amount (10% by weight or less) of ethylene and / or another α-olefin. The polymerization catalyst used in the present invention is as follows. The solid component (hereinafter, referred to as component A) used in the present invention contains magnesium, titanium, halogen and an electron donating compound as essential components, and such components are usually magnesium compounds, titanium compounds and electron donating compounds, Further, when each of the compounds is a compound having no halogen, the compound is prepared by contacting the compound with a halogen.

(1) Magnesium Compound The magnesium compound is represented by the general formula MgR ¹ R ² . In the formula, R ¹ and R ² represent the same or different hydrocarbon groups, OR ′ groups (R ′ is a hydrocarbon group), and halogen atoms. More specifically, the hydrocarbon group of R ¹ and R ² includes an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group having 1 to 20 carbon atoms, and the OR ′ group includes R ′ having a carbon number of 1 to 20 carbon atoms. Examples of the halogen atom include 1 to 12 alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine. Specific examples of these compounds are shown below, but in the chemical formula,
Me: methyl, Et: ethyl, Pr: propyl, Bu:
Butyl, He: hexyl, Oct: octyl, Ph: phenyl and cyHe: cyclohexyl are respectively shown.

MgMe ₂ , MgEt ₂ , Mgi-Pr
₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgEt
Bu, MgPh ₂ , MgcyHe ₂ , Mg (OMe)
₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OH
e) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg
(OcyHe) ₂ , EtMgCl, BuMgCl, He
MgCl, i-BuMgCl, t-BuMgCl, Ph
MgCl, PhCH ₂ MgCl, EtMgBr, BuM
gBr, PhMgBr, BuMgI, EtOMgCl,
BuOMgCl, HeOMgCl, PhOMgCl, E
tOMgBr, BuOMgBr, EtOMgI, MgC
_{l 2, MgBr 2, MgI 2} .

The above magnesium compound can be prepared from metallic magnesium or other magnesium compounds when the component A is prepared. Examples thereof include metallic magnesium, halogenated hydrocarbons and alkoxy group-containing compounds of the general formula X _n M (OR) _mn wherein X is a hydrogen atom, a halogen atom or a C 1-20
Hydrocarbon groups, M is a boron, carbon, aluminum, silicon or phosphorus atom, R is a hydrocarbon group having 1 to 20 carbon atoms, m is a valence of M, and m> n ≧ 0. ] Is contacted.

The hydrocarbon groups of X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr), i-propyl (i-P
r), butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct) and other alkyl groups, cyclohexyl (cyHe), methylcyclohexyl and other cycloalkyl groups, allyl, propenyl, butenyl, etc. And phenyl (Ph), tolyl, xylyl and other aryl groups, and phenethyl and 3-phenylpropyl and other aralkyl groups. Among these, an alkyl group having 1 to 10 carbon atoms is particularly desirable. Hereinafter, specific examples of the alkoxy group-containing compound will be described.

Compounds wherein M is carbon C (OMe) ₄ , C (OE) contained in formula C (OR) ₄
t) ₄ , C (OPr) ₄ , C (OBu) ₄ , C (Oi-
Bu) ₄ , C (OHe) ₄ , C (OOct) ₄ : Formula XC
HC (OMe) ₃ , HC (OE) contained in (OR) ₃
t) ₃ , HC (OPr) ₃ , HC (OBu) ₃ , HC
(OHe) ₃ , HC (OPh) ₃ , MeC (OMe)
₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , EtC
(OEt) ₃ , cyHeC (OEt) ₃ , PhC (OM
e) ₃ , PhC (OEt) ₃ , CH ₂ ClC (OEt)
₃ , MeCHBrC (OEt) ₃ ; MeCHClC (O
Et) ₃ ; ClC (OMe) ₃ , ClC (OEt) ₃ ,
_{ClC (Oi-Bu) 3,} BrC (OEt) 3; wherein X ₂
MeCH (OMe) ₂ , MeC contained in C (OR) ₂
H (OEt) ₂ , CH ₂ (OMe) ₂ , CH ₂ (OE
t) ₂ , CH ₂ ClCH (OEt) ₂ , CHCl ₂ CH
(OEt) ₂ , CCl ₃ CH (OEt) ₂ , CH ₂ Br
CH (OEt) ₂ , PhCH (OEt) _{2 and the} like.

Compound when M is Silicon Si (OMe) ₄ , Si contained in formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (OE) contained in the formula XSi (OR) ₃
t) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ , H
Si (OPh) ₃ ; MeSi (OMe) ₃ , MeSi
(OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OPh)
₃ ; ClSi (OMe) ₃ , ClSi (OEt) ₃ , C
lSi (OBu) ₃ , ClSi (OPh) ₃ , BrSi
(OEt) _3; Me ₂ included in the formula X ₂ Si (OR) ₂
Si (OMe) ₂ , Me ₂ Si (OEt) ₂ , Et ₂ S
i (OEt) ₂ ; MeClSi (OEt) ₂ ; CHCl
₂ SiH (OEt) ₂ ; CCl ₃ SiH (OEt) ₂ ;
MeBuSi (OEt) ₂ : M contained in X ₃ SiOR
e ₃ SiOMe, Me ₃ SiOEt, Me ₃ SiOB
u, Me ₃ SiOPh, Et ₃ SiOEt, Ph ₃ Si
OEt etc. are mentioned.

Compounds wherein M is boron B (OEt) ₃ , B (OB) contained in formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) _{3 and the} like. Compound when M is aluminum Al (OMe) ₃ , Al contained in formula Al (OR) ₃
(OEt) ₃ , Al (OPr) ₃ , Al (Oi-Pr)
₃ , Al (OBu) ₃ , Al (Ot-Bu) ₃ , Al
(OHe) ₃ , Al (OPh) _{3 and the} like. Compound when M is phosphorus P (OMe) ₃ , P (OE) contained in formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) _{3 and the} like.

Further, as the magnesium compound, a complex with an organic compound of a metal (M) of Group II or Group IIIa of the periodic table can be used. The complex has the general formula MgR ¹
R ² · n (MR ³ _m ). As the metal,
Aluminum, zinc, calcium, etc., and R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. M represents the valence of the metal M, and n represents a number of 0.1 to 10. Specific examples of the compound represented by MR ³ _m include AlMe ₃ , AlEt ₃ ,
_{Ali-Bu 3, AlPh 3,} ZnMe 2, ZnEt
₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaPh ₂
And the like.

(2) Titanium compound Titanium compound is a compound of divalent, trivalent and tetravalent titanium. Examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium and dichlorotitanium. Examples thereof include rudiethoxytitanium, dichlorodibutoxytitanium, dichlorodiphenoxytitanium, chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium, and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

(3) Electron-donating compound As the electron-donating compound, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines,
Examples include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic, and antimony compounds bonded to an organic group via carbon or oxygen, phosphoamides, thioethers, thioesters, and carbonate esters. Of these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols and ethers are preferably used.

Specific examples of the carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid and crotonic acid, and malonic acid. , Succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, p-tert-butyl benzoic acid, naphthoic acid, aromatic monocarboxylic acids such as cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
And aromatic polycarboxylic acids such as melitic acid. As the carboxylic acid anhydride, the acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, and pivalic acid. Isobutyl, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate,
Monomethyl fumarate, diethyl fumarate, diisobutyl fumarate,

Diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate;
ethyl p-tert-butyl benzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate,
Dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate,
Examples thereof include diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, and tetrabutyl pyromellitate.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used.
Specific examples thereof include acetate chloride, acetate bromide, acetate iodide, propionate chloride, butyrate clomid,
Butyric acid bromide, Butyric acid iodide, Pivalic acid chloride, Pivalic acid bromide, Acrylic acid chloride, Acrylic acid bromide, Acrylic acid iodide, Methacrylic acid chloride, Methacrylic acid bromide, Methacrylic acid iodide, Crotonic acid chloride, Malonic acid chloride, Malonic acid bromide, Succinic chloride, succinic bromide,
Glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride,
Sebacic acid bromide, maleic acid chloride, maleic acid bromide,

Fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide,
-Cyclohexene carboxylic acid chloride, cis-4-methylcyclohexene carboxylic acid chloride, cis-4-methylcyclohexene carboxylic acid bromide, benzoyl chloride, benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride , P-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride and phthalic acid butyl chloride can also be used.

Alcohols are represented by the general formula R ⁴ OH. In the formula, R ⁴ is alkyl having 1 to 12 carbons,
Alkenyl, cycloalkyl, aryl and aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol,
Benzyl alcohol, allyl alcohol, phenol,
Cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol and the like.

The ethers are represented by the general formula R ⁵ OR ⁶ . In the formula, R ⁵ and R ⁶ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R ⁵ and R ⁶ may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether,
Diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether and the like.

The component A is prepared by contacting a magnesium compound (component 1), a titanium compound (component 2) and an electron donating compound (component 3) in that order, and after contacting the components 1 and 3 with each other. , Component 2 may be contacted, component 1, component 2 and component 3 may be contacted at the same time. It is also possible to contact the halogen-containing compound before contacting the component 2. Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, halides of Group IIIa, IVa, and Va elements of the periodic table (hereinafter referred to as metal halides). Can be mentioned.

Halogenated hydrocarbons include those having 1 to 1 carbon atoms.
Mono- and poly-halogen substituents of 12 saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons. Specific examples of such compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane,

Methyl chloroform, methyl bromoform, methyl iodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffins and the like, alicyclic compounds include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane and the like, and aromatic compounds include chlorobenzene, bromobenzene, o-dichloro. Examples thereof include benzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride and p-chlorobenzotrichloride. These compounds may be used alone or in combination of two or more.

As the halogen-containing alcohol, one or two or more hydrogen atoms other than a hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are substituted with a halogen atom. Compound. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and a chlorine atom is preferable. Examples of these compounds include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, and 4-chloro-1-.
Butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p) -Chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m,
o) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chlorophenol,

4-chloro-1-naphthol, (m, o,
p) -chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-chlororesorcin, 2-chlorophenol
Bromoethanol, 3-bromo-1-propanol, 1
-Bromo-2-propanol, 1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-
Naphthol, 6-bromo-2-naphthol, (m, o,
p) -bromophenol, 4-bromoresorcinol,
(M, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro-1 -(Α-chloromethyl) -1-propanol, 2,3-dibromo-1-propanol,
1,3-dibromo-2-propanol,

2,4-dibromophenol, 2,4-dibromo-1-naphthol: 2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol,
β, β, β-trichloro-tert-butanol, 2,
3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol,
2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,6-triiodophenol: 2,3
4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, tetra Fluororesorcin and the like.

Examples of the silicon halide compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , and H ₃ S
iCl, H (CH ₃ ) SiCl ₂ , H (C ₂ H ₅ ) Si
_{Cl 2, H (t-C} 4 H 9) SiCl 2, H (C 6 H
_{5) SiCl 2, H (CH} 3) 2 SiCl, H (i-C
_{3 H 7) 2 SiCl, H} 2 (C 2 H 5) SiCl, H 2
_{(N-C 4 H 9)} SiCl, H 2 (C 6 H 4 CH 3) S
iCl, H (C ₆ H ₅ ) ₂ SiCl and the like. As metal halides, B, Al, Ga, In, Tl, S
i, Ge, Sn, Pb, As, Sb and Bi include chlorides, fluorides, bromides and iodides, especially BCl ₃ , B
Br ₃ , BI ₃ , AlCl ₃ , AlBr ₃ , GaCl
_{3, GaBr 3, InCl 3,} TlCl 3, SiCl
₄ , SnCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferred.

The contact with the component 1, the component 2 and the component 3, and the halogen-containing compound which can be brought into contact with the component, if necessary, can be carried out by mixing or stirring in the presence or absence of an inert medium, or by mechanical stirring. This is done by co-milling. The contact can be performed under heating at 40 to 150 ° C. As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used. A preferable method for preparing the component A in the present invention is described in JP-A-63-264607 and JP-A-6-264607.
8-198503, 62-146904 and the like.

More specifically, contacting (a) metallic magnesium, (b) halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the above alkoxy group-containing compound). A method of contacting the magnesium-containing solid obtained by (2) with a halogen-containing alcohol, and then with (e) an electron-donating compound and (f) a titanium compound (JP-A-63)
-264607), (a) magnesium dialkoxide and (b) hydrogen-
After contacting a silicon halide compound having a silicon bond, (c) a titanium halide compound is contacted, and then (d) an electron-donating compound (if necessary, further contacted with a titanium halide compound). Method (JP-A-62-146904),

(A) A method in which a magnesium dialkoxide and (b) a silicon halide compound having a hydrogen-silicon bond are brought into contact with each other, followed by (c) an electron donating compound, and then (d) a titanium compound. (JP-A-58
-198503). Among these, a particular method is most desirable.
The component A is prepared as described above, and the component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

The organoaluminum compound that can be used (hereinafter referred to as the component B) is represented by the general formula R ⁷ _n AlX ′ _3-n (provided that R
Represents an alkyl group or an aryl group, X ′ represents a halogen atom, an alkoxy group or a hydrogen atom, and n is an arbitrary number within the range of 1 ≦ n ≦ 3. ), For example, a trialkylaluminum, a dialkylaluminum monohalide, a monoalkylaluminum dihalide, an alkylaluminum sesquihalide, a dialkylaluminum monoalkoxide, a dialkylaluminum monohydride, etc., having 1 to 18 carbon atoms, preferably a carbon atom. Especially preferred are alkylaluminum compounds of the number 2 to 6 or mixtures or feedstocks thereof. Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum iodide, diisobutyl aluminum chloride, etc. Dialkyl aluminum monohalide,

Monoalkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, dimethyl Aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxide such as diisobutyl aluminum phenoxide, dimethyl aluminum hydride,
Dialkylaluminum hydrides such as diethylaluminum hydride, dipropylaluminum hydride and diisobutylaluminum hydride are exemplified. Among these, trialkyl aluminum, particularly triethyl aluminum and triisobutyl aluminum are desirable.

Organosilicon Compound The organosilicon compound (C), which is one component of the catalyst of the present invention (hereinafter referred to as component C), has the general formula R ^{1 as} described above.
Si (OR ² ) _x (OR ³ ) _y (1) In the formula, R ¹ , R ² and R ³ are each a hydrocarbon group having 1 to 10 carbon atoms. R ¹ is preferably a chain or cyclic alkyl group having 1 to 6 carbon atoms, R ² and R
³ is preferably an alkyl group having 1 to 5 carbon atoms, and R ²
And R ³ are not the same substituent at the same time, x is 1 or 2, y is 1 or 2, and x + y = 3. Examples of R ¹ include methyl group, ethyl group, n-propyl group, i-
Examples thereof include a propyl group, an s-butyl group, a t-butyl group, a t-amyl group and a cyclopentyl group. Examples of R ² and R ³ include a methyl group, an ethyl group, an n-propyl group and i.
-Propyl group, s-butyl group, t-butyl group, t-amyl group and the like.

Specifically, i-propoxycyclopentyldimethoxysilane, s-butoxycyclopentyldimethoxysilane, t-butoxycyclopentyldimethoxysilane, t-amylcyclopentyldimethoxysilane,
i-propoxycyclopentyldiethoxysilane, s-
Butoxycyclopentyldiethoxysilane, t-butoxycyclopentyldiethoxysilane, t-amylcyclopentyldiethoxysilane, t-butoxymethyldimethoxysilane, t-butoxyethyldimethoxysilane, t
-Butoxy-s-butyldimethoxysilane, t-butoxy-t-butyldimethoxysilane, t-butoxy-t-
Amyldimethoxysilane, t-butoxy-n-propyldimethoxysilane, t-butoxymethyldiethoxysilane, t-butoxyethyldiethoxysilane, t-butoxy-s-butyldiethoxysilane, t-butoxy-t-
Butyldiethoxysilane, t-butoxy-n-propyldiethoxysilane, t-butoxy-t-amyldiethoxysilane, di-i-propoxymethoxy-n-propylsilane, di-s-butoxymethoxy-n-propylsilane , Di-t-butoxymethoxy-n-propylsilane,
Di-t-amylmethoxy-n-propylsilane, di-s
-Butoxymethylmethoxysilane, di-s-butoxyethylmethoxysilane, di-s-butoxybutylmethoxysilane, di-n-propoxymethylmethoxysilane, di-n-propoxyethylmethoxysilane, di-n-propoxypropylmethoxysilane Etc.

Preliminary Polymerization In the present invention, the prepolymerization of component A may or may not be carried out, and when prepolymerization is carried out, it is essential to use the component (C) in at least one of prepolymerization and main polymerization. And when the prepolymerization is not carried out, the main polymerization is the component (C).
It is essential to use Specifically, when carrying out the prepolymerization of the component A, the prepolymerization is carried out in the presence of an organoaluminum (component B) and, if necessary, an organosilicon compound (component C), an olefin (hereinafter referred to as the component D). It is done by contacting with.

If necessary, an electron-donating compound (hereinafter referred to as component E) is preferably added together with the components B and C during the prepolymerization of the component A. As the electron-donating compound, an electron-donating compound composed of an organic silicon compound and an electron-donating compound containing a hetero atom such as nitrogen, sulfur, oxygen, and phosphorus can be used. Among them, the organic silicon compound is preferable. As the organosilicon compound, a compound in which an alkyl group and an alkoxy group are bonded to a total of four silicon atoms is preferable. These alkyl groups and alkoxy groups may be chain-like, and some of them are heteroelements such as O, N, and S. May be substituted.

Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane and methyltrimethoxy. Silane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltri Butoxysilane, butyltriphenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane,

Allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, Dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, Examples include diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane.

Specific examples of the electron-donating compound containing a hetero atom include compounds containing a nitrogen atom:
6,6-tetramethylpiperidine, 2,6-dimethylpiperidine, 2,6-diethylpiperidine, 2,6-diisopropylpiperidine, 2,6-diisobutyl-4-methylpiperidine, 1,2,2,6,6- Pentamethylpiperidine, 2,2,5,5-tetramethylpyrrolidine,
2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-diisopropylpyrrolidine, 1,2,
2,5,5-pentamethylpyrrolidine, 2,2,5-trimethylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-diisopropylpyridine, 2,6-diisobutylpyridine, 1, 2,
4-trimethylpiperidine, 2,5-dimethylpiperidine, methyl nicotinate,

Ethyl nicotinate, nicotinic acid amide, benzoic acid amide, 2-methylpyrrole, 2,5-dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, paratoluidine,
Orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine and the like, as a compound containing a sulfur atom, thiophenol, thiophene, ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2- Methyl thiophene, methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, butyl mercaptan, diethyl thioether, diphenyl thioether, methyl benzenesulfonate, methyl sulphite, ethyl sulphite and the like, as a compound containing an oxygen atom, tetrahydrofuran,

2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2-ethyltetrahydrofuran, 2,2,5,5-tetraethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyl Tetrahydropyran, 2,2,6,6-tetramethyltetrahydropyran, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, o-tolyl-t-butyl ketone, Methyl-2,6-di-t-butylphenylketone, ethyl 2-furarate, isoamyl 2-furarate, methyl 2-furarate, propyl 2-furarate and the like are compounds containing a phosphorus atom. , Triphenylphosphine, tributylphosphine, triphenyl phosphite, tribenzyl phosphite, diethyl phosphate, and diphenyl phosphate and the like.

Two or more kinds of these electron donating compounds may be used. Further, these electron donating compounds may be used when an organoaluminum compound is used in combination with a catalyst component, or may be used after being contacted with the organoaluminum compound in advance. As olefins, in addition to ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-
Alpha-olefins such as pentene may be used. The prepolymerization is preferably performed in the presence of the above-mentioned inert medium. The prepolymerization is usually performed at a temperature of 100 ° C or lower, preferably -30.
C. to + 30.degree. C., more preferably -20.degree. C. to + 15.degree. The polymerization system may be either a batch system or a continuous system, or may be performed in two or more stages. When the reaction is carried out in multiple stages, the polymerization conditions can of course be changed.

Component B has a concentration of 10 to 5 in the prepolymerization system.
It is used in an amount of 00 mmol / l, preferably 30 to 200 mmol / l, and 1 to 50,000 mol, preferably 2 to 1,000 mol, per gram atom of titanium in component A. Used. Component C has a concentration in the prepolymerization system of 1 to 1,000 mmol /
It is used so as to be 1 liter, preferably 5 to 200 mmol / liter. The olefin polymer is incorporated into the component A by the prepolymerization, but the amount of the polymer is preferably 0.1 to 200 g, particularly 0.5 to 50 g per 1 g of the component A. Although the catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium, it is particularly preferable to wash the catalyst component from the viewpoint of preventing the storage component from deteriorating in storage. After washing, it may be dried if necessary. Also, when storing the catalyst component, it is desirable to store it at a low temperature as much as possible.
° C, especially the temperature range of -20 ° C to + 5 ° C is recommended.

Main Polymerization The catalyst component obtained by prepolymerization as described above is propylene alone in the presence of a catalyst comprising the organoaluminum compound (component B) and, if necessary, the organosilicon compound (C). Polymerization or main polymerization such as copolymerization with other olefins is performed to obtain crystalline polypropylene having a relationship between the frequency ω _p determined from dynamic viscoelasticity and the melt flow rate (MFR) represented by the above formula (1). be able to. That is,
When the component C is not used in the prepolymerization, it is essential to use the component C in the main polymerization, and when the component C is used in the prepolymerization, the component C may not be used in the main polymerization. In addition to C, the organosilicon compound represented by the electron donating compound (component E) can also be used. When the prepolymerization is not carried out, the main polymerization such as the homopolymerization of propylene or the copolymerization with other olefins is carried out in the presence of the catalyst composed of the components A, B and C, and the frequency obtained from the dynamic viscoelasticity is obtained. A crystalline polypropylene having a relationship between ω _p and melt flow rate (MFR) represented by the above formula (1) can be obtained.

Examples of the organoaluminum compound (component B) that can be used include the compounds as described in the above-mentioned "organoaluminum compound". Trialkylaluminum is another organoaluminum compound, for example, industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or a mixture or feed compound thereof. It can be used together with.
An organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Examples of such compounds include

[0054]

Embedded image Etc. can be exemplified.

The amount of the organoaluminum compound used with respect to the catalyst component of the present invention is usually 1 to 2,000 gram mol, particularly 20 to 5 gram atom per 1 gram atom of titanium in the catalyst component.
00 grams mole is desirable. When an electron donating compound is used, the ratio of the organoaluminum compound to the electron donating compound is 0.1 to 40, preferably 1 to 25 gram atom of the organoaluminum compound as aluminum per 1 mol of the electron donating compound. It is selected in the range of.

The propylene polymerization reaction may be carried out in either a gas phase or a liquid phase. When the polymerization is carried out in the liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in an inert hydrocarbon and a liquid monomer. The polymerization temperature is usually -8.
It is in the range of 0 ° C to + 150 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atm. Adjustment of the molecular weight of the resulting polymer is performed by the presence of hydrogen or other known molecular weight regulators. The polymerization reaction is carried out by a continuous or batch-type reaction, and the condition may be a commonly used condition. Further, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

[0057]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. Melt flow rate (MFR)
Is a value measured according to ASTM-D1238.
The boiling n-heptane extraction residual quantity (HI) represents the residual quantity in% by weight when extracted with boiling n-heptane for 6 hours using a modified Soxhlet extractor. The frequency ω _p obtained from the dynamic melt viscoelasticity at 200 ° C. is relative to the frequency ω of η ″ which is the imaginary part of the complex viscosity η ^* (= η′−i · η ″) measured under the following measurement conditions. Ask for a response. The obtained values are plotted as η ″ on the vertical axis and ω on the horizontal axis as shown in FIG. 1, and from the obtained η ″ -ω curve, ω is 0.01 (rad / rad /
sec) to 100 (rad / sec), the value of ω at which η ″ is maximum is defined as ω _p .

Measurement conditions Device: RMS-800 (trade name) manufactured by Rheometrics
Viscoelasticity measuring device Measuring temperature: 200 ° C. Strain: 15% Measuring frequency range: 0.01 to 100 rad / sec Plate: parallel plate Sample shape and procedure up to measurement: A press-formed product having a thickness of 2 mm and a diameter of 25 mm is used as a sample. , Measurement temperature 20
After stabilizing at 0 ° C, compress it to 1.5 mm, scrape out the extra sample protruding around the plate, and stabilize it for another 20 minutes before starting the measurement.

Example 1 Preparation of solid catalyst component In a 1 liter reaction vessel equipped with a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity 99.5) was prepared.
%, Average particle size 1.6 mm) 8.3 g and n-hexane 2
After adding 50 ml and stirring at 68 ° C. for 1 hour, magnesium metal was taken out and dried at 65 ° C. under reduced pressure to obtain preactivated magnesium metal. Next, 140 ml of n-butyl ether and n-butyl ether were added to the metallic magnesium.
A suspension containing 0.5 ml of n-butyl ether solution (1.75 mol / l) of butylmagnesium chloride was kept at 55 ° C., and n-butyl ether was added to 50 ml of n-butyl ether.
-A solution containing 38.5 ml of butyl chloride dissolved in 50
In minutes. After conducting the reaction at 70 ° C. for 4 hours with stirring, the reaction solution was kept at 25 ° C.

Next, HC (OC ₂ H ₅ ) was added to this reaction solution.
₃ 55.7 ml was added dropwise over 1 hour. After dropping, 60
The reaction was carried out at 15 ° C. for 15 minutes, and the solid produced by the reaction was washed six times with 300 ml each of n-hexane, and dried under reduced pressure at room temperature for 1 hour.
31.6 g of a magnesium-containing solid containing 19.0% of magnesium and 28.9% of chlorine was recovered. Under a nitrogen gas atmosphere, a magnesium-containing solid 6.3 was placed in a 300 ml reaction vessel equipped with a reflux condenser, a stirrer, and a dropping funnel.
g and 50 ml of n-heptane to form a suspension, and while stirring at room temperature, 2,2,2-trichloroethanol 20 m
A mixed solution of 1 (0.02 mmol) and 11 ml of n-heptane was added dropwise from a dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The obtained solid was separated by filtration, washed four times with 100 ml each of n-hexane at room temperature, and further washed with 10 ml of toluene each.
After washing twice with 0 ml, a solid component was obtained.

40 ml of toluene was added to the above solid component, titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. Under stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. The obtained solid substance was separated by filtration at 90 ° C. and washed at 90 ° C. twice with 100 ml each of toluene. Further, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene became 3/2, and the mixture was stirred at 120 ° C. for 2 hours, and then stirred at room temperature for 1 hour.
After washing 7 times with 00 ml of n-hexane, 5.5 g of the component was obtained.
I got

In a 5-liter stainless steel autoclave equipped with a main polymerization stirrer, 6 ml of a solution of triisobutylaluminum (hereinafter abbreviated as TIBAL) in n-heptane (0.1 mol / liter) and t-in a nitrogen gas atmosphere. Butoxy-t-
N-Heptane solution of butyldimethoxysilane (0.01
Mol / liter) 6 ml was mixed and held for 5 minutes. Then, hydrogen gas 1.3 as a molecular weight control agent
After pressurizing 1 liter and 3 liters of liquid propylene,
The reaction system was heated to 70 ° C. Catalyst component 1 obtained above
After charging 5.1 mg into the reaction system, propylene was polymerized for 1 hour. After the polymerization was completed, unreacted propylene was purged to obtain 487.7 g of white polypropylene powder.
Polypropylene production amount (CE) per gram of solid catalyst component
Was 32.3 kg. The polymerization conditions are shown in Table 1. The polypropylene obtained had an MFR of 0.65 g / 10 minutes, a thermal heptane insoluble content (HI) of 97.8% by weight, a dynamic viscoelasticity measurement ω _p of 0.176 rad / sec, and a flexural modulus of 16,400 kg. / Cm ² , and the melt tension was 14.2 g. Table 2 shows the results.

(Examples 2 and 3) Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1. Table 2 shows the results of measuring the physical properties of these polypropylenes.

Example 4 In a 500 ml reactor equipped with a prepolymerization stirrer, under nitrogen gas atmosphere, 3.5 g of the solid catalyst component obtained in Example 1 and n were added.
300 ml of heptane were added and cooled to 0 ° C. with stirring. Next, n-heptane solution (2.0 mol / liter) of triethylaluminum (hereinafter abbreviated as TEAL) and s-butoxycyclopentyldimethoxysilane were added to the reaction system so that the concentrations of TEAL and s-butoxycyclopentyldimethoxysilane were each 100 mmol. / L and 10 mmol / L, and stirred for 5 minutes. Next, after depressurizing the system, propylene gas was continuously supplied to polymerize propylene for 2 hours. After completion of the polymerization, propylene in the gas phase was purged with nitrogen gas, and the solid phase portion was washed with 100 ml of n-hexane three times at room temperature. Further, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a preliminary weight catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 2.5 g per 1 g of the component. Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1 using the catalyst component obtained as a result of the above preliminary polymerization. Table 2 shows the results of evaluating the physical properties of the obtained polypropylene.

(Comparative Examples 1 to 5) Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1. Table 2 shows the polymerization and physical property measurement results of these polypropylenes. (Comparative Example 6) Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1. Table 2 shows the results of polymerization and physical property measurement of this polypropylene. As apparent from Table 2, polypropylene omega _p dynamic viscoelasticity measurement is in the range of the present invention, omega _p
However, it is found that the flexural modulus and melt tension are higher than those outside the range of the present invention, and the rigidity and heat resistance are improved. (Example 5) Polymerization was carried out in the same manner as in Example 4 under the conditions shown in Table 1. Table 2 shows the results of evaluating the physical properties of the obtained polypropylene.

[0066]

[Table 1]

[0067]

[Table 2] Formula (1) 0.966 · log (MFR) -0.436 Flexural modulus According to JIS K-6758. Heat distortion temperature According to JIS K-7202. Melt tension: Using a melt tension tester manufactured by Toyo Seiki Seisakusho, extrusion speed 10 mm / min, winding speed 2
The measurement was performed at 00 rpm and a temperature of 200 ° C.

[0068]

As is apparent from the examples of the present invention, the frequency ω _p determined from the dynamic melt viscoelasticity at 200 ° C.
The polypropylene within the scope of the present invention has a higher flexural modulus and melt tension, improved rigidity and heat resistance, and is also excellent in moldability and impact resistance as compared with those where ω _p is outside the range. In particular, it is suitable for extrusion, sheet and blow molding applications. Therefore, since the crystalline polypropylene of the present invention has high rigidity, in a molded article for the same purpose as the conventional one, it is possible to reduce the thickness and weight, and it is effective in terms of resource saving and productivity, and By improving rigidity and heat resistance, it has become possible to replace the applications that have traditionally used polystyrene, ABS resin, etc.

[Brief description of the drawings]

[Fig. 1] η "-ω in which η" is plotted on the vertical axis and ω is plotted on the horizontal axis.
An example of a curve is shown.

FIG. 2 is a chart of a catalyst used in the present invention.

Claims (2)

[Claims] 1. The melt flow rate (MFR) measured according to ASTM-D1238 is in the range of MFR ≦ 5, and the residual amount (HI, wt%) after extraction with boiling n-heptane exceeds 90. , And the frequency ω _p and MFR obtained from the dynamic melt viscoelasticity at 200 ° C. are log (ω _p ) <0.966 · log (MFR) −0.
Crystalline polypropylene characterized by satisfying the relation 2. A polypropylene obtained by polymerizing propylene in the presence of a catalyst comprising the following component (A) and component (B), which is used for prepolymerization and / or prepolymerization and / or main polymerization, Alternatively, the crystalline polypropylene according to claim 1, which is obtained by further using the following component (C) together during the main polymerization when the preliminary polymerization is not carried out. (A) Solid component containing magnesium, titanium, halogen and an electron donating compound as essential components (B) Organoaluminum compound (C) Organosilicon compound represented by the following general formula (1) R ¹ Si (OR ² ) _x ( OR ³ ) _y (1) (In the formula, R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are the same at the same time. Not a substituent, x is 1 or 2, y is 1
Alternatively, it is 2 and x + y = 3. )