JP3468962B2 - Crystalline polypropylene - Google Patents

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 and AB are used as materials for molded products 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. . Moreover, since a thin molded product can be finished, 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 relation, 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 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 used in the present invention (hereinafter referred to as component A) contains magnesium, titanium, halogen and an electron donating compound as essential components, and such a component is usually a magnesium compound, a titanium compound and an electron donating compound, Further, in the case where each of the above compounds is a compound having no halogen, it is prepared by bringing the halogen-containing compound into contact with each other.

(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 is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and the OR ′ group is R ′ having a carbon number. Examples of the halogen atom include 1 to 12 alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups, and 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. As an example thereof, a compound containing metal magnesium, a halogenated hydrocarbon and an alkoxy group represented by the general formula X _n M (OR) _mn [wherein X is a hydrogen atom, a halogen atom or a carbon number of 1 to 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. ] The method of making it contact is mentioned.

The hydrocarbon groups represented by X and R in the general formula of the alkoxy group-containing compound include methyl (Me), ethyl (Et), propyl (Pr) and 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. Specific examples of the alkoxy group-containing compound will be given below.

C (OMe) ₄ and C (OE contained in the compound formula C (OR) ₄ when M is carbon
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 ; Formula X ₂
MeCH (OMe) ₂ and 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
Examples include CH (OEt) ₂ and PhCH (OEt) ₂ .

Si (OMe) ₄ , Si included in the compound formula Si (OR) ₄ when M is silicon
(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 ;
M contained in MeBuSi (OEt) ₂ : 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.

B (OEt) ₃ and B (OB contained in the compound formula B (OR) ₃ in the case where M is boron
u) ₃ , B (OHe) ₃ , B (OPh) _{3 and the} like. Al (OMe) ₃ , Al included in the compound formula Al (OR) ₃ when M is aluminum
(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 can be mentioned. When M is phosphorus, P (OMe) ₃ , P (OE) contained in the compound formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) ₃ etc. are mentioned.

Further, as the magnesium compound, a complex with an organic compound of Group II or IIIa metal (M) of the periodic table can be used. The complex has the general formula MgR ¹
It is represented by R ² · n (MR ³ _m ). As the metal,
It is aluminum, zinc, calcium or the like, and R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. Further, m represents the valence of the metal M, and n represents the 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
Etc.

(2) Titanium Compound The titanium compound is a divalent, trivalent or tetravalent titanium compound, and examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium and dichlorotitanium. Examples thereof include rudiethoxy titanium, dichlorodibutoxy titanium, dichlorodiphenoxy titanium, chlorotriethoxy titanium, chlortributoxy titanium, tetrabutoxy titanium and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxy titanium, dichlorodibutoxy titanium, and dichlorodiphenoxy titanium are preferable, and titanium tetrachloride is particularly preferable.

(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 thereof include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic acid esters and the like. Of these, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols and ethers are preferably used.

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

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, 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-tertiary 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, di2-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 pyromellitic acid, tetraethyl pyromellitic acid and tetrabutyl pyromellitic acid.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used,
As specific examples thereof, acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride,
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 acid chloride, succinic acid 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, 1
-Cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic 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. Also, a monoalkyl halide of a dicarboxylic acid such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, phthalic acid butyl chloride may 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,
Examples include cresol, xylenol, ethylphenol, isopropylphenol, p-tertiarybutylphenol, 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,
Examples include diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether.

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 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.

The halogenated hydrocarbon has 1 to 1 carbon atoms.
Twelve saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbon mono- and polyhalogen substitutes. Specific examples of those compounds include, in aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, and tetrachloride. 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, any one or two or more hydrogen atoms other than the hydroxyl group in a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule are substituted with halogen atoms. It is a compound. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and 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-chlororesorcinol, 2-
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-bromoresorcin,
(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 Examples thereof include fluororesorcin.

As the silicon halide compound having a hydrogen-silicon bond, HSiCl ₃ , H ₂ SiCl ₂ , H ₃ S may be used.
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
Examples thereof include iCl and H (C ₆ H ₅ ) ₂ SiCl. Metal halides include B, Al, Ga, In, Tl, S
Examples thereof include chlorides, fluorides, bromides, and iodides of i, Ge, Sn, Pb, As, Sb, and Bi, particularly 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 preferable.

The contact with Component 1, Component 2 and Component 3, and optionally with a halogen-containing compound, which can be optionally contacted, is carried out by mixing and stirring in the presence or absence of an inert medium, or by mechanical stirring. It is made 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, the most preferable method is the most preferable method.
Although the component A is prepared as described above, the component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

Organoaluminum Compound As an organoaluminum compound that can be used (hereinafter referred to as component B), a compound represented by the general formula R ⁷ _n AlX ′ _3-n (where R is
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 and 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,
Dialkyl aluminum hydrides such as diethyl aluminum hydride, dipropyl aluminum hydride and diisobutyl aluminum hydride can be mentioned. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable.

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
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 the component A may or may not be carried out, and when the prepolymerization is carried out, it is essential to use the component (C) in at least one of the prepolymerization and the main polymerization. And when the prepolymerization is not carried out, the main polymerization is the component (C).
Is mandatory. 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 or phosphorus can be used, but of these, an organic silicon compound is preferable. The organosilicon compound is preferably one in which an alkyl group and an alkoxy group are bonded to four silicon atoms in total, and the alkyl group and the alkoxy group may be chain-like, and a part of them is a hetero element such as O, N or S. May be replaced with.

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, dimethyldi
Sopropoxysilane, dimethyldibutoxysilane, dime
Tyldihexyloxysilane, dimethyldiphenoxy
Orchid, diethyldiethoxysilane, diethyldiisobuto
Xysilane, diethyldiphenoxysilane, dibutyldi
Isopropoxysilane, dibutyldibutoxysilane, di
Butyldiphenoxysilane, diisobutyldiethoxy
Orchid, diisobutyldiisobutoxysilane, diphenyl
Dimethoxysilane, diphenyldiethoxysilane, dif
Phenyldibutoxysilane, dibenzyldiethoxysila
, Divinyldiphenoxysilane, diallyldipropoxy
Sisilane, diphenyldiallyloxysilane, methyl
Phenyldimethoxysilane, chlorophenyldiethoxysilane
Examples include orchids.

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, Two
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 carried out 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 method may be a batch method or a continuous method, or may be a multi-step polymerization of two or more steps. When carrying out in multiple stages, it goes without saying that the polymerization conditions can be changed.

Component B has a concentration of 10 to 5 in the prepolymerization system.
It is used in an amount of 00 mmol / liter, preferably 30 to 200 mmol / liter, and is 1 to 50,000 mol, preferably 2 to 1,000 mol, per gram atom of titanium in the 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. The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium, but it is particularly preferable to wash it from the viewpoint of preventing storage deterioration of the catalyst component. 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.
A temperature range of 0 ° C, especially -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 component A, the component B and the component 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.
Further, an organoaluminum 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]

[Chemical 1] Etc. can be illustrated.

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 atmospheres. Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator. The polymerization reaction is carried out by a continuous or batch reaction, and the conditions therefor may be those usually used. Moreover, the polymerization reaction may be carried out in one step or in two or more steps.

[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 .

Measuring condition device: RMS-800 (trade name) manufactured by Rheometrics
Viscoelasticity measuring device Measurement temperature: 200 ° C. Strain: 15% Measurement frequency range: 0.01 to 100 rad / sec Plate: Parallel plate Sample shape and procedure until measurement: 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, metallic magnesium was taken out and dried under reduced pressure at 65 ° C. to obtain pre-activated metallic magnesium. Next, 140 ml of n-butyl ether and n-butyl ether were added to the magnesium metal.
A suspension of 0.5 ml of n-butyl ether solution of butylmagnesium chloride (1.75 mol / l) was kept at 55 ° C., and 50 ml of n-butyl ether was added with n.
-A solution containing 38.5 ml of butyl chloride dissolved in 50
Dropped in minutes. After the reaction was carried out 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 performed at 15 ° C for 15 minutes, the reaction product solid was washed 6 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% magnesium and 28.9% chlorine was recovered. In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, magnesium-containing solid 6.3 in a nitrogen gas atmosphere.
g and n-heptane (50 ml) were added to form a suspension, and 2,2,2-trichloroethanol (20 m) was stirred at room temperature.
A mixed solution of 1 (0.02 mmol) and 11 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour. The solid obtained was filtered off, washed four times with 100 ml of room temperature n-hexane each time, and further with 10 parts each toluene.
It was washed twice with 0 ml to obtain a solid component.

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. With stirring, a mixed solution of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, and then the mixture was stirred at 120 ° C. for 2 hours. The solid substance obtained was filtered off at 90 ° C. and washed twice with 100 ml of toluene each time at 90 ° C. Further, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° C. for 2 hours and then at room temperature for each 1
After washing 7 times with 00 ml of n-hexane, 5.5 g of the component
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. The results are shown in Table 2.

(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.

[0064] (Example 4) in reactor 500ml fitted with a prepolymerization stirrer, under a nitrogen gas atmosphere, the solid catalyst component obtained in Example 1 3.5 g and n
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 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.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-6-184215 (JP, A) JP-A-7-118323 (JP, A) JP-A-9-132611 (JP, A) JP-A-9- 104711 (JP, A) JP-A-7-104710 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210/18 C08F 4/64-4/69

Claims (2)

(57) [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 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. )