JPH07118345A - Crystalline polypropylene - Google Patents

Abstract

PURPOSE:To obtain the crystalline PP useful for obtaining a thin-wall molding excellent in rigidity, heat resistance, impact resistance, moldability, wear resistance, etc., by selecting a specified crystalline PP. CONSTITUTION:A crystalline PP satisfying the relationship: IPF>=1.65logomega0-1.15 logG0+99.3 (wherein omega0 is the frequency at which the storage modulus G' and the loss modulus G'' become equal in the dynamic melt viscoelasticity measurement; G0 is the modulus at this frequency; and IPF is the isotactic pentad fraction in <13>C-NMR measurement) is selected. This PP is obtained desirably by polymerizing propylene by using an alpha-olefin polymerization catalyst component prepared by bringing a solid component essentially consisting of Mg, Ti, halogen and an electron donating compound into contact with an olefin in the presence of an organoaluminum compound and a specified organosilicon compound [e.g. bis(oxacyclopent-3-yl)dimethoxysilane].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to crystalline polypropylene, and more particularly to crystalline polypropylene having excellent rigidity and heat resistance.

[0002]

2. Description of the Related Art Polypropylene has excellent heat resistance, chemical resistance, and electrical properties, and also has excellent rigidity, tensile strength, optical characteristics, and processability, and is injection molded, film molded, sheet molded, blow molded, etc. In addition, polypropylene has a light specific gravity and is widely used in fields such as containers and packaging materials. However, these properties are not sufficiently satisfied depending on the application, and the use is often restricted. Among the performances mentioned above,
In terms of rigidity and heat resistance, polypropylene is inferior to polystyrene and ABS resin. Therefore, polypropylene cannot be used as a material for producing a molded product that is required to have rigidity and heat resistance, and as a material for a molded product that is required to have rigidity and heat resistance, the polystyrene or ABS resin Instead, if polypropylene is intentionally used, in order to satisfy the above properties, a thick molded product must be formed, which prevents the molded product from being thin and increases the cost of the molded product, that is, The applications of polypropylene or polypropylene compositions cannot be expanded. If polypropylene has excellent rigidity,
Given that it has chemical resistance, formability, heat resistance, hardness, etc., such polypropylene is
As an alternative to BS resin, it can be used for a wider range of applications. Moreover, because it is possible to finish thin molded products,
Resource saving and cost reduction can be expected.

As a known technique for improving the rigidity of crystalline polypropylene, for example, it is molded by adding an organic nucleating agent such as paratertiarybutyl benzoic acid aluminum salt or 1,8-2,4-dibenzylidene sorbitol. Although there is a method, there is a drawback that the cost is high and it is not economical, and the addition thereof greatly reduces gloss, impact strength, tensile elongation and the like. As another means for improving rigidity, there is a method of using various inorganic fillers such as talc, calcium carbonate, mica, valium sulfate, asbestos, and calcium silicate, but the lightness and transparency characteristic of polypropylene are impaired. In addition, there is a drawback that impact strength, gloss, tensile elongation, workability, etc. are deteriorated. Therefore, it is necessary to develop polypropylene with high crystallinity in order to increase the rigidity and heat resistance of polypropylene, and attempts have been made to develop crystalline polypropylene by devising the polymerization catalyst and polymerization method, but they have slightly improved rigidity. However, even if the rigidity is still insufficient and the transparency is insufficient, and even if the aim is to develop polypropylene with high isotacticity, the isotacticity is still within the range of conventional technology. The effect of improving the rigidity of the molded product is still insufficient.

[0004]

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 homopolymer having excellent properties.

[0005]

As a result of intensive studies, the inventors of the present invention have found that it is necessary to improve the crystallinity in order to improve the rigidity and heat resistance of polypropylene. However, high rigidity and high heat resistance are required. It has been found that the crystallinity for developing is not more than a certain value and changes depending on the elastic modulus and frequency in the dynamic melt viscoelasticity of polypropylene, and
When the crystallinity of polypropylene is represented by the isotactic pentad fraction (IPF), the frequency ω ₀ and the elastic modulus G ₀ in IPF and viscoelasticity are expressed by the equation: IPF ≧ 1.65log ω ₀ −1.15logG ₀ +9
When the relation of 9.3 was satisfied, it was found that the crystalline polypropylene exhibited high rigidity and high heat resistance, and completed the first invention of the present application. 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. The inventors have found the second invention of the present application.

That is, the gist of the present invention is that the frequency at which the storage elastic modulus G'in the dynamic melt viscoelasticity measurement and the loss elastic modulus G "match is ω ₀ , and the elastic modulus at that time is G _0. , Between these and the isotactic pentad fraction in ¹³ C-NMR measurement: IPF IPF ≧ 1.65 log ω ₀ −1.15 log G ₀ +9
9.3 is a crystalline polypropylene characterized by satisfying the following relation, and (B) a solid component containing magnesium, titanium, a halogen and an electron-donating compound as essential components, and (B) an organoaluminum compound. And (C) in the presence of an organosilicon compound represented by the following general formula (1),

[Chemical 2] [Wherein R ¹ is a cyclic substituent containing an ether or thioether bond in the ring, an oxy group of a cyclic substituent containing an ether bond in the ring, a cyclic substituent containing a ketone bond in the ring, a heterocyclic substituent containing a nitrogen atom, a silicon atom] Containing heterocyclic substituent, substituent having lactone skeleton structure, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O—, R ⁵ ₃ Si— or R ⁶ ₃
SiO-, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 0 or 1, z is 2 or 3, x +
y + z = 4, R ⁴ is a hydrocarbon group having 3 to 10 carbon atoms, and R ⁵ and R ⁶ are hydrocarbon groups having 1 to 10 carbon atoms. ] (D) A polypropylene obtained by polymerizing propylene using an α-olefin polymerization catalyst component which is brought into contact with an olefin, wherein the storage elastic modulus G'and the loss elastic modulus G are measured in dynamic melt viscoelasticity measurement. Where ω ₀ is the frequency at which "" matches and G ₀ is the elastic modulus at that time, IPF ≧ 1.65 log ω ₀ − between these and the isotactic pentad fraction in ¹³ C-NMR measurement: IPF. 1.15 logG ₀ +9
A crystalline polypropylene characterized by satisfying the relationship of 9.3.

Here, the elastic modulus G ₀ and the frequency ω ₀ in the viscoelasticity measurement of polypropylene in the present invention are values obtained by the following method. Using a dynamic melt viscoelasticity measuring device, for example, Rheometrics RMS-800 viscoelasticity measuring device, measurement temperature: 200 ° C., strain: γ = 15%,
Frequency: 0.01-100 rad / sec, Plate:
Parallel plate, sample: thickness 2mm, diameter 25m
1.5m after stabilizing the press molded product of m at the measurement temperature
Under the measurement conditions such as compression to m, the response of the storage elastic modulus G ′ and the loss elastic modulus G ″ to a certain range of the frequency ω is measured, and the obtained response values are plotted on the vertical axis and the elastic modulus G on the horizontal axis. Plotted in a diagram with the frequency ω on the axis, drawn G′-ω curve and G ″ -ω curve, and define the coordinates (G ₀ , ω ₀ ) of the intersection of these curves as the elastic modulus G ₀ and frequency ω ₀ . . FIG. 1 shows a schematic diagram of the G ₀ , ω ₀ measuring method.

Further, the isotactic pentad fraction (IPF) in the present invention means Macromolecule.
s, 6 , 925 (1973), ie ¹³
It is an isotactic fraction in a pentad unit in a polypropylene molecular chain measured by a method using C-NMR. In other words, the isotactic pentad fraction is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded. However, regarding attribution of peaks, Macromo
leules, 8 , 687 (1975). Specifically, the isotactic pentad unit is measured as the intensity fraction of the mmmm peak in all the absorption peaks in the methyl carbon region of the ¹³ C-NMR spectrum.

The value of the isotactic pentad fraction in the present invention is the value of the obtained crystalline polymer as it is, and is not the value of the polymer after extraction, fractionation and the like. In the polypropylene of the present invention, it is necessary that the frequency ω ₀ is 0.1 or more and the elastic modulus G ₀ is 600,000 or less, ω ₀ is less than 0.1, and G ₀ is 6
When it exceeds 100,000, the moldability of the obtained polypropylene deteriorates. Further, the isotactic pentad fraction of polypropylene in the present invention: IPF is IPF <
If it is 1.65 log ω ₀ −1.15 log G ₀ +99.3, the rigidity and heat resistance are insufficient, and preferably IP.
F ≧ 1.65 log ω ₀ −1.15 log G ₀ +99.
It is 5.

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-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, 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-mentioned magnesium compound can be prepared from metallic magnesium or other magnesium compounds when preparing the component A. As one example thereof, metal magnesium, a halogenated hydrocarbon and an alkoxy group-containing compound of the general formula X _n M (OR) _mn [wherein, X is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, 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, phenethyl, 3-phenylpropyl, and other aralkyl groups, and the like. 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.

Compound where M is carbon C (OMe) ₄ , C (OE contained in the 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 (OM
e) ₃ , MeC (OEt) ₃ , EtC (OMe) ₃ , E
tC (OEt) ₃ , cyHeC (OEt) ₃ , PhC
(OMe) ₃ , PhC (OEt) ₃ , CH ₂ ClC (O
Et) ₃ , MeCHBrC (OEt) ₃ ; MeCHCl
C (OEt) ₃ ; ClC (OMe) ₃ , ClC (OE
t) ₃ , ClC (Oi-Bu) ₃ , BrC (OE
t) ₃ ; MeCH (OM included in the formula X ₂ C (OR) ₂
e) ₂ , MeCH (OEt) ₂ , CH ₂ (OMe) ₂ ,
CH ₂ (OEt) ₂ , CH ₂ ClCH (OEt) ₂ , C
HCl ₂ CH (OEt) ₂ , CCl ₃ CH (OE
t) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OE
t) _{2 and the} like.

Compound where M is Silicon Si (OMe) ₄ , Si Included 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 (OP
h) ₃ ; ClSi (OMe) ₃ , ClSi (OE
t) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ ; Formula X ₂ Si (OR) ₂
Included in Me ₂ Si (OMe) ₂ and Me ₂ Si (OE
t) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (OE
t) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ Si
H (OEt) ₂ ; MeBuSi (OEt) ₂ : X ₃ Si
Me ₃ SiOMe, Me ₃ SiOEt contained in OR,
Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ SiOE
t, Ph ₃ SiOEt and the like.

Compound in which M is Boron B (OEt) ₃ and 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 included in the 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 can be mentioned. Compound in which M is phosphorus P (OMe) ₃ , P (OE contained in the 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, ZnE
t ₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaPh
₂ etc.

(2) Titanium Compound The 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 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, p
-Ethyl 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, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromelliticate, tetraethyl pyromelliticate, tetrabutyl pyromelliticate. Etc.

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,
Examples thereof include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and 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. Ethers are
It is represented by the general formula R ⁵ OR ⁶ . In the formula, R ⁵ , R ⁶
Is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl, 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, 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. After contacting component 1 and component 3, component 2 is contacted. A method such as contacting component 1, component 2 and component 3 at the same time can be adopted. 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, methylchloroform, methylbromoform, methyliodoform, 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 hydroxyl groups 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 are 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 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
-Chlor-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-
Chlorresorcin, 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-
Bromresorcin, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3- Chlor-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-tribrom-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, tetrafluororesorcin and the like can be mentioned.

Halogenated silicon having a hydrogen-silicon bond
As a compound, HSiCl₃, H₂SiCl₂, H₃S
iCl, H (CH₃) SiCl₂, H (C₂H_Five) Si
Cl₂, H (t-C_FourH₉) SiCl₂, H (C
₆H_Five) SiCl₂, H (CH₃)₂SiCl, H (i
-C₃H₇)₂SiCl, H₂(C₂H_Five) SiCl,
H₂(N-C_FourH₉) SiCl, H₂(C₆H_FourC
H₃) SiCl, H (C₆H_Five) ₂For example, SiCl
Be done. Metal halides include B, Al, Ga, In,
Salts of Tl, Si, Ge, Sn, Pb, As, Sb, Bi
And fluoride, bromide and iodide, especially BC
l₃, BBr₃, BI₃, AlCl₃, AlBr₃, G
aCl₃, GaBr₃, InCl₃, TlCl₃, Si
Cl_Four, SnCl_Four, SbCl_Five, SbF_FiveAnd so on
is there.

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-58-198.
No. 503, No. 62-146904, and the like. More specifically, (a) magnesium metal, (b) halogenated hydrocarbon, (c) general formula X _n M (OR) _The magnesium-containing solid obtained by contacting the _mn compound (the same as the above-mentioned alkoxy group-containing compound) is contacted with (d) halogen-containing alcohol, and then (e) electron donating compound and (f) titanium compound. Method (JP-A-63 / 1988)
-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). (JP-A-62-146904), (a) magnesium dialkoxide and (b) hydrogen-
After contacting with a silicon halide compound having a silicon bond, (c) contact with an electron donating compound, and then (d)
Method of contacting with titanium compound (JP-A-58-1985)
No. 03), and among these, the most preferable method is. 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 Specific examples of the organoaluminum compound (hereinafter referred to as component B) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and the like. To be

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula (1). In the formula, R ¹ is a cyclic substituent containing an ether or thioether bond in the ring, an oxy group of a cyclic substituent containing an ether bond in the ring, a cyclic substituent containing a ketone bond in the ring, a heterocyclic substituent containing a nitrogen atom, and silicon. Atom-containing heterocyclic substituent,
A substituent having a lactone skeleton structure, R ² has 1 to 1 carbon atoms
0 hydrocarbon groups, R ⁴ O-, R ⁵ ₃ Si- or R
⁶ ₃ SiO—, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 0 or 1, z is 2 or 3,
x + y + z = 4, R ⁴ is a hydrocarbon group having 3 to 10 carbon atoms, and R ⁵ and R ⁶ are hydrocarbon groups having 1 to 10 carbon atoms. Specific examples of R ^{1 will be} given. Each of the following is RA,
RB ... etc.

[0031]

[Chemical 3]

[0032]

[Chemical 4] R ² in the above general formula of the component C represents a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O, R ⁵ ₃ Si or R ⁶ ₃ SiO, and R ⁴ is a hydrocarbon group having 3 to 10 carbon atoms. The groups R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10 carbon atoms. Examples of these hydrocarbon groups include alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups and aralkyl groups.

Examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, As the alkenyl group such as a decyl group, vinyl, allyl, propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,
1-octenyl, 1-decenyl, 1-methyl-1-pentynyl, 1-methyl-1-heptenyl and the like, cycloalkyl groups such as cyclopentyl, cyclohexyl and methylcyclohexyl groups, and cycloalkenyl groups such as cyclopentenyl. , A cyclohexenyl group, a methylcyclohexenyl group, etc., a cycloalkadienyl group, a cyclopentadienyl group, a methylcyclopentadienyl group, an indenyl group, etc., and an aryl group, a phenyl group, a tolyl group, a xylyl group, etc. Examples of the alkyl group include benzyl, phenethyl and 3-phenylpropyl groups. Hereinafter, the component C will be exemplified. In the following, symbols such as [RA], [RB] ... Correspond to the above symbols of R ¹ in the general formula (1) of the component C, Me is methyl, Et is ethyl, Pr is propyl and Bu. Represents butyl, CyPe represents cyclopentyl, and CyHe represents a cyclohexyl group.

[RA] ₂ Si (OMe) ₂ , [RA]
(I-PrO) Si (OMe) ₂ , [RB] (i-Pr
O) Si (OMe) ₂ , [RD] (t-Bu) Si (O
Me) ₂ , [RD] (Me ₃ SiO) Si (OM
e) ₂ ; [RA] (Me ₃ SiO) Si (OEt) ₂ ,
[RA] (i-Pr) Si (OEt) ₂ , [RC] (i
-PrO) Si (OEt) _2, [RD] (Me ₃ Si
O) Si (OEt) ₂ , [RD] (t-Bu) Si (O
Et) ₂ ; [RA] Si (OMe) ₃ , [RD] Si
(OMe) ₃ , [RE] Si (OMe) ₃ ; [RA] S
i (OEt) ₃ , [RD] Si (OEt) ₃ , [RB]
Si (OEt) ₃ ; [RD] MeSi (OMe) ₂ ,
[RF] MeSi (OMe) ₂ , [RF] (i-Pr
O) Si (OMe) ₂ , [RF] (t-Bu) Si (O
Me) ₂ , [RG] MeSi (OMe) ₂ , [RG]
(CyPe) Si (OMe) ₂ , [RG] (CyHe)
Si (OMe) ₂ , [RH] (CyHe) Si (OM
e) ₂ ; [RI] (i-PrO) Si (OMe) ₂ ,
[RJ] Si (OEt) ₃ , [RK] Si (OMe) ₃
[RL] (i-Pr) Si (OEt) ₂ ; [RM] Si
(OMe) ₃ , [RM] Si (OSiMe ₃ ) (OM
e) ₂ , [RN] Si (OMe) ₃ , [RN] Si (O
SiMe ₃ ) (OMe) ₂ , [RO] Si (OE
t) ₃ , [RP] Si (OEt) ₃ , [RQ] Si (O
SiMe ₃ ) (OMe) ₂ ; [RR] Si (OE
t) ₃ ; [RS] Si (OEt) ₃ , [RT] Si (O
Et) ₃ , [RU] Si (OMe) ₃ ; [RV] Si
(OEt) ₃ , [RW] Si (OMe) ₃ , [RX] S
i (OMe) ₃ , [RY] Si (OEt) ₃ , [RZ]
Si (OMe) ₃ .

Prepolymerization The prepolymerization of the solid component (component A) is carried out by contacting it with an olefin (component D) in the presence of an organoaluminum compound (component B) and an organosilicon compound (component C). Further, if necessary, it is preferable to add an electron donating compound (hereinafter referred to as component E) 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 organic silicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane and methyltrimethoxy. Silane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltri Phenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, Methyl dihexyl silane,
Dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, Examples thereof include diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, 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, 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, thiol Phenol, thiophene,
Ethyl 2-thiophenecarboxylate, Ethyl 3-thiophenecarboxylate, 2-Methylthiophene, Methyl mercaptan, Ethyl mercaptan, Isopropyl mercaptan, Butyl mercaptan, Diethyl thioether, Diphenyl thioether, Methyl benzene sulfonate, Methyl sulfite, Ethyl sulfite, etc. Is, 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-tetraethyltetrahydropyran, 2,2,6,6-tetramethyl Tetrahydropyran, 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-butylphenyl ketone, 2-ethyl ethyl furarate, isoamyl 2-furarate, methyl 2-furarate, 2
-Propyl furarate and the like, as a compound containing a phosphorus atom, triphenylphosphine, tributylphosphine,
Examples thereof include triphenyl phosphite, tribenzyl phosphite, diethyl phosphate, 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 is used so that the concentration in the prepolymerization system is 5 to 1000 mmol / liter, preferably 10 to 200 mmol / liter. The olefin polymer is incorporated into the component A by the prepolymerization, and the amount of the polymer is 0.1 to 200 g, particularly 0.5 to 50 g per 1 g of the component A.
Is desirable. 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 temperature as low as possible.
A temperature range of + 30 ° C, especially -20 ° C to + 5 ° C, is recommended.

Main Polymerization The catalyst component obtained as described above is used in combination with an organometallic compound and, if necessary, an electron donating compound, for homopolymerization of propylene or copolymerization with other monoolefins. Polymerization was performed to obtain the isotactic pentad fraction: IPF and the elastic modulus G ₀ determined by dynamic melt viscoelasticity measurement,
Crystalline polypropylene having a relationship with the frequency ω _{0 represented} by the above formula can be obtained.

Organometallic compounds that can be used are organic compounds of metals of groups I to III of the periodic table, and as the compound, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. Organoaluminum compounds that can be used include those represented by the general formula R ⁷ _n A
lX ′ _3-n (wherein R is 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 and the like having 1 carbon atom.
Particularly preferred are alkylaluminum compounds having 1 to 18, preferably 2 to 6 carbon atoms, or a mixture or feedstock thereof. Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, and trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum iodide, diisobutyl aluminum chloride, etc. Alkyl aluminum sesquichlorides such as dialkyl aluminum monohalide, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, and methyl aluminum sesquichloride. Harai Dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide and other dialkyl aluminum monoalkoxides, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl Examples include dialkyl aluminum hydrides such as aluminum hydride. Among these,
Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are particularly preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially available diethylaluminum chloride, ethylaluminum dichloride,
It can be used in combination with ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, a mixture thereof or a feed compound.

It is also possible to use an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such compounds include

[Chemical 5] Etc. can be illustrated.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride and diethylzinc, and LiAl (C
Examples thereof include compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . The amount of the organometallic compound used with respect to the catalyst component of the present invention is usually 1 to 2,000 gram moles, and particularly preferably 20 to 500 gram moles, per gram atom of titanium in the catalyst component. When an electron-donating compound is used, the ratio of the organometallic compound to the electron-donating compound is 0.1 to 40, preferably 1 to 25 g atom of the organometallic compound as aluminum to 1 mol of the electron-donating compound. It is selected in the range of.

The propylene polymerization reaction may be carried out in a gas phase or a liquid phase, and when the polymerization is carried out in a 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.

[0045]

EXAMPLES The present invention will be specifically described with reference to examples and application examples. The percentages (%) in the examples are by weight unless otherwise specified. (Example 1) Preparation of component A 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. Then, 55.7 ml of HC (OC ₂ H ₅ ) _{3 was} added dropwise to this reaction solution over 1 hour. After completion of dropping, the reaction was carried out at 60 ° 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 to obtain 19.0% magnesium and 28.9% chlorine. 31.6 g of a magnesium-containing solid containing was recovered.

In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, 6.3 g of magnesium-containing solid and 50 ml of n-heptane were put into a suspension under a nitrogen gas atmosphere to make a suspension, which was stirred at room temperature for 2,2. A mixed solution of 20 ml (0.02 mmol) of 2-trichloroethanol 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 with 100 ml of n-hexane at room temperature four times each, and further washed twice with 100 ml each of toluene 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.
Wash twice with ml at 90 ° C. Furthermore, 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 100 m at room temperature.
The product was washed 7 times with 1 n-hexane to obtain 5.5 g of the component.

A 500 ml reactor equipped with a prepolymerization stirrer was charged with 3.5 g of the component A obtained above and 300 ml of n-heptane under a nitrogen gas atmosphere and cooled to 0 ° C. with stirring. Next, an n-heptane solution (2.0 mol / liter) of triisobutylaluminum (hereinafter abbreviated as TIBAL) and bis (oxacyclopent-3-yl) dimethoxysilane were added to TIBAL and bis (oxa) in the reaction system. The concentrations of cyclopent-3-yl) dimethoxysilane are 80 mmol / l and 10 mmol / l, respectively.
It was added so as to be liter and stirred for 5 minutes. Then, after depressurizing the system, propylene gas was continuously supplied to polymerize propylene for 3 hours. After the completion of the polymerization, the propylene in the gas phase was purged with nitrogen gas, and 100 ml of n
-The solid phase was washed with hexane three times at room temperature. Furthermore,
The solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 3.0 g per component Alg.

In a 5 liter stainless steel autoclave equipped with the main polymerization stirrer, 6 ml of an n-heptane solution of TIBAL (0.1 mol / liter) and an n-heptane solution of a dineopentyldimethoxysilane (0 0.01 ml / liter) 6 ml were mixed and held for 5 minutes.
Next, 5.2 liters of hydrogen gas as a molecular weight controlling agent and 3 liters of liquid propylene were injected under pressure, and then the reaction system was heated to 70 ° C. 50.2 m of the catalyst component obtained above
After charging g to the reaction system, propylene was polymerized for 1 hour. After the polymerization was completed, unreacted propylene was purged, and
09.3 g of white polypropylene powder was obtained. Ingredient Al
Polypropylene production amount (CE) per g is 40.6 kg
Met. The ω ₀ of this polypropylene is 250.00,
G ₀ is 258,700, isotactic pentad fraction (IPF) is 97.3%, and flexural modulus is 18,100.
The kgf / cm ² and heat distortion temperature were 120 ° C. The results are shown in Table 3.

(Examples 2 to 4) Prepolymerization and main polymerization were carried out in the same manner as in Example 1 under the conditions shown in Tables 1 and 2. Table 3 shows the results of measuring the polymerization and physical properties of these polypropylenes. (Comparative Examples 1 and 2) Main polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 2 except that prepolymerization was not carried out. Table 3 shows the results of measuring the polymerization and physical properties of these polypropylenes. As is clear from Table 3, polypropylene having an isotactic pentad fraction (IPF) within the range of the present invention has higher flexural modulus and heat distortion temperature than those outside the range, and has higher rigidity and heat resistance. You can see that it is improving.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3] Flexural modulus According to JIS K-6758. Heat distortion temperature According to JIS K-7202.

[0053]

As is apparent from the examples of the present invention, polypropylene having an isotactic pentad fraction (IPF) within the range of the present invention has a flexural modulus and a heat distortion temperature outside the ranges. It has higher rigidity, heat resistance, and moldability and impact resistance.
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 is a schematic diagram illustrating a method for measuring G ₀ and ω ₀ .

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masashi Nakajima 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Corporation Research Institute (72) Inventor Satoshi Ueki Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture 1- 3-1 Inside Tonen Research Institute

Claims (2)

[Claims] 1. When the frequency at which the storage elastic modulus G ′ in the dynamic melt viscoelasticity measurement and the loss elastic modulus G ″ match is ω ₀ and the elastic modulus at that time is G ₀ , these and ¹³ C− NM
Isotactic pentad fraction in R measurement: IP
Between F and IPF ≧ 1.65 log ω ₀ −1.15 log G ₀ +9
A crystalline polypropylene characterized by satisfying the relationship of 9.3. 2. A solid component containing (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
In the presence of (B) an organoaluminum compound and (C) an organosilicon compound represented by the following general formula (1), [Wherein R ¹ is a cyclic substituent containing an ether or thioether bond in the ring, an oxy group of a cyclic substituent containing an ether bond in the ring, a cyclic substituent containing a ketone bond in the ring, a heterocyclic substituent containing a nitrogen atom, a silicon atom] Containing heterocyclic substituent, substituent having lactone skeleton structure, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O—, R ⁵ ₃ Si— or R ⁶ ₃
SiO-, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 0 or 1, z is 2 or 3, x +
y + z = 4, R ⁴ is a hydrocarbon group having 3 to 10 carbon atoms, and R ⁵ and R ⁶ are hydrocarbon groups having 1 to 10 carbon atoms. ] (D) A polypropylene obtained by polymerizing propylene using an α-olefin polymerization catalyst component which is brought into contact with an olefin, wherein the storage elastic modulus G'and the loss elastic modulus G are measured in dynamic melt viscoelasticity measurement. Where ω ₀ is the frequency at which "" matches and G ₀ is the elastic modulus at that time, IPF ≧ 1.65 log ω ₀ − between these and the isotactic pentad fraction in ¹³ C-NMR measurement: IPF. 1.15 logG ₀ +9
A crystalline polypropylene characterized by satisfying the relationship of 9.3.