JPH08188616A - Crystalline polypropylene - Google Patents

Abstract

PURPOSE: To obtain a crystalline polypropylene having improved rigidity and heat resistance and high hardness, and being excellent in fatigue resistance, abrasion resistance, dimensional stability, chemical resistance, moldability, etc., by forming a polymer having specified properties by using a specified catalyst. CONSTITUTION: A crystalline polypropylene obtained by using an α-olefin polymerization catalyst component prepared by bringing a solid component essentially consisting of a metal oxide, Mg, Ti, a halogen and an electron-donating compound into contact with an olefin in the presence of an organoaluminum compound and an organosilicon compound represented by the formula: R<1> Si(OR<2> )x (OR<3> )y (wherein R<1> is a 5-7 C alicyclic hydrocarbon group; R<2> is 2-ethoxyethyl or 2-methyl-3-butin-2-yl; R<3> is methyl or ethyl; (x) is 1-2; (y) is 1-2; and x+y=3), having a weight-average molecular weight(Mw) of 5000-1000000 as measured by GPC and satisfying the relationship: Tp>=114.42+0.90971logMw (wherein Tp is the elution peak temperature as determined by the climbing temperature fractionation).

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 low specific gravity and is widely used in the fields of containers, packaging materials and the like. However, depending on the application, these properties are not sufficiently satisfied, and their use is limited.

Among the performances mentioned above, polypropylene is polystyrene and ABS because of its rigidity and heat resistance.
Inferior to resin. Therefore, polypropylene cannot be used as a material for producing a molded product requiring rigidity and heat resistance, and instead of the polystyrene or ABS resin as a material for a molded product requiring rigidity and heat resistance. , If polypropylene is intentionally used, in order to satisfy the above-mentioned properties, it is necessary to form a thick molded product, which prevents the molded product from being thin and increases the cost of the molded product. Or the application of the polypropylene composition cannot be expanded.

If polypropylene has excellent rigidity, chemical resistance, moldability, heat resistance, hardness, etc., such polypropylene is polystyrene or AB.
As an alternative to the S resin, the application can be expanded and a thin molded product can be finished, so resource saving and cost reduction can be expected.

As a known technique for improving the rigidity of crystalline polypropylene, for example, an organic nucleating agent such as paratertiary butyl 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 of the organic nucleating agent significantly reduces gloss, impact strength, tensile elongation and the like. As another means for improving rigidity, there is a method of adding various inorganic fillers such as talc, calcium carbonate, mica, valium sulfate, asbestos, and calcium silicate. In addition, there is a defect that impact strength, gloss, tensile elongation, workability, etc. are deteriorated.

Therefore, it is necessary to develop polypropylene having high crystallinity in order to improve the rigidity and heat resistance of polypropylene, and various crystalline polypropylenes have been attempted to be developed by devising a polymerization catalyst and a polymerization method. Although the rigidity is slightly improved, it 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. Yes The effect of improving the rigidity of molded products is still insufficient.

[0007]

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.

[0008]

As a result of intensive studies, the present inventors have found that it is necessary to improve the stereoregularity in order to increase the rigidity and heat resistance of polypropylene, but the stereoregularity is increased. When the elution peak temperature (Tp) in the temperature rising fractionation method is used as a measure of the stereoregularity depending on the elution temperature by the temperature fractionation measurement, the Tp value for expressing high rigidity and high heat resistance is a constant value. However, it was found that Tp and Mw were changed according to the weight average molecular weight (Mw) of polypropylene, and the stereoregularity of polypropylene was expressed by the elution peak temperature (Tp) in the temperature rising fractionation method. When the relation of the formula Tp ≧ 114.42 + 0.9097 log Mw is satisfied, it was found that the crystalline polypropylene exhibits high rigidity and high heat resistance, and the present invention has been completed.

SUMMARY OF THE INVENTION That is, the gist of the present invention is that (A) a solid component containing a metal oxide, magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organoaluminum compound and (C). In the presence of the organosilicon compound represented by the following general formula,

Embedded image R ¹ Si (OR ² ) _x (OR ³ ) _y [wherein R ¹ is an alicyclic hydrocarbon group having 5 to 7 carbon atoms, R ^1
2 is a 2-ethoxyethyl group or a 2-methyl-3-butyn-2-yl group, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 1 or 2, x + y
= 3. ]

(D) a polypropylene obtained by polymerizing propylene using an α-olefin polymerization catalyst component that is brought into contact with an olefin, and having a weight average molecular weight (measured by gel permeation chromatography (GPC) ( Mw) is 5,000 to 1,0
It is a crystalline polypropylene characterized in that the elution peak temperature (Tp) determined from the temperature rise fractionation measurement and Mw satisfy the relationship of Tp ≧ 114.42 + 0.9097 log Mw in the range of 0,000.

Here, the elution peak temperature (Tp) obtained from the temperature rising fractionation measurement in the present invention means the temperature of the column after the sample solution is introduced into the column and the sample is adsorbed by the packing material in the column. It is measured by increasing the temperature of the polymer and detecting the concentration of the polymer eluted at each temperature.The analysis chart between each temperature and the concentration of the polymer is created, and the peak when the largest peak appears. The position (temperature). Further, the weight average molecular weight (M
w) is a gel permeation chromatograph (GP
C) and polystyrene under the same conditions. Makromol. Chem 179,211
7 is a value calibrated based on the universal calibration principal described in 7 (1978).

The polypropylene of the present invention must have a weight average molecular weight (Mw) in the range of 5,000 to 1,000,000, and the weight average molecular weight (Mw) is
If it is less than 5,000, the impact resistance is lowered,
If it exceeds 100,000, the moldability will decrease.

The elution peak temperature (Tp) determined by the temperature-raising fractional measurement of the polypropylene of the present invention is 11
4.42 + 0.9097 log Mw or more, preferably 1
14.67 + 0.9097 log Mw or more, more preferably 114.92 + 0.9097 log Mw or more, if the value is less than 114.42 + 0.9097 log Mw, the rigidity and heat resistance of polypropylene are insufficient,
Molded products with high rigidity and high heat resistance cannot be obtained. The polymerization catalyst used in the present invention is as follows.

The solid component (hereinafter referred to as component A) used in the present invention contains metal oxides, magnesium, titanium, halogens and electron donating compounds as essential components. Such components are usually metal oxides, A magnesium compound, a titanium compound and an electron donating compound, and in the case where each of the above compounds does not have a halogen, a halogen-containing compound is prepared by bringing them into contact with each other.

(1) Metal Oxide The metal oxide used in the present invention can be selected from Group II to Periodic Table.
An oxide of an element selected from the group of Group IV elements,
Examples thereof are B ₂ O ₃ , MgO, Al ₂ O ₃ and S.
iO ₂ , CaO, TiO ₂ , ZnO, ZrO ₂ , SnO
₂ , BaO, ThO _{2 and the} like. Among these, B ₂ O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , TiO ₂ ,
ZrO ₂ is preferable, and SiO ₂ is particularly preferable. Furthermore,
Complex oxides containing these metal oxides, such as SiO ₂ −
_{MgO, SiO 2 -Al 2 O 3} , SiO 2 -TiO 2,
_{SiO 2 -V 2 O 3, SiO} 2 -Cr 2 O 3, SiO 2
-TiO ₂ -MgO and the like may also be used.

The shape of these metal oxides is usually powdery. Since the shape and shape of the powder often affect the shape of the olefin polymer to be obtained, it is desirable to adjust it appropriately. The metal oxide is
For the purpose of removing poisonous substances in use, it is desirable to burn at a temperature as high as possible and handle it so that it does not come into direct contact with the atmosphere.

(2) Magnesium Compound The magnesium compound is represented by the general formula MgR ⁴ R ⁵ . In the formula, R ⁴ and R ⁵ represent the same or different hydrocarbon groups, OR ′ groups (R ′ is a hydrocarbon group), and halogen atoms. More specifically, the hydrocarbon group of R ⁴ and R ⁵ 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. In the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, cyHe: cyclohexyl, respectively. Show.

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 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 a 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
Indicates the valence of M, 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.

Compound where M is carbon C (OMe) ₄ , C (OE contained in formula C (OR) ₄
t) ₄ , C (OPr) ₄ , C (OBu) ₄ , C (Oi-
Bu) ₄ , C (OHe) ₄ , C (OOct) ₄ ; Formula XC
HC (OMe) ₃ , HC (OE) contained in (OR) ₃
t) ₃ , HC (OPr) ₃ , HC (OBu) ₃ , HC
(OHe) ₃ , HC (OPh) ₃ , MeC (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 .

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.

Compound in which M is Boron B (OEt) ₃ , B (OB) included in Formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) ₃ . Compound when M is aluminum Al (OMe) ₃ , Al contained 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 . Compound in which M is phosphorus P (OMe) ₃ , P (OE) included in the formula P (OR) ₃
t) ₃ , P (OBu) ₃ , P (OHe) ₃ , P (OP
h) ₃ .

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 ⁴
It is represented by R ⁵ · n (MR ⁶ _m ). As the metal,
It is aluminum, zinc, calcium or the like, and R ⁶ 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 ⁶ _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.

(3) 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.

(4) 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 anhydrides, carboxylic esters, carboxylic 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 ⁷ OH. In the formula, R ⁷ 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 ⁸ OR ⁹ . In the formula, R ⁸ and R ⁹ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R ⁸ and R ⁹ 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 metal oxide (component 1), a magnesium compound (component 2), a titanium compound (component 3) and an electron donating compound (component 4) in that order. After contacting the ingredient 2 with
Component 4 and component 3 are contacted in that order, component 1 and component 2 are contacted, then component 3 and component 4 are contacted simultaneously, component 2 and component 3 are contacted, and then component 4 and component 1
Are contacted in that order, components 2 and 4 are contacted, and then components 3 and 1 are contacted in that order. A method of contacting the component 2, the component 3, and the component 4 at the same time, and then contacting the component 1, or the like can be adopted. It is also possible to contact the halogen-containing compound before contacting component 3.

Examples of the halogen-containing compound include halogenated hydrocarbons, halogen-containing alcohols, halogenated silicon compounds having a hydrogen-silicon bond, and IIIa of the periodic table.
Examples thereof include halides of Group IVa, IVa, and Va elements (hereinafter referred to as metal halides).

The halogenated hydrocarbon has 1 to 10 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.

Examples of the halogenated silicon compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ and H
_{3 SiCl, H (CH 3)} SiCl 2, H (C 2 H 5)
_{SiCl 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)
_{SiCl, H (C 6 H 5} ) 2 SiCl and the like.

As the metal halide, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
Examples thereof include chlorides, fluorides, bromides and iodides of i, particularly BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ and AlBr.
₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TlC
l ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF ₅
Etc. are suitable.

The contact with the component 1, the component 2, the component 3 and the component 4, and the halogen-containing compound which can be optionally contacted is carried out by mixing and stirring in the presence of an inert medium or in the absence thereof. This is done by mechanical co-milling. The contact can be performed under heating at 40 to 150 ° C. The inert medium, hexane, heptane, saturated aliphatic hydrocarbons such as octane, cyclopentane, saturated alicyclic hydrocarbons such as cyclohexane, benzene, toluene,
Aromatic hydrocarbons such as xylene can be used.

A preferable method for preparing the component A in the present invention is described in JP-A-58-162607 and JP-A-55-94909.
No. 55-115405, No. 57-108107.
No. 61-21109, 61-174204,
The methods disclosed in JP-A Nos. 61-174205, 61-174206, 62-7706 and the like can be mentioned. More specifically, a method in which a reaction product of a metal oxide and a magnesium alkoxide is contacted with an electron donating compound and a tetravalent titanium halide (JP-A-58-162607),

A method of bringing a reaction product of an inorganic oxide and a magnesium hydrocarbyl halide compound into contact with a Lewis base compound and titanium tetrachloride (JP-A-55-9).
4909), a method in which a reaction product of a porous carrier such as silica with an alkyl magnesium compound is contacted with an electron donating compound and a silicon halide compound before contacting with a titanium compound (JP-A-55-115405). , Ibid. 57-108
No. 107),

A method of contacting a metal oxide, an alkoxy group-containing magnesium compound, an aromatic polyvalent carboxylic acid having a carboxyl group at the ortho position or a derivative thereof, and a titanium compound (JP-A-61-174204), metal oxide , An alkoxy-containing magnesium compound,
Method of contacting a silicon compound having a hydrogen-silicon bond, an electron-donating compound and a titanium compound (JP-A-61-161)
174205),

A method of contacting a metal oxide, an alkoxy-containing magnesium compound, a halogen element or a halogen-containing compound, an electron donating compound and a titanium compound (JP-A-61-174206), metal oxide, dihydrocarbyl magnesium and halogen. A method of bringing a reaction product obtained by bringing a contained alcohol into contact with an electron-donating compound and a titanium compound (JP-A-61-21109),

A solid obtained by contacting a metal oxide, a hydrocarbyl magnesium and a hydrocarbyloxy group-containing compound (corresponding to the alkoxy group-containing compound) is contacted with a halogen-containing alcohol, and further contacted with an electron donating compound and a titanium compound. The method (Japanese Patent Laid-Open No. 62-7706). Among these, the method (1) is preferable, and the method (3) is particularly preferable. 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 The organoaluminum compound (hereinafter referred to as component B) is
General formula

Embedded image AlR ₃ [wherein R represents an alkyl group having 1 to 12 carbon atoms]. ]
It is represented by. Specific examples include trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum and the like.

Organosilicon Compound An organosilicon compound which is one component of the catalyst of the present invention (hereinafter, referred to as
It is called component C. ) Is the following general formula

Embedded image R ¹ Si (OR ² ) _x (OR ³ ) _y is represented. In the formula, R ¹ is an alicyclic hydrocarbon group having 5 to 7 carbon atoms, R ² is a 2-ethoxyethyl group or 2-methyl-3-butyn-2-yl group, and R ³ is a methyl group or ethyl. A group, x is 1 or 2, y is 1
Or 2, x + y = 3.

Specific examples of the component C will be listed below. Cyclopentyl (2-ethoxyethoxy) dimethoxysilane, cyclopentyldi (2-ethoxyethoxy) methoxysilane, cyclopentyl (2-ethoxyethoxy) diethoxysilane, cyclopentyldi (2 -Ethoxyethoxy) ethoxysilane, cyclohexyl (2-ethoxyethoxy) dimethoxysilane, cyclohexyldi (2-
Ethoxyethoxy) methoxysilane, cyclohexyl (2-ethoxyethoxy) diethoxysilane, cyclohexyldi (2-ethoxyethoxy) ethoxysilane, cycloheptyl (2-ethoxyethoxy) dimethoxysilane, cycloheptyldi (2-ethoxyethoxy) methoxysilane , Cycloheptyl (2-ethoxyethoxy) diethoxysilane, cycloheptyldi (2-ethoxyethoxy) ethoxysilane, cyclopentyl (2-methyl-
3-butyne-2-oxy) dimethoxysilane, cyclopentyldi (2-methyl-3-butyne-2-oxy) methoxysilane, cyclopentyl (2-methyl-3-butyne-2-oxy) diethoxysilane, cyclopentyldi ( 2-methyl-3-butyne-2-oxy) ethoxysilane, cyclohexyl (2-methyl-3-butyne-2-oxy) dimethoxysilane, cyclohexyldi (2-methyl-3-butyne-2-oxy) methoxysilane, Cyclohexyl (2-methyl-3-butyne-2-oxy) diethoxysilane, cyclohexyldi (2-methyl-3-butyne-2-oxy) ethoxysilane, cycloheptyl (2-methyl-3-butyne-2-oxy) ) Dimethoxysilane, cycloheptyldi (2-methyl-3-butyne-2)
-Oxy) methoxysilane, cycloheptyl (2-methyl-3-butyne-2-oxy) diethoxysilane, cycloheptyldi (2-methyl-3-butyne-2-oxy)
Examples include ethoxysilane.

The prepolymerization of prepolymerized solid component (component A), the presence of an organoaluminum compound (component B) and organic silicon compound (component C), is done by contacting the olefin (component D). 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 consisting of an organic silicon compound and an electron-donating compound containing a hetero atom such as nitrogen, sulfur, oxygen or phosphorus can be used. preferable. The organosilicon compound is preferably one in which a total of four alkyl groups and alkoxy groups are bonded to silicon atoms, these alkyl groups and alkoxy groups may be chain-like, and some of them are hetero elements such as O, N and S. May be replaced with.

Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane,
Tetrabenzyloxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane , Butyltributoxysilane, butyltriphenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane,
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 organometallic compound is used in combination with a catalyst component, or may be used after being brought into contact with the organometallic compound in advance. As the olefin, in addition to ethylene, α-, such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene
Olefins can 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 ° C., more preferably −30 ° C.
It is performed at a temperature of 20 ° C to + 15 ° C. 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 50 to 5 in the prepolymerization system.
It is used in an amount of 00 mmol / liter, preferably 80 to 200 mmol / liter, and is 4 to 50,000 mol, preferably 6 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 1 to 100 mmol / liter, preferably 5 to 50 mmol / liter. The olefin polymer is incorporated into the component A by the prepolymerization.
It is desirable that the amount is 0.1 to 200 g, especially 0.5 to 50 g.

The catalyst component of the present invention prepared as described above can be diluted or washed with the above-mentioned inert medium, but from the viewpoint of preventing storage deterioration of the catalyst component,
It is particularly desirable to wash. After washing, it may be dried if necessary. When the catalyst component is stored, it is desirable to store it at a low temperature as much as possible, and a temperature range of -50 ° C to + 30 ° C, particularly -20 ° C to + 5 ° C is recommended.

Main Polymerization The catalyst component obtained as described above can be used in combination with an organometallic compound and, if necessary, an electron donating compound to homopolymerize propylene or copolymerize with other monoolefins. A crystalline polypropylene in which the relationship between the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) after polymerization, and the elution peak temperature (Tp) and Mw obtained from the temperature rising fractionation measurement is 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. 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 _n AlX ′ _3-n (wherein R is an alkyl group or an aryl group, X ′ is a halogen atom, an alkoxy group or a hydrogen atom, and n is 1 ≦ n). Is an arbitrary number within the range of ≦ 3), and examples thereof include trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride. Particularly preferred is an alkylaluminum compound having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, or a mixture or complex compound thereof. Specifically, such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, diisobutyl aluminum chloride, etc. Dialkyl aluminum monohalide, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide,
Monoalkyl aluminum dihalides such as isobutyl aluminum dichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide And dialkylaluminum hydride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and the like. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable. Further, these trialkylaluminums are other organic aluminum compounds, for example, industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or complex compound thereof. Etc. can be used together.

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

Embedded image Etc. can be illustrated.

Examples of organic compounds other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, and other LiAl (C
Examples thereof include compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . The electron-donating compound that can be optionally combined with the catalyst component and the organometallic compound of the present invention is appropriately selected from electron-donating compounds that may be used in the prepolymerization of the component A. .

Two or more kinds of these electron donating compounds may be used. Further, these electron donating compounds may be used when an organometallic compound is used in combination with a catalyst component,
It may be used after being brought into contact with the organometallic compound in advance. The amount of the organometallic compound used with respect to the catalyst component of the present invention is usually 1 to 2,0 per 1 gram atom of titanium in the catalyst component.
00 gram moles, especially 20 to 500 gram moles are desirable. When an electron donating compound is used, the ratio of the organometallic compound to the electron donating compound is 0.1 mol of the organometallic compound as aluminum per 1 mol of the electron donating compound.
~ 40, preferably selected in the range of 1 to 25 gram atoms.

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.

[0064]

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. The elution peak temperature (Tp) obtained from the temperature rise fractionation measurement was carried out by introducing the sample solution into the column at 140 ° C. under the following conditions, cooling to 40 ° C. over 70 minutes, and stabilizing the temperature. The measurement was carried out by the measurement procedure of starting and detecting the polymer concentration eluted at each temperature, and the temperature at the position of highest elution concentration was taken as Tp.

Solvent: Ortho-dichlorobenzene Flow rate: 1 ml / min Temperature raising conditions: 100 ° C. or higher, step by 2 ° C., 40 min
Detector: Infrared detector for liquid chromatography Detection wavelength: 3.42 μm Column: 4 mmφ × 250 mm Filler: Glass beads Sample concentration: 4 mg / ml Injection volume: 0.5 ml Column temperature distribution: within 0.1 ° C

The weight average molecular weight (Mw) is measured by gel permeation chromatograph (GPC), and the measuring method is Model 150C manufactured by Waters Co., Ltd., Mixed B column 30 cm × 3 by Polymer Laboratory Co.
The measurement was carried out using a book, using a measurement temperature of 140 ° C. and a measurement solvent orthodichlorobenzene. For the molecular weight, polystyrene was measured under the same conditions, and Makromol. Che
m 179 , 2117 (1978), the calibration was carried out based on the universal calibration principal.

(Example 1) Preparation of component A A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. Into this flask, 5 g of silicon oxide (manufactured by DAVISON, trade name G-952) fired in a nitrogen stream at 200 ° C. for 2 hours and further 5 hours at 700 ° C. and 40 ml of n-heptane were put.
Further, 20 ml of a 20% n-heptane solution of n-butylethylmagnesium (hereinafter referred to as "BEM") (trade name: MAGALA BEM, manufactured by Texas Alkyls) was added, and the mixture was stirred at 90 ° C for 1 hour.

After the above suspension was cooled to 0 ° C., a solution of 11.2 g of tetraethoxysilane dissolved in 20 ml of n-heptane was added dropwise from the dropping funnel over 30 minutes. After the dropping is completed, the temperature is raised to 50 ° C over 2 hours, and the temperature is 50 ° C.
For 1 hour. After the reaction was completed, the supernatant was removed by decantation, and the produced solid was mixed with 60 ml of n-
It was washed with heptane at room temperature, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed 4 times.

To the above solid, 50 ml of n-heptane was added to form a suspension, and a solution of 8.0 g of 2,2,2-trichloroethanol dissolved in 10 ml of n-heptane was added to the suspension at 25 ° C. from a dropping funnel. Was added dropwise over 15 minutes. After completion of dropping, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, the mixture was washed twice with 60 ml of n-heptane and three times with 60 ml of toluene at room temperature. When the obtained solid (solid component I) was analyzed, S
iO ₂ 36.6%, magnesium 5.1%, chlorine 38.
It contained 5%.

10 ml of n-heptane and 40 ml of titanium tetrachloride were added to the solid component I obtained above, the temperature was raised to 90 ° C., and di-n-phthalate dissolved in 5 ml of n-heptane was added.
0.6 g of butyl was added over 5 minutes. Then 11
The temperature was raised to 5 ° C. and the reaction was performed for 2 hours. After cooling to 90 ° C., the supernatant was removed by decantation, and the mixture was washed twice with 70 ml of n-heptane. Furthermore, n-heptane 1
5 ml and 40 ml of titanium tetrachloride were added and reacted at 115 ° C. for 2 hours. After the reaction is completed, the solid substance obtained is treated with 60 m
It was washed with 1 n-hexane at room temperature eight times. Then, it was dried at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a catalyst component (component A). This component A contained 3.1% of titanium, silicon oxide, magnesium, chlorine and di-n-butyl phthalate.

In a 500 ml reactor equipped with a prepolymerization stirrer, 1.9 g of the component A obtained above and 280 ml of n-heptane were placed under a nitrogen gas atmosphere and cooled to 5 ° C. with stirring. Next, triethylaluminum (hereinafter abbreviated as TEAL).
N-heptane solution (2.0 mol / l) and cyclohexyl (2-ethoxyethoxy) diethoxysilane n-heptane solution (1.0 mol / l) were added to TEAL and cyclohexyl (2-ethoxyethoxy) in the reaction system. ) Diethoxysilane was added so that the concentrations thereof were 100 mmol / liter and 10 mmol / liter, respectively, and the mixture was stirred for 5 minutes. Next, 40 mm in the system
After decompressing Hg, propylene gas was supplied to polymerize propylene for 2.0 hours. After completion of the polymerization, propylene in the gas phase was purged with nitrogen gas, n-heptane at 5 ° C was added, and the mixture was diluted 5-fold. In this way, a slurry of the catalyst component was prepared. A part of the slurry was taken out, dried, and the amount of magnesium contained in the catalyst component was measured. As a result, the amount of preliminary polymerization was 2.9 g per component Alg.

In a 5-liter stainless steel autoclave equipped with a main polymerization stirrer, 6 ml of an n-heptane solution (0.1 mol / liter) of triisobutylaluminum (hereinafter abbreviated as TIBAL) and propyltriene were added in a nitrogen gas atmosphere. 6 ml of an n-heptane solution of ethoxysilane (0.01 mol / liter) was mixed and held for 5 minutes. Then, 11.9 liters of hydrogen gas (normal temperature and normal pressure) 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. After charging 68.0 mg of the catalyst component obtained above into the reaction system, propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene was purged to obtain 526.6 g of white polypropylene powder. Polypropylene production amount (CE) per component Alg
Was 30.2 kg.

The weight average molecular weight (M
w) is 83,000, elution peak temperature (Tp) is 12
0.3 ° C., flexural modulus 18,200 kgf / cm ² ,
The heat distortion temperature was 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 elution peak temperature (Tp) within the range of the present invention has higher flexural modulus and heat distortion temperature than those outside the range,
It can be seen that the rigidity and heat resistance are improved.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

As is apparent from the examples of the present invention, polypropylene having an elution peak temperature (Tp) within the range of the present invention has higher flexural modulus and heat distortion temperature than those outside the range. Its rigidity and heat resistance are improved, and it is also excellent in 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 wall thickness and reduce the weight, which is effective in terms of resource saving and productivity,
Also, due to improved rigidity and heat resistance, conventional polystyrene, A
It has become possible to replace the applications that used BS resin etc.

[Brief description of drawings]

FIG. 1 is a flow chart diagram of a catalyst of the present invention.

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

Claims (1)

[Claims] 1. A solid component containing (A) a metal oxide, magnesium, titanium, a halogen, and an electron-donating compound as essential components, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following general formula. In the presence of R ¹ Si (OR ² ) _x (OR ³ ) _y [wherein R ¹ is an alicyclic hydrocarbon group having 5 to 7 carbon atoms, R ^1
2 is a 2-ethoxyethyl group or a 2-methyl-3-butyn-2-yl group, R ³ is a methyl group or an ethyl group, x is 1 or 2, y is 1 or 2, x + y
= 3. ] (D) A polypropylene obtained by polymerizing propylene using an α-olefin polymerization catalyst component that is brought into contact with an olefin, and having a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). Is 5,000 to 1,0
A crystalline polypropylene characterized in that it is in the range of 0,000 and the elution peak temperature (Tp) determined from the temperature-raising fractional measurement and Mw satisfy the relationship of Tp ≧ 114.42 + 0.9097 log Mw.