JPH07206921A - Crystalline polypropylene - Google Patents

Abstract

PURPOSE:To obtain a crystalline polypropylene having high modulus in flexure and heat distortion temperature, improved rigidity, heat resistance, moldability and impact resistance, being thinned due to rise in rigidity, capable of being lightened, effective in terms of reduction in resources and productivity, substitutable in uses conventionally using polystyrene resin, ABS resin, etc., by improvement in rigidity and heat resistance. CONSTITUTION:This crystalline polypropylene has 0.01-1.000 melt flow rate(MFR) measured according to ASTM D-1,238 and a heat of fusion (DELTAHm) and a modulus of elasticity G0 obtained by differential scanning calorimetry (DSC) and MFR which satisfy correlation DELTAHm>=24.50+1.583log MFR+0.1991log G0. The crystalline polypropylene is obtained by using a specific magnesium chloride- supported type stereoregular catalyst.

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, depending on the application, these properties are not sufficiently satisfied, and there are many cases where the use is restricted.

Among the above-mentioned performances, polypropylene is polystyrene, AB
It is inferior to S resin. Therefore, polypropylene cannot be used as a material for producing a molded product requiring rigidity and heat resistance, and the above-mentioned polystyrene or A is used as a material for a molded product requiring rigidity and heat resistance.
When polypropylene is intentionally used instead of the BS resin, 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. That is, it prevents expansion of the application of polypropylene or polypropylene composition. If polypropylene has excellent rigidity, chemical resistance, moldability, heat resistance, hardness, etc., such polypropylene can be used as polystyrene or AB.
As an alternative to the S resin, the application can be expanded, and since a thin molded product can be finished, 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 paratertiarybutyl benzoic acid aluminum salt or 1,3-2,4-dibenzylidene sorbitol is added for molding. 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, in order to improve the rigidity and heat resistance of polypropylene, it is necessary to develop polypropylene having high crystallinity, and attempts have been made to develop crystalline polypropylene by devising a polymerization catalyst and a polymerization method. Although slightly improved, it is still inadequate, 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.

[0006]

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.

[0007]

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. And the heat of fusion (ΔH) obtained from differential scanning calorimetry (DSC)
When using m), ΔHm that exhibits high rigidity and high heat resistance
It was found that the value of was not a constant value but changed according to the melt flow rate (MFR) of polypropylene, and the stereoregularity of polypropylene was measured by the differential scanning calorimetry (DSC) with the heat of fusion (ΔHm). When expressed, when ΔHm and MFR satisfy the relationship ΔHm ≧ 24.50 + 1.583 log MFR, it was found that the crystalline polypropylene exhibits high rigidity and high heat resistance, and the first invention of the present application was completed. It was Furthermore, although the crystalline polypropylene can be produced by various polymerization catalysts and polymerization means, the crystalline polypropylene can be easily produced by using the specific stereoregular polymerization catalyst previously invented by the present inventors. This led to the completion of the second invention of the present application.

SUMMARY OF THE INVENTION That is, the gist of the present invention is that a melt flow rate (MFR) measured according to ASTM D-1238 is 0.0.
It is in the range of 1 to 1,000, and the differential scanning calorimetry (DS
C) is a crystalline polypropylene characterized in that the heat of fusion (ΔHm) and MFR satisfy the relationship ΔHm ≧ 24.50 + 1.583 log MFR, and (A) magnesium, titanium, halogen and electrons. Α-Olefin obtained by contacting a solid component containing a donor compound as an essential component with (D) an olefin in the presence of (B) an organoaluminum compound and (C) an organosilicon compound represented by the following general formula (1). A polypropylene obtained by polymerizing propylene using a polymerization catalyst component, having a melt flow rate (MFR) measured according to ASTM D-1238 in the range of 0.01 to 1,000, and having a differential scanning calorimetry ( Relationship between heat of fusion (ΔHm) obtained from DSC) and MFR: ΔHm ≧ 24.50 + 1.583 log MFR Crystalline polypropylene characterized by satisfying a.

[0009]

[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 an ring, a cyclic substituent containing a ketone bond in a ring, a heterocyclic substituent containing a nitrogen atom, a silicon atom] Containing heterocyclic substituent, substituent having lactone skeleton structure, R ² has 1 to 1 carbon atoms
0 hydrocarbon group, 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, and R ⁴ has 3 to 10 carbon atoms.
10 hydrocarbon groups, R ⁵ and R ⁶ have 1 to 1 carbon atoms
It is 0 hydrocarbon groups. ]

Here, the heat of fusion (ΔHm) obtained from the differential scanning calorimetry (DSC) in the present invention means that the sample is enclosed in an aluminum pan and the heat of fusion is measured while the temperature is raised to 200 ° C. In this case, the peak between 85 ° C. and 175 ° C. is taken as the melting peak, and the corresponding heat quantity is divided by the sample quantity to calculate the heat of fusion (unit cal / g). Also,
Melt flow rate (MFR) is ASTM D-12
Value measured according to No. 38, 230 ° C., load 2.1.
It is a value obtained by measuring the mass of the sample extruded for 10 minutes under the condition of 6 kg. The polypropylene of the present invention needs to have a melt flow rate (MFR) in the range of 0.01 to 1,000, and when the melt flow rate (MFR) is less than 0.01, moldability decreases, Again 1,000
If it exceeds, the impact resistance decreases.

Further, the heat of fusion (ΔHm) obtained by differential scanning calorimetry (DSC) of polypropylene in the present invention
Is 24.50 + 1.583 log MFR or more,
Preferably 24.55 + 1.583 log MFR or more,
More preferably, it is 24.60 + 1.583 log MFR or more, and the value is 24.50 + 1.583 log MFR.
If the amount is less than 1, the rigidity and heat resistance of polypropylene are insufficient, and a molded product having high rigidity and high heat resistance cannot be obtained. The polymerization catalyst used in the present invention is as follows.

Solid Component Solid component used in the present invention (hereinafter referred to as component A)
Is an essential component of magnesium, titanium, halogen and an electron donating compound. Such components are usually a magnesium compound, a titanium compound and an electron donating compound, and in the case where each of the above compounds is a compound having no halogen,
It is prepared by contacting each of the halogen-containing compounds. (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. In the chemical formulas, Me: methyl, Et: ethyl, Pr: propyl,
Bu: Butyl, He: Hexyl, Oct: Octyl, P
h: phenyl and cyHe: cyclohexyl are shown respectively.

MgMe ₂ , MgEt ₂ , Mgi-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ ,
MgEtBu, MgPh ₂ , MgcyHe ₂ , Mg
(OMe) ₂ , Mg (OEt) ₂ , Mg (OBu)
₂ , Mg (OHe) ₂ , Mg (OOct) ₂ , Mg
(OPh) ₂ , Mg (OcyHe) ₂ , EtMgC
l, BuMgCl, HeMgCl, i-BuMgCl,
t-BuMgCl, PhMgCl, PhCH ₂ MgC
1, EtMgBr, BuMgBr, PhMgBr, Bu
MgI, EtOMgCl, BuOMgCl, HeOMg
Cl, PhOMgCl, EtOMgBr, BuOMgB
r, EtOMgI, MgCl ₂ , MgBr ₂ , Mg
I ₂ .

The above magnesium compound can be prepared from metallic magnesium or other magnesium compounds when the component A is prepared. As one example thereof, metal magnesium, a halogenated hydrocarbon and an alkoxy group-containing compound represented by 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. Alkenyl group, phenyl (Ph), tolyl, aryl group of xylyl group, phenethyl, aralkyl such as 3-phenylpropyl, 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 in which M is carbon C (OMe) ₄ , C (O contained in the formula C (OR) ₄
Et) ₄ , C (OPr) ₄ , C (OBu) ₄ , C
(Oi-Bu) ₄ , C (OHe) ₄ , C (OOc
t) ₄ : HC (OM included in formula XC (OR) ₃
e) ₃ , HC (OEt) ₃ , HC (OPr) ₃ ,
HC (OBu) ₃ , HC (OHe) ₃ , HC (OP
h) ₃ , MeC (OMe) ₃ , MeC (OEt)
₃ , EtC (OMe) ₃ , EtC (OEt) ₃ ,
cyHeC (OEt) ₃ , PhC (OMe) ₃ , P
hC (OEt) ₃ , CH ₂ ClC (OEt) ₃ ,
MeCHBrC (OEt) ₃ ; MeCHClC (OE
t) ₃ ; ClC (OMe) ₃ , ClC (OE
t) ₃ , ClC (Oi-Bu) ₃ , BrC (OE
t) ₃ ; MeCH contained in the formula X ₂ C (OR) _2.
(OMe) ₂ , MeCH (OEt) ₂ , CH
₂ (OMe) ₂ , CH ₂ (OEt) ₂ , CH
₂ ClCH (OEt) ₂ , CHCl ₂ CH (OE
t) ₂ , CCl ₃ CH (OEt) ₂ , CH ₂ B
rCH (OEt) ₂ , PhCH (OEt) _{2 and the} like can be mentioned.

Compound when M is Silicon Si (OMe) ₄ , S contained in the formula Si (OR) ₄
i (OEt) ₄ , Si (OBu) ₄ , Si (Oi-
Bu) ₄ , Si (OHe) ₄ , Si (OOct)
_4, Si _{(OPh) 4:} Formula XSi _{(OR) HSi} included in _{3 (OEt) 3, HSi (} OBu) 3,
HSi (OHe) ₃ , HSi (OPh) ₃ ; MeS
i (OMe) ₃ , MeSi (OEt) ₃ , MeSi
(OBu) ₃ , EtSi (OEt) ₃ , PhSi
(OEt) ₃ , EtSi (OPh) ₃ ; ClSi
(OMe) ₃ , ClSi (OEt) ₃ , ClSi
(OBu) ₃ , ClSi (OPh) ₃ , BrSi
(OEt) ₃ ; Me ₂ Si (OMe) ₂ , Me ₂ Si (OEt) contained in the formula X ₂ Si (OR) _2.
2 , Et ₂ Si (OEt) ₂ ; MeClSi (O
Et) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CC
l ₃ SiH (OEt) ₂ ; MeBuSi (OEt)
₂ : Me ₃ SiOMe contained in X ₃ SiOR,
Me ₃ SiOEt, Me ₃ SiOBu, Me ₃ S
_{iOPh, Et 3 SiOEt, Ph 3} SiOEt and the like.

Compound in which M is Boron B (OEt) ₃ and B (O contained in Formula B (OR) ₃
Bu) ₃ , B (OHe) ₃ , B (OPh) _{3 and the} like. Compound when M is Aluminum Al (OMe) ₃ , A included in Formula Al (OR) ₃
l (OEt) ₃ , Al (OPr) ₃ , Al (Oi-
Pr) ₃ , Al (OBu) ₃ , Al (Ot-Bu)
₃ , Al (OHe) ₃ , Al (OPh) _{3 and the} like. Compound where M is phosphorus P (OMe) ₃ , P (O included in formula P (OR) ₃
Et) ₃ , P (OBu) ₃ , P (OHe) ₃ , P
(OPh) _{3 and the} like.

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
It is represented by ¹ R ² · n (MR ³ _m ). The metal includes aluminum, zinc, calcium, etc.,
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. MR
Specific examples of the compound represented by ³ _m include AlM
_{e 3, AlEt 3, Ali-} Bu 3, AlPh
₃ , ZnMe ₂ , ZnEt ₂ , ZnBu ₂ , Z
nPh _2, CaEt _2, CaPh _2, and the like.

(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, the 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 general formula, R ⁴ is alkyl having 1 to 12 carbons, alkenyl, cycloalkyl, aryl or aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol,
Examples include isopropylphenol, p-tertiarybutylphenol, and n-octylphenol.

The ethers are represented by the general formula R ⁵ OR ⁶ . In the general formula, R ⁵ and R ⁶ have 1 to 1 carbon atoms.
It is 12 alkyl, alkenyl, cycloalkyl, aryl, 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, and after contacting the components 1 and 3 with each other. , Component 2 may be contacted, component 1, component 2 and component 3 may be contacted at the same time. It is also possible to contact the halogen-containing compound before contacting component 2.

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

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 the hydroxyl group in a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule are substituted with a halogen atom. 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, HSiCl_Three, H _TwoSiCl_Two，
H_ThreeSiCl, H (CH_Three) SiCl_Two, H (C
_TwoH₅) SiCl_Two, H (t-C_FourH₉) Si
Cl_Two, H (C₆H₅) SiCl_Two, H (CH
_Three)_TwoSiCl, H (i-C_ThreeH₇)_TwoSiC
l, H_Two(C_TwoH₅) SiCl, H_Two(N-C
_FourH₉) SiCl, H_Two(C₆H_FourC
H_Three) SiCl, H (C₆H₅)_TwoSiCl, etc.
Is mentioned.

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 ,
_{AlBr 3, GaCl 3, GaBr 3} , InCl
₃ , TlCl ₃ , SiCl ₄ , SnCl ₄ , S
bCl ₅ , SbF _{5 and the} like are preferable. The contact with Component 1, Component 2 and Component 3, and optionally with a halogen-containing compound that can be contacted, is carried out by mixing or stirring in the presence or absence of an inert medium, or mechanically co-milling. Done by. 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. . Preferred methods for preparing the component A in the present invention are described in JP-A-63-264607, JP-A-58-198503 and JP-A-6-198503.
No. 2-146904 and the like, and more specifically, (a) metallic magnesium, (ii) halogenated hydrocarbon, (iii) general formula X _n M (OR) _m-n The magnesium-containing solid obtained by contacting the compound (1) with 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-63-264607), (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 gazette). Among these, the most preferable method is the most preferable method. Although the component A is prepared as described above, the component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

Organoaluminum Compound 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 an ring, a cyclic substituent containing a ketone bond in a ring, a heterocyclic substituent containing a nitrogen atom, and 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 methyl or 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. Hereinafter, the respective groups are referred to as RA, RB ...

[0037]

[Chemical 3]

[0038]

[Chemical 4]

R in the above general formula of the component C^TwoIs charcoal
Hydrocarbon radicals having a prime number of 1 to 10, R^Four O, R⁵ _ThreeSi
Or R⁶ _ThreeIndicates SiO, R^FourHas 3 to 10 carbon atoms
Hydrocarbon groups, R⁵And R⁶Is 1 to 10 carbon atoms
Shows a hydrocarbon group of. These hydrocarbon groups include
Alkyl group, alkenyl group, cycloalkyl group, cycloalkyl group
Lucenyl group, cycloalkadienyl group, aryl group,
And alkyl groups.

As the alkyl group, 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.

The component C is exemplified below. In the following,
The 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, Bu is butyl,
CyPe represents cyclopentyl, and CyHe represents a cyclohexyl group.

[RA] ₂ Si (OMe) ₂ , [R
A] (i-PrO) Si (OMe) ₂ , [RB] (i-
PrO) Si (OMe) ₂ , [RD] (t-Bu) S
i (OMe) ₂ , [RD] (Me ₃ SiO) Si
(OMe) ₂ ; [RA] (Me ₃ SiO) Si (O
Et) ₂ , [RA] (i-Pr) Si (OEt) ₂ ,
[RC] (i-PrO) Si (OEt) ₂ , [RD]
(Me ₃ SiO) Si (OEt) ₂ , [RD] (t
-Bu) Si (OEt) ₂ ; [RA] Si (OMe)
₃ , [RD] Si (OMe) ₃ , [RE] Si (O
Me) ₃ ; [RA] Si (OEt) ₃ , [RD] S
i (OEt) ₃ , [RB] Si (OEt) ₃ ; [R
D] MeSi (OMe) ₂ , [RF] MeSi (OM
e) ₂ , [RF] (i-PrO) Si (OMe) ₂ ,
[RF] (t-Bu) Si (OMe) ₂ , [RG] M
eSi (OMe) ₂ , [RG] (CyPe) Si (O
Me) ₂ , [RG] (CyHe) Si (OM
e) ₂ , [RH] (CyHe) Si (OMe) ₂ ;
[RI] (i-PrO) Si (OMe) ₂ , [RJ]
Si (OEt) ₃ , [RK] Si (OMe) ₃ ,
[RL] (i-Pr) Si (OEt) ₂ ; [RM] S
i _{(OMe) 3,} [RM] Si (OSiMe ₃₎
(OMe) ₂ , [RN] Si (OMe) ₃ , [R
N] _{Si (OSiMe 3) (OMe)} 2, [RO] S
i (OEt) ₃ , [RP] Si (OEt) ₃ , [R
Q] Si (OSiMe ₃ ) (OMe) ₂ ; [RR]
Si (OEt) ₃ ; [RS] Si (OEt) ₃ , [R
T] Si (OEt) ₃ , [RU] Si (OM
e) ₃ ; [RV] Si (OEt) ₃ , [RW] Si
(OMe) ₃ , [RX] Si (OMe) ₃ , [R
Y] Si (OEt) ₃ , [RZ] Si (OM
e) ₃ .

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.

Examples of the electron donating compound include an electron donating compound composed of an organic silicon compound, nitrogen, sulfur, oxygen,
An electron donating compound containing a hetero atom such as phosphorus can be used, but an organic silicon compound is preferable among them. The organic silicon compound has a total of 4 alkyl and alkoxy groups.
Those bonded to individual silicon atoms are preferred, and these alkyl groups and alkoxy groups may be chain-like, and some of them may be O,
It may be substituted with a hetero element such as N or S.

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 to homopolymerize propylene or copolymerize with other monoolefins. Polymerization can be performed to obtain crystalline polypropylene having a relationship between the heat of fusion (ΔHm) determined by differential scanning calorimetry (DSC) and the melt flow rate (MFR) represented by the above formula.

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. As an organoaluminum compound that can be used, a compound represented by the general formula R ⁷ _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 an arbitrary number within the range of 1≤n≤3). Such as trialkylaluminum,
Alkyl aluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as dialkyl aluminum monohalides, monoalkyl aluminum dihalides, alkyl aluminum sesquihalides, dialkyl aluminum monoalkoxides and dialkyl aluminum monohydrides, or mixtures thereof. Particularly preferred are the compounds.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutylaluminum. Dialkyl aluminum monohalides such as chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide,
Monoalkyl aluminum dihalides such as ethyl aluminum diiodide and isobutyl aluminum dichloride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum Ethoxide,
Dialkyl aluminum monoalkoxides such as diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride,
Examples thereof include dialkyl aluminum hydrides such as dipropyl aluminum hydride and diisobutyl aluminum hydride. Among these, trialkylaluminums, particularly triethylaluminum and triisobutylaluminum are preferable. Further, these trialkylaluminums are other organoaluminum compounds, for example, industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride or a mixture or feed 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

[Chemical 5] Etc. can be illustrated.

Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc and the like, and LiAl (C
Compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be mentioned. The amount of the organometallic compound used with respect to the catalyst component of the present invention is usually 1 to 2,000 gram mol, particularly 20 to 50 gram atom per 1 gram atom of titanium in the catalyst component.
0 gram mol is desirable. When an electron donating compound is used, the ratio of the organometallic compound and the electron donating compound is
The organometallic compound is selected as aluminum in an amount of 0.1 to 40, preferably 1 to 25 gram atom per mol of the electron-donating compound.

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.

[0055]

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. Differential scanning calorimetry (DSC)
Perkin Elmer DSC7 (7700Data
Station), punch out about 10 mg of 0.5 mm thick sheet press-molded at 210 ° C. for 1 minute, enclose in an aluminum pan, hold at 230 ° C. for 10 minutes, and then hold at 10 ° C.
The temperature is decreased to 50 ° C. at a heating rate of 50 ° C./min, and then the temperature is raised to 200 ° C. at a rate of 10 ° C./min. And the heat of fusion (unit cal / g) was calculated.

(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 0.5 ml of an n-butyl ether solution of n-butyl magnesium chloride (1.75 mol / liter) were added to this metallic magnesium, and the suspension was kept at 55 ° C. n
-N-butyl chloride 3 in 50 ml of butyl ether
A solution in which 8.5 ml was dissolved was added dropwise over 50 minutes. After the reaction was carried out at 70 ° C for 4 hours with stirring, the reaction solution was kept at 25 ° C. Then, HC (OC ₂ H ₅ ) was added to the reaction solution.
The ₃ 55.7 ml was added dropwise over 1 hour. 6 after the dropping
The reaction was performed at 0 ° 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 a magnesium-containing solid containing 19.0% magnesium and 28.9% chlorine. 31.6 g 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. 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. and washed twice with 100 ml of toluene each time at 90 ° C. Further, titanium tetrachloride was newly added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the mixture was stirred at 120 ° C. for 2 hours and then at room temperature for 1
After washing 7 times with 00 ml of n-hexane, 5.5 g of the component
Got

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 5 ° C. with stirring. Next, n-heptane solution (2.0 mol / liter) of triethylaluminum (hereinafter abbreviated as “TEAL”) and 2,3,4-trimethyl-3-azacyclopentyltrimethoxysilane were added to TEAL and Two
The 3,4-trimethyl-3-azacyclopentyltrimethoxysilane was added so that the concentrations thereof were 100 mmol / liter and 10 mmol / liter, respectively, and the mixture was stirred for 5 minutes. Then, after depressurizing the system, propylene gas was continuously supplied to polymerize propylene for 2.2 hours. After completion of the polymerization, propylene in the gas phase was purged with nitrogen gas, and the solid phase portion was washed with 100 ml of n-hexane three times at room temperature. Further, the solid phase portion was dried under reduced pressure at room temperature for 1 hour to prepare a catalyst component. As a result of measuring the amount of magnesium contained in the catalyst component, the amount of preliminary polymerization was 3.1 g per 1 g of component A.

In a 5-liter stainless steel autoclave equipped with a main polymerization stirrer, 6 ml of an n-heptane solution of TEAL (0.1 mol / liter) and n-heptane of di (1-methylbutyl) dimethoxysilane were placed in a nitrogen gas atmosphere. 6 ml of the solution (0.01 mol / l) was mixed and held for 5 minutes. Next, 0.1 liters of hydrogen gas as a molecular weight controlling agent and 3 liters of liquid propylene were injected under pressure, and then the temperature of the reaction system was raised to 70 ° C. Catalyst component 6 obtained above
After charging 4.7 mg into the reaction system, propylene was polymerized for 1 hour. After the completion of the polymerization, unreacted propylene was purged to obtain 487.6 g of white polypropylene powder.
Polypropylene yield (CE) per gram of ingredient A is 3
It was 0.9 kg. This polypropylene has a melt rate (MFR) of 0.35 and a heat of fusion (ΔHm) of 2
4.63 cal / g, flexural modulus 18,100 kgf
/ Cm ² , and the heat distortion temperature was 117 ° 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, the heat of fusion (ΔH
Polypropylene in which m) is within the scope of the present invention has higher flexural modulus, heat distortion temperature than those outside the range, and rigidity,
It can be seen that the heat resistance is improved. The flexural modulus is in accordance with JIS K-6758, and the heat distortion temperature is JI.
It was measured according to SK-7202.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

As is apparent from the examples and comparative examples of the present invention, polypropylene having a heat of fusion (ΔHm) within the range of the present invention is better than a polypropylene having a flexural modulus and a heat distortion temperature out of the ranges. Is also high, rigidity and heat resistance are improved,
In addition, since it has excellent moldability and impact resistance, and therefore the crystalline polypropylene of the present invention has high rigidity, the molded product for the same purpose as before can be thinned and reduced in weight. , Effective in terms of resource saving and productivity, and improved in rigidity and heat resistance.
It has become possible to replace the applications that used S resin.

 ─────────────────────────────────────────────────── ─── 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. A melt flow rate (MFR) measured according to ASTM D-1238 of 0.01 to 1.00.
A crystalline polypropylene characterized in that the heat of fusion (ΔHm) determined by differential scanning calorimetry (DSC) and MFR satisfy the relationship ΔHm ≧ 24.50 + 1.583 log MFR in the range of 0. 2. A solid component containing (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
Propylene is polymerized using (B) an organoaluminum compound and (C) an α-olefin polymerization catalyst component which is brought into contact with (D) an olefin in the presence of an organosilicon compound represented by the following general formula (1). Which has a melt flow rate (MFR) measured according to ASTM D-1238 in the range of 0.01 to 1,000, and has a heat of fusion (ΔHm) and MFR obtained from differential scanning calorimetry (DSC). A crystalline polypropylene characterized in that and satisfy the relationship ΔHm ≧ 24.50 + 1.583 log MFR. [Chemical 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 an ring, a cyclic substituent containing a ketone bond in a ring, a heterocyclic substituent containing a nitrogen atom, a silicon atom] Containing heterocyclic substituent, substituent having lactone skeleton structure, R ² has 1 to 1 carbon atoms
0 hydrocarbon group, 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, and R ⁴ has 3 to 10 carbon atoms.
10 hydrocarbon groups, R ⁵ and R ⁶ have 1 to 1 carbon atoms
It is 0 hydrocarbon groups. ]