JPH11302316A - Production of propylene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene-ethylene block copolymer excellent in balance between rigidity and impact resistance and a propylene-ethylene random copolymer excellent in balance between transparency and rigidity. Providing a way. (A) A solid component comprising magnesium, titanium, a halogen and an electron donating compound as essential components,
(B) (R ^k ) _r Al (Y) _3-r (R ^k is an alkyl group, an aryl group, Y is an alkoxy group, an aryloxy group, r
Is an organoaluminum compound represented by 0 ≦ r ≦ 3 or an organoaluminum compound in which two or more Al are bonded via O or N, (C) an alkylalkoxysilane compound, and (D) MetR _x (Met is Mg, B, Al, Ga,
Ge, In, Sn, Sb or a transition metal element, R is a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, and x is a valence of Met. ). Propylene and ethylene are copolymerized in the presence of a polymerization catalyst comprising the compound represented by the formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a propylene-ethylene copolymer, and more particularly to a propylene-ethylene block copolymer excellent in balance between rigidity and impact resistance, or a balance between transparency and rigidity. The present invention relates to a method for producing a propylene-ethylene random copolymer excellent in water resistance.

[0002]

2. Description of the Related Art A propylene-ethylene copolymer is used as a polypropylene resin having improved impact resistance.
It is excellent in heat resistance, chemical resistance, electrical properties, and has good rigidity, tensile strength, optical characteristics, workability, and is used for injection molding, film molding, sheet molding, blow molding, etc. The propylene-ethylene copolymer has a low specific gravity, and is widely used in the fields of industrial materials such as automobiles and home appliances and general goods.

[0003] Propylene polymerization catalysts comprising a catalyst component containing Mg, Ti, a halogen and an electron donating compound as essential components, an organoaluminum compound and a silane compound are well known. At this time, the stereoregularity of the obtained polypropylene can be changed by changing the silane compound (Japanese Patent Application Laid-Open No. 7-109309). Thus, the stereoregularity of polypropylene has been improved, and its rigidity has been improved. Furthermore, improvement of impact resistance and transparency according to each industrial application by copolymerization with other olefins such as ethylene has been studied.

For example, as a method for improving the balance between the rigidity and the impact resistance of a copolymer, various methods have been proposed in which stepwise polymerization is performed while changing the polymerization ratio of propylene and other olefins, that is, a multistage polymerization method. (For example, Japanese Patent Publication No. 3-4456). It is also known that a silicon compound is present during copolymerization as another improvement method (Japanese Patent Application Laid-Open No. Hei 6-73113). However, none of these methods has yielded a propylene-ethylene copolymer sufficiently excellent in balance between rigidity and physical properties of impact resistance.

As a means for improving the transparency, there is known a method of producing a random copolymer by adding a small amount of ethylene when polymerizing propylene. However,
As the amount of ethylene added increases, the transparency improves, but the crystallinity of polypropylene is disturbed, so that the rigidity is lost. On the other hand, various methods for improving rigidity have been proposed, and most of them are methods for performing post-treatment such as adding a nucleating agent to polypropylene. Therefore,
In addition to an increase in cost in terms of process, the appearance of some additives is impaired. Methods for improving rigidity by a polymerization method have also been proposed, but all have insufficient rigidity.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a method for obtaining a propylene-ethylene block copolymer having a good balance between rigidity and impact resistance among propylene-ethylene block copolymers. In a propylene-ethylene random copolymer, an object is to provide a method for obtaining a copolymer excellent in balance between transparency and rigidity.

[0007]

Means for Solving the Problems The present inventors have repeatedly studied a method for producing a propylene-ethylene copolymer. As a result, the present inventors carried out homopolymerization of propylene in the presence of a specific metal halide, and subsequently conducted propylene homopolymerization. By copolymerizing ethylene, a copolymer with excellent balance between rigidity and impact resistance is obtained.By performing random copolymerization of propylene and ethylene in the presence of a specific metal halide, transparency and rigidity are obtained. It has been found that a copolymer excellent in the balance of can be produced, and the present invention has been completed.

That is, the present invention provides (A) a solid component comprising magnesium, titanium, halogen and an electron donating compound as essential components, (B) a general formula (R ^k ) _r Al (Y)
_3-r (where R ^k is each independently an alkyl group and an aryl group, Y is each independently a group selected from an alkoxy group and an aryloxy group,
Is an arbitrary number in the range of 0 ≦ r ≦ 3. ), At least one or more selected from the organoaluminum compounds in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom, (C) an alkylalkoxysilane compound, and ( D) General formula MetR _X (where Met is M
g, B, Al, Ga, Ge, In, Sn, Sb or a transition metal element, R represents a halogen atom or a hydrocarbon-containing group, at least one is a halogen atom, and x is M
Shows the valence of et. A method for producing a propylene-ethylene copolymer, comprising copolymerizing propylene and ethylene in the presence of a polymerization catalyst comprising the compound represented by the formula (1).

An embodiment of the present invention will be described below. (A) The process for producing a propylene-ethylene copolymer as described above, wherein the solid component of (A) is a solid component containing magnesium, titanium, halogen, metal oxide and an electron donating compound as essential components. (B) The method for producing the propylene-ethylene copolymer, wherein the component (B) is a trialkylaluminum. (C) The method for producing the propylene-ethylene copolymer, wherein the component (B) is trimethylaluminum. (D) The component (C) has the general formula R ¹ Si (OR ² ) (OCH
₃ ) ₂ (wherein, R ¹ is a branched or cyclic alkyl group having 3 to 6 carbon atoms, and R ² is a branched alkyl group, alkenyl group or alkynyl group having 3 to 6 carbon atoms.) The method for producing the propylene-ethylene copolymer, which is an alkyltrialkoxysilane represented by the formula: (E) The component (D) is represented by the general formula MetR _X (where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n represents R, a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, and x represents Met
The valence of The method for producing the propylene-ethylene copolymer, which is a compound represented by the formula: (F) The component (D) has the general formula MetR _X (where Met
Represents B or Al, R represents a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, and x represents the valency of Met. The method for producing the propylene-ethylene copolymer, which is a compound represented by the formula: (G) The component (D) has the general formula MetR _X (where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n represents R, a halogen atom or a hydrocarbon-containing group, at least two or more of which are halogen atoms;
Shows the valence of et. The method for producing the propylene-ethylene copolymer, which is a compound represented by the formula: (H) The component (D) is represented by the general formula MetR _X (where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n is shown, R represents a halogen atom or a hydrocarbon-containing group, contains at least one of Br and I, and x shows the valence of Met. The method for producing the propylene-ethylene copolymer, which is a compound represented by the formula: (I) The component (D) has the general formula MetR _X (where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n is shown, R shows a halogen atom or a hydrocarbon containing group, Br or I contains two or more, and x shows the valence of Met. The method for producing the propylene-ethylene copolymer, which is a compound represented by the formula: (N) The component (D) is represented by the general formula MetR _X (where Met
Is Ti, Mg, B, Al, Co, Rh, Ni, Pd, Z
n is shown, R shows a halogen atom or a hydrocarbon-containing group, contains two or more Br, and x shows the valence of Met. The method for producing the propylene-ethylene copolymer, which is a compound represented by the formula: (I) wherein the component (D) is tribromoboron, ethylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquiiodide, palladium bromide, zinc bromide, boron chloride, aluminum bromide, or boron iodide. A method for producing a propylene-ethylene copolymer. (ヲ) (A) a solid component containing magnesium, titanium, halogen and an electron donating compound as essential components, (B) a general formula (R ^k ) _r Al (Y) _3-r (where R ^k is each independently An alkyl group and an aryl group, Y is each independently a group selected from an alkoxy group and an aryloxy group, and r is an arbitrary number in the range of 0 ≦ r ≦ 3.) At least one of the organoaluminum compounds to be bonded or two or more aluminum bonded via an oxygen atom or a nitrogen atom.
One or more selected organoaluminum compounds, (C) an alkylalkoxysilane compound, (D) a general formula MetR
_X (where Met is Mg, B, Al, Ga, Ge, I
n, Sn, Sb or a transition metal element, R represents a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, and x represents a valence of Met. Wherein propylene and ethylene are copolymerized in the presence of a polymerization catalyst comprising a compound represented by formula (I) and a zinc compound represented by (E) ZnR ₂ (wherein R represents an alkyl group). -A method for producing an ethylene copolymer. (W) (A) a solid component containing magnesium, titanium, halogen and an electron donating compound as essential components, (B) a general formula (R ^k ) _r Al (Y) _3-r (where R ^k is each independently An alkyl group and an aryl group, Y is each independently a group selected from an alkoxy group and an aryloxy group, and r is an arbitrary number in the range of 0 ≦ r ≦ 3.) At least one of the organoaluminum compounds to be bonded or two or more aluminum bonded via an oxygen atom or a nitrogen atom.
One or more selected organoaluminum compounds, (C) an alkylalkoxysilane compound, (D) a general formula MetR
_X (where Met is Mg, B, Al, Ga, Ge, I
n, Sn, Sb or a transition metal element, R represents a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, and x represents a valence of Met. A zinc compound represented by (E) ZnR ₂ (wherein R represents an alkyl group); and (F) AlR
₃ (wherein R is each independently a hydrogen atom or an alkyl group, and at least one is a hydrogen atom). Copolymerizing propylene and ethylene in the presence of a polymerization catalyst comprising a compound represented by the formula: Propylene characterized by the following
A method for producing an ethylene copolymer. (F) (A) a solid component containing magnesium, titanium, halogen and an electron donating compound as essential components, (B) a general formula (R ^k ) _r Al (Y) _3-r (where R ^k is each independently An alkyl group and an aryl group, Y is each independently a group selected from an alkoxy group and an aryloxy group, and r is an arbitrary number in the range of 0 ≦ r ≦ 3.) At least one of the organoaluminum compounds to be bonded or two or more aluminum bonded via an oxygen atom or a nitrogen atom.
One or more selected organoaluminum compounds, (C) an alkylalkoxysilane compound, (D) a general formula MetR
_X (where Met is Mg, B, Al, Ga, Ge, I
n, Sn, Sb or a transition metal element, R represents a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, and x represents a valence of Met. A zinc compound represented by (E) ZnR ₂ (wherein R represents an alkyl group); (F) AlR
₃ (wherein, R is independently hydrogen atom or an alkyl group, at least one of which is a hydrogen atom.) Compounds represented by and at (G) in the general formula Cp _n MY _4-n (wherein,
Cp is a substituted or unsubstituted cyclopentadienyl group, M is T
i is an element selected from Zr, Hf, Y is a group selected from hydrogen, halogen, an alkoxy group, an amino group, an alkyl or aryl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. A method for producing a propylene-ethylene block copolymer, comprising copolymerizing propylene and ethylene in the presence of a polymerization catalyst comprising the compound represented by the formula (1). α
-An olefin polymerization catalyst.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Component consisting of magnesium, titanium, halogen and an electron donating compound Component (A) in the catalyst of the present invention contains magnesium, titanium, halogen and an electron donating compound as essential components, and optionally contains a metal oxide. Can be included. Component (A) is a component known per se. Such a component is usually adjusted by contacting a magnesium compound, a titanium compound, an electron-donating compound, and, when the compound is a compound having no halogen, a halogen-containing compound. Hereinafter, each component will be described.

(1) Magnesium A magnesium compound is represented by the general formula MgR ^{a Rb} .
Here, ^Ra and ^Rb represent the same or different hydrocarbon groups, OR groups (R is a hydrocarbon group), and halogen atoms. More specifically, as the hydrocarbon group of R ^a and R ^b, Tansomoto 20
Alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups are OR groups, and R is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group is a halogen atom. Chlorine, bromine, iodine, fluorine and the like.

Specific examples of these compounds are shown below. In the following chemical formula, Me: methyl, Et: ethyl, Pr:
Propyl, i-Pr: isopropyl, Bu: butyl, i
-Bu: isobutyl, t-Bu: tertiary butyl,
He: hexyl, Oct: octyl, Ph: phenyl,
cyHe: represents cyclohexyl.

MgMe ₂ , MgEt ₂ , Mg (i-Pr)
₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgEtB
u, MgPh ₂ , MgcyHe ₂ , Mg (OMe) ₂ , M
g (OEt) ₂ , Mg (OBu) ₂ , Mg (OHe) ₂ ,
Mg (OOct) ₂ , Mg (OPh) ₂ , Mg (OcyH
e) ₂ , EtMgCl, BuMgCl, HeMgCl,
i-BuMgCl, t-BuMgCl, PhMgCl,
PhCH ₂ MgCl, EtMgBr, BuMgBr, P
hMgBr, BuMgI, EtOMgCl, BuOMg
Cl, HeOMgCl, PhOMgCl, EtOMgB
r, BuOMgBr, EtOMgI, MgCl ₂ , Mg
Br ₂ , MgI ₂ .

The above magnesium compound can be prepared from metallic magnesium or another magnesium compound when preparing component A. Examples thereof include metallic magnesium, halogenated hydrocarbons and alkoxy group-containing compounds of the general formula X _n M (OR) _mn (wherein X
Is a hydrogen atom, a halogen atom or a 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
Represents the valence of M and m> n ≧ 0. ) Is contacted.

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

Compounds wherein M is carbon C (OMe) ₄ , C (OEt) contained in formula C (OR) _4
4 , C (OPr) ₄ , C (OBu) ₄ , C (Oi-B
u) ₄ , C (OHe) ₄ , C (OOct) ₄ : Formula XC (O
R) ₃ contained in HC (OMe) ₃ , HC (OEt) ₃ ,
HC (OPr) ₃ , HC (OBu) ₃ , HC (OH
e) ₃ , HC (OPh) ₃ ; MeC (OMe) ₃ , Mec
(OEt) ₃ , EtC (OMe) ₃ , EtC (OE
t) ₃ , cyHeC (OEt) ₃ , PhC (OMe) ₃ ,
PhC (OEt) ₃ , CH ₂ ClC (OEt) ₃ , MeC
HBrC (OEt) ₃ , MeCHClC (OEt) ₃ ; C
1C (OMe) ₃ , ClC (OEt) ₃ , ClC (Oi-
Bu) ₃ , BrC (OEt) ₃ ; MeCH (OMe) ₂ , MeCH (OEt) ₂ , CH contained in the formula X ₂ C (OR) _2
2 (OMe) ₂ , CH ₂ (OEt) ₂ , CH ₂ ClCH (O
Et) ₂ , CHCl ₂ CH (OEt) ₂ , CCl ₃ CH (O
Et) ₂ , CH ₂ BrCH (OEt) ₂ , PhCH (OE
t) ₂ .

Compound when M is silicon Si (0Me) ₄ , Si (O) contained in the formula Si (OR) ₄
Et) ₄ , Si (OBu) ₄ , Si (Oi-Bu) ₄ , S
i (OHe) ₄ , Si (OOct) ₄ , Si (OP
h) ₄ : HSi (OEt) contained in the formula XSi (OR) _3
3 , HSi (OBu) ₃ , HSi (OHe) ₃ , HSi
(OPh) ₃ ; MeSi (OMe) ₃ , MeSi (OE
t) ₃ , MeSi (OBu) ₃ , EtSi (OEt) ₃ ,
PhSi (OEt) ₃ , EtSi (OPh) ₃ ; ClSi
(OMe) ₃ , ClSi (OEt) ₃ , ClSi (OB
u) ₃ , ClSi (OPh) ₃ , BrSi (OEt) ₃ ;
Me ₂ Si (OMe) ₂ in an expression X ₂ Si (OR) _2,
Me ₂ Si (OEt) ₂ , Et ₂ Si (OEt) ₂ ; MeC
1Si (OEt) ₂ ; CHCl ₂ SiH (OEt) ₂ ; C
Cl ₃ SiH (OEt) ₂ ; MeBuSi (OEt) ₂ :
Me ₃ SiOMe, Me ₃ SiO contained in X ₃ SiOR
Et, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

Compound when M is Boron B (OEt) ₃ , B (OBu) contained in formula B (OR) _3
3 , B (OHe) ₃ , B (OPh) ₃ .

Compound when M is aluminum Al (OMe) ₃ , Al (O) contained in the formula Al (OR) ₃
Et) ₃ , Al (OPr) ₃ , Al (Oi-Pr) ₃ , A
l (OBu) ₃ , Al (Ot-Bu) ₃ , Al (OHe)
₃ , Al (OPh) ₃ .

Compound when M is phosphorus P (OMe) ₃ , P (OEt) contained in formula P (OR) _3
3 , P (OBu) ₃ , P (OHe) ₃ , P (OPh) ₃ .

Further, as the magnesium compound, a complex with an organic compound of a metal (M ') of Group II or Group IIIa of the periodic table can be used. The complex has the general formula MgR
represented by ^{a R b · p (M'R c} q) (R a and R ^b are as defined above). As the metal (M '), aluminum, zinc, and calcium, and the like, R ^C is alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group. Also, q is the valence of the metal M 'and p is 0.
The number of 1-10 is shown. Specific examples of the compound represented by M′R ^C _q include AlMe ₃ , AlEt ₃ , Al (i-B
u) ₃ , AlPh ₃ , ZnMe ₂ , ZnEt ₂ , ZnB
_{u 2, ZnPh 2, CaEt 2} , CaPh 2 , and the like.

(2) Titanium Titanium compounds are trivalent and tetravalent titanium compounds. Examples thereof include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethoxytitanium and dichlorotitanium. Examples thereof include titanium dibutoxy, dichlorodiphenoxy titanium, chlorotriethoxy titanium, chlorotributoxy titanium, tetrabutoxy titanium, and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

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

(A) Carboxylic acids Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid and crotonic acid. Carboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, aliphatic carboxylic acids such as tartaric acid,
Cycloaliphatic carboxylic acids such as cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid,
Anisic acid, p-tert-butyl benzoic acid, naphthoic acid, aromatic monocarboxylic acids such as cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemimeltic acid, trimesic acid, pyromellitic acid, And aromatic polycarboxylic acids such as melitic acid.

(B) Carboxylic anhydride As the carboxylic anhydride, anhydrides of the above carboxylic acids can be used.

(C) Carboxylic acid ester As the carboxylic acid ester, mono- or polyhydric esters of the above carboxylic acids can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, Propyl pivalate, isobutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, glutaric acid Dibutyl, 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, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, methyl p-toluate, p-tert-butyl,
Ethyl benzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate,
Monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate,
Dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, trimellitic acid Tributyl, tetramethyl pyromellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate and the like can be mentioned.

(D) Carboxylic acid halide As the carboxylic acid halide, acid halides of the above carboxylic acids can be used. Specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, and the like. 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, cinnamate chloride, cinnamate bromide, phthalic dichloride, phthalic dibromide,
Isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, and butyl phthalate chloride can also be used.

(E) Alcohols Alcohols are represented by the general formula R ^d OH. In the formula, R ^d is alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol isobutanol,
Pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol and the like.

[0029] (f) ethers ethers represented by the general formula R ^e OR ^f. In the formula, R ^e , R ^f is alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbons,
^Re and ^Rf may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether,
Dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether and the like.

(4) Halogen The halogen-containing compounds include halogenated hydrocarbons, halogen-containing alcohols, silicon halide compounds having a hydrogen-silicon bond, groups IIIa and IVa of the periodic table,
Halides of Va group elements (hereinafter referred to as metal halides) and the like can be mentioned.

(A) Halogenated Hydrocarbon As the halogenated hydrocarbon, mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms are used. You. Specific examples of such compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-
Dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,2
2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane,
Chlorinated paraffin and the like can be mentioned. Examples of the alicyclic compound include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane. Examples of the aromatic compound include chlorobenzene, bromobenzene, o-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. These compounds may be used alone or in combination of two or more.

(B) Halogen-Containing Alcohol As the halogen-containing alcohol, one or two or more hydrogen atoms other than a hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are exemplified. Compounds substituted with halogen atoms can be used. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, and a chlorine atom is preferable.

Examples of these compounds include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol,
3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol,
(M, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol,
6-chloro- (m, o) -cresol, 4-chloro-
3,5-dimethylphenol, chlorohydroquinone,
2-benzyl-4-chlorophenol, 4-chloro-1
-Naphthol, (m, o, p) -chlorophenol, p
-Chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-
Chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol,
1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-
Naphthol, (m, o, p) -bromophenol, 4-
Bromoresorcin, (m, o, p) -fluorophenol, p-iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro -1- (α-chloromethyl) -1-propanol, 2,3-dibromo-
1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-
1-naphthol: 2,2,2-trichloroethanol,
1,1,1-trichloro-2-propanol, β, β,
β, -trichloro-tert-butanol, 2,3,4
-Trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4
6-tribromophenol, 2,3,5-tribromo-
2-hydroxytoluene, 2,3,5-tribromo-4
-Hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol,
2,4,6-triiodophenol: 2,2,4,6-
Tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-
And propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like.

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

(D) Metal halides As metal halides, B, Al, Ga, In, Tl,
Chloride of Si, Ge, Sn, Pb, As, Sb, Bi,
Fluoride, bromide and iodide, especially BC
l ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlBr ₃ , GaC
l ₃ , GaBr _3, InCl ₃ , TlCl ₃ , SiCl ₄ , S
nCl ₄ , SbCl ₅ , SbF _{5 and the} like are preferred.

(5) Metal Oxide As the component (A), a metal oxide can be used as a carrier. Metal oxides are listed in Groups II to IV of the Periodic Table of the Elements.
Oxides of elements selected from the group consisting of B ₂ O ₃ , MgO, Al ₂ O ₃ , SiO ₂ , Ca
O, TiO ₂ , ZnO, ZrO ₂ , SnO _2, BaO, Th
O _{2 and the} like. Among them, B ₂ O ₃ , MgO,
Al ₂ O ₃ , SiO ₂ , TiO ₂ and ZrO ₂ are preferred, and SiO ₂ is particularly preferred. Further, composite oxides containing these metal oxides, for example, SiO ₂ —MgO, SiO ₂ —Al
₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —
Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO or the like can also be used.

These metal oxides are usually used in the form of powder. Since the form such as the size and shape of the powder often affects the form of the obtained olefin polymer, it is desirable to appropriately adjust the form. It is desirable that the metal oxide be fired at as high a temperature as possible for the purpose of removing poisonous substances when used, and that the metal oxide be handled so as not to come into direct contact with the atmosphere.

(6) Preparation of Component (A) Magnesium compound (component 1), titanium compound (component 2), electron donating compound (component 3), and metal oxides and halogens which can be contacted if necessary The contact with the containing compound is performed by mixing and stirring or mechanically co-milling in the presence or absence of an inert medium. 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.

In the present invention, the component (A) is preferably prepared in the case of a solid component (A) containing magnesium, titanium, halogen and an electron-donating compound as essential components, as described in JP-A-63-264607. Id 58-1985
No. 03, No. 62-146904 and the like. More specifically, it is obtained by contacting (a) metallic magnesium, (b) a halogenated hydrocarbon, and (c) a compound of the general formula X _n M (OR) _mn (the same as the above-mentioned alkoxy group-containing compound). A method of contacting a magnesium-containing solid with (d) a halogen-containing alcohol and then with (e) an electron-donating compound and (f) a titanium compound (JP-A-63-163).
No. 264607), (a) contacting a magnesium dialkoxide with a (ii) silicon halide compound having a hydrogen-silicon bond, (c) contacting a titanium halide compound, and then (d) an electron donating compound (Optionally contacting with a titanium halide compound)
JP-A-146904), (a) contacting a magnesium dialkoxide with (b) a silicon halide compound having a hydrogen-silicon bond, (c) contacting with an electron donating compound, and then (d)
A method of contacting a titanium compound (JP-A-58-1985)
03 publication). Among these, the method is desirable.

The component (A) is prepared as described above, and the component (A) may be washed with the above-mentioned inert medium, if necessary, and further dried. In component (A),
Preferably, 5 to 40% by weight of Mg, 1 to 2.5% by weight of Ti, 30 to 70% by weight of halogen, and 0 to 20% by weight of an electron donating compound are contained.

Also, magnesium, titanium, halogen,
A desirable method for preparing the solid component (A ') containing a metal oxide and an electron donating compound as essential components is disclosed in
No. 162607, No. 55-94909, No. 55-115405, No. 57-108107, No. 61-21109, No. 61-174204
JP-A-61-174205 and JP-A-61-174
No. 206, 62-7706 and the like. More specifically, a method in which a reaction product of a metal oxide and a magnesium dialkoxide is brought into contact with an electron-donating compound and a tetravalent titanium halide (JP-A-58-162607); A method in which a reaction product of a hydrocarbyl halide compound is contacted with a Lewis base compound and titanium tetrachloride (Japanese Patent Application Laid-Open No. 55-94909), a reaction product of a porous carrier such as silica and an alkylmagnesium compound is treated with titanium. A method of contacting with an electron donating compound and a silicon halide compound before contacting with a compound (Japanese Patent Application Laid-Open Nos. 55-115405 and 57-1)
08107), metal oxides, alkoxy-containing magnesium compounds,
A method of contacting an aromatic polycarboxylic acid having a carboxyl group at the ortho position or a derivative thereof and a titanium compound (JP-A-61-174204), a metal oxide, an alkoxy group-containing magnesium compound,
A method of contacting a silicon compound having a hydrogen-silicon bond, an electron donating compound, and a titanium compound
-174205), a metal oxide, an alkoxy group-containing magnesium compound,
A method of contacting a halogen element or a halogen-containing compound, an electron-donating compound and a titanium compound (JP-A-6
No. 1-174206), a method of contacting a reaction product obtained by contacting a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron-donating compound and a titanium compound (JP-A-61-21109). ), Contacting a solid obtained by contacting a metal oxide, hydrocarbylmagnesium and a hydrocarbyloxy group-containing compound (in charge of the alkoxy group-containing compound) with a halogen-containing alcohol, and further with an electron-donating compound and a titanium compound (Japanese Patent Laid-Open No. Sho 62-7706). Among these ~
The above method is particularly preferable.

In component (A '), Mg is preferably 2
-12%, Ti 1-5%, halogen 10-35% by weight, metal oxide 30-70% by weight, and electron-donating compound 0-20% by weight.

2. Component (B) General formula (R ^k ) _r Al
(Y) _3-r (where R ^k is each independently an alkyl group and an aryl group, Y is each independently a group selected from an alkoxy group and an aryloxy group, and r is 0 ≦ at least one selected from the group consisting of an organoaluminum compound represented by the formula: and an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Aluminum Compound The component (B) organoaluminum compound has a general formula: (R ^k ) _r Al (Y) _3-r (where R ^k is independently a group selected from an alkyl group and an aryl group, Y is each independently a group selected from chlorine, an alkoxy group and an aryloxy group, and r is an arbitrary number in the range of 0 ≦ r ≦ 3.) You. Preferably, one or a combination of two or more of the following compounds is selected,
Can be used.

(I) dialkylaluminum monoalkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dipropylaluminum ethoxide, diisopropylaluminum ethoxide,
Examples thereof include diisobutylaluminum ethoxide, di (n-butyl) aluminum ethoxide, di (n-hexyl) aluminum ethoxide, and di (n-octyl) aluminum ethoxide.

(Ii) alkylaluminum dialkoxides, for example, methylaluminum diethoxide, ethylaluminum diethoxide, propylaluminum diethoxide, n-butylaluminum diethoxide, isobutylaluminum diethoxide, n-hexylaluminumdiethoxide And n-octyl aluminum diethoxide.

(Iii) trialkoxy aluminum
For example, trimethoxyaluminum, triethoxyaluminum and the like can be mentioned.

(Iv) Alkyl aluminoxanes such as methylaluminoxane and ethylaluminoxane.

(V) Dialkylaluminum monophenoxides, for example, diethylaluminum phenoxide, diisobutylaluminum phenoxide and the like.

(Vi) trialkylaluminums such as trimethylaluminum, triethylaluminum,
Examples include tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, and trihexylaluminum.

The alkyl group preferably has 1 carbon atom.
To 18 alkyl groups, and the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms. An aryl group is
For example, it is a phenyl group and the like, and the aryloxy group is a phenoxy group and the like.

Among them, trialkylaluminum is preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable, and trimethylaluminum is most preferable from the viewpoint of improving MFR. Also, trialkyl aluminum is
It can be used in combination with other organic aluminum compounds.

Alternatively, an organic aluminum compound other than the above, in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom, can be used. Such compounds include, for example, (C ₂ H ₅ ) ₂
AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C _{4
H 9) 2, (C 2} H 5) 2 AlN (C 2 H 5) Al (C 2 H 5) 2
And the like.

3. Component (C) Alkylalkoxysilane Compound The component (C) alkylalkoxysilane compound of the present invention may be, for example, a compound represented by the following formula: (R ¹ ) _s Si (OR ² ) _{4 -s} (wherein R ¹ is each independently , Carbon number 1-6
(Preferably 3 to 5) alkyl groups and cycloalkyl groups, wherein R ² is each independently
(S is a number in the range of 1 ≦ s ≦ 3). However, it is not limited to these.

Examples of R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a sec-butyl group, a tert-amyl group, a cyclopentyl group and a cyclohexyl group. R ¹ is preferably selected from a propyl group, a cyclopentyl group, an isopropyl group and a tert-butyl group. As R ² , for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a sec-butyl group, a te
Examples thereof include an rt-amyl group, a cyclopentyl group, a cyclohexyl group, a 2-methyl-3-butenyl group, a 3-methyl-2-butenyl group, and a 2-methyl-3-butynyl group. R ² is preferably selected from a methyl group, an ethyl group, an isopropyl group, a sec-butyl group and a tert-butyl group.

As specific compounds, for example, tert-
Butoxycyclopentyldimethoxysilane, isopropoxycyclopentyldimethoxysilane, sec-butoxycyclopentyldimethoxysilane, di-sec-butoxypropylmethoxysilane, propyltriethoxysilane, tert-butylcyclopentyldimethoxysilane, tert-amyloxycyclopentyldimethoxysilane, (2- Methyl-3-butene-2-oxy) cyclopentyldimethoxysilane, (3-methyl-2-butene-1-oxy) cyclopentyldimethoxysilane,
(2-methyl-3-butene-2-oxy) cyclopentyldimethoxysilane, tert-butoxycyclohexyldimethoxysilane, isopropoxycyclohexyldimethoxysilane, sec-butoxycyclohexyldimethoxysilane, tert-amyloxycyclohexyldimethoxysilane, (2-methyl- (3-butene-2-oxy) cyclohexyldimethoxysilane, (3-methyl-2-butene-1-oxy) cyclohexyldimethoxysilane, (2-methyl-3-butene-2-oxy) cyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane , Dicyclopentyldimethoxysilane,
Cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxylan, cyclopentyltrimethoxylan and the like can be mentioned.

As the alkylalkoxysilane compound,
In addition to the above, a lactone group, an alkylalkoxylan containing a carboxyl group, a silicon atom as a ring-constituting atom,
Alkylalkoxysilanes having a heterocyclic substituent having a nitrogen atom can also be preferably used.

The preferred component (C) is a silane compound having a branched alkyl or alkoxy group or an alicyclic group, and particularly preferred is isopropoxycyclopentyldimethoxysilane, sec-butoxycyclopentyldimethoxylan, cyclohexylmethyldimethoxysilane. Silane, dicyclopentyldimethoxysilane, dise
At least one selected from c-butoxypropylmethoxysilane, tert-butylcyclopentyldimethoxysilane, and tert-amioloxycyclopentyldimethoxysilane.

4. Component (D) Component (D) of the present invention is a compound represented by the general formula MetR _X. Where Met is Mg, B, Al, Ga, G
e, In, Sn, Sb or a transition metal element, preferably Ti, Mg, B, Al, Co, Rh, Ni, Pd,
Zn, and more preferably B and Al. R represents a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, preferably two or more halogen atoms, more preferably at least one of Br and I, more preferably Br, I , And most preferably contains 2 or more Br. Examples of the hydrocarbon-containing group include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and octyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, alkoxy groups such as t-butoxy, aryl groups such as phenyl, phenoxy and the like. And a phosphine group such as a triphenylphosphine group. x is the valence of Met described above. Specific compounds include boron bromide, boron iodide, boron chloride, ethyl dibromoboron, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquiiodide,
Ethyl aluminum dibromide, aluminum bromide,
Examples include palladium bromide, bis (triphenylphosphine) palladium dibromide, nickel bromide, zinc bromide, magnesium bromide and the like.

5. Component (E) Furthermore, in the present invention, a zinc compound of the component (E) can be added and used as necessary. The zinc compound is Z
It is an alkyl zinc represented by nR ₂ , and examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms. Specific examples include diethyl zinc and dimethyl zinc.

6. Component (F) In the present invention, if necessary, component (F)
An aluminum hydride compound can be added and used. By using the component (F), MFR can be further increased while maintaining stereoregularity. As aluminum hydride compounds, AlR ₃ (R
Is an independent hydrogen or alkyl group, at least one of which is hydrogen. ) And does not correspond to the organoaluminum compound of the component (B). Specific examples include aluminum hydride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and the like.

7. Component (G) In the production of the propylene-ethylene block copolymer of the present invention, a metallocene compound may be added as component (G), if necessary. The metallocene compounds of the general formula Cp _n MY _4-n (wherein, Cp
Is a substituted or unsubstituted cyclopentadienyl group, M is Ti,
An element selected from Zr and Hf, Y is a group selected from hydrogen, a halogen, an alkoxy group, an amino group, an alkyl or aryl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. ). Of these compounds, bis (cyclopentadienyl) titanium dichloride and bis (cyclopentadienyl) titanium dibromide are preferred.

8. (A), (B), (C), (D),
The proportions of the components (E), (F) and (G) The catalyst of the present invention comprises the above-mentioned components. Preferably, the component (B) is added in an amount of 7 per mole of titanium in the component (A).
0 to 600 mol, 10 to 30 mol of the component (C) and 2 to 200 mol of the component (D) are blended. More preferably, 90 moles of component (B) per mole of titanium in component (A).
４００400 mol, 15 to 25 mol of component (C) and 9 to 150 mol of component (D) are blended. Component (E),
When (F) and (G) are used, 9 to 600 mol of the component (E), 20 to 300 mol of the component (F) and 0.2 to 300 mol of the component (G) per 1 mol of titanium in the component (A). 0001
It is preferred to use １1 mol.

9. Prepolymerization In the present invention, the component (A) may or may not be subjected to prepolymerization. In the case of performing prepolymerization, the prepolymerization is carried out in the presence of an organoaluminum (component H) and optionally an organosilicon compound (component I). It is performed by contacting with an olefin. The organoaluminum (composed HE) can be used by selecting one or more compounds from the compounds described in the component (B). Among them, trialkyl aluminum,
Particularly, triethylaluminum and triisobutylaluminum are preferable. As the organosilicon compound (component I), any of the compounds described in the above-mentioned component (C) can be used, but other compounds having a total of four alkyl groups and alkoxy groups bonded to a silicon atom can also be used. It is possible.
For example, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane ethyltriisobutoxy Silane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyl Diphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diphenyldimethoxysilane,
Examples include diphenyldiethoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane. Preferred organosilicon compounds (component I) include t-butoxycyclopentyldimethoxysilane, isopropoxycyclopentyldimethoxysilane and s-butoxycyclopentyldimethoxysilane.

Examples of the olefin used for the prepolymerization include, in addition to ethylene, α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. Prepolymerization is normal butane, isobutane,
Normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene,
It is preferably carried out in an inert hydrogen such as xylene. The prepolymerization is usually carried out at a temperature of 100 ° C or lower, preferably -30 ° C to +
The reaction is performed at a temperature of 30 ° C, more preferably -20 ° C to + 20 ° C. The polymerization system may be either a batch system or a continuous system, and may be performed in two or more stages.

The component (H) has a concentration of 10 to 10 in the prepolymerized system.
It is used in an amount of 500 mmol / l, preferably 30 to 200 mmol / l, and 1 to 50,000 mol per 1 mol of titanium in the component (A).
It is preferably used in an amount of 2 to 1,000 mol. When the component (F) is used, the concentration in the prepolymerized system is from 1 to 1,000 mmol / L, preferably from 5 to 2 mmol / L.
It is used to be 00 mmol / liter. The olefin polymer is incorporated into the component (A) by the prepolymerization, and the amount of the polymer is preferably 0.1 to 200 g, particularly preferably 0.5 to 50 g per 1 g of the component (A). The catalyst component thus prepared can be diluted or washed with the above-mentioned inert medium, but it is particularly preferable to wash it from the viewpoint of preventing catalyst deterioration.
After washing, it may be dried if necessary. When storing the catalyst, it is preferable to store it at a temperature as low as possible.
A temperature range of 0 ° C to + 30 ° C, especially -20 ° C to + 5 ° C, is recommended.

10. Copolymerization of propylene and ethylene Component (A), component (B), component (C) and component (D) pre-polymerized or not pre-polymerized as described above,
Alternatively, propylene and ethylene are copolymerized in the presence of a catalyst comprising a component (E), a component (F) and a component (G) as required. The propylene-ethylene block copolymer and the propylene-ethylene random copolymer are performed as follows.

(1) Propylene-ethylene block copolymer The propylene-ethylene block copolymer is obtained by polymerizing propylene to obtain a highly crystalline polypropylene (a).
And a step (b) of copolymerizing propylene and ethylene. (A) Polymerization of propylene In the step (a), propylene is polymerized. As the reaction conditions in the polymerization of propylene, conventional conditions can be used. For example, -80 to + 150 ° C, preferably 0 to 12
At a temperature of 0 ° C, more preferably 40-120 ° C, 1-6
Performed at 0 atm for 0.5-7 hours. The polymerization reaction may be performed in a gas phase or a liquid phase. When performing in the liquid phase,
It can be carried out in the above-mentioned inert medium or in a liquid monomer. Further, the polymerization may be performed in either a batch system or a continuous system. In order to control the molecular weight of the produced polymer, a known molecular weight controlling agent such as hydrogen can be present in the polymerization reaction system. In the step (a), it is preferable that the polypropylene obtained therefrom accounts for 50 to 98% by weight, particularly 70 to 95% by weight of the finally obtained block copolymer.

(B) Copolymerization of propylene and ethylene Next, in step (b), propylene and ethylene are copolymerized. The copolymerization is carried out by contacting and reacting propylene with ethylene so that the ethylene content in the copolymer obtained therefrom is preferably 30 to 95% by weight, more preferably 40 to 80% by weight. . The conditions of the copolymerization reaction can be appropriately selected from the polymerization reaction conditions described in the step (a). Further, a molecular weight controlling agent can be present in the copolymerization reaction system. It is preferable that the amount of the copolymer block obtained in the step (b) be 50 to 2% by weight, particularly 30 to 5% by weight of the finally obtained block copolymer. In the present invention, step (a) and step (b) are preferably performed in that order,
Steps (a) and (b) can each be performed any number of times.

(2) Propylene-ethylene random copolymer Conventional reaction conditions can be used for the random copolymerization of propylene and ethylene. For example, -80 to +1
50 ° C, preferably 0-120 ° C, more preferably 40 ° C
It is carried out at a temperature of １２０120 ° C. and at a pressure of 1６０60 atm for 0.5 to 7 hours. The polymerization reaction may be performed in a gas phase or a liquid phase. When the reaction is carried out in a liquid phase, the reaction can be carried out in the above-mentioned inert medium or in a liquid monomer. Further, the polymerization may be performed in either a batch system or a continuous system. In order to control the molecular weight of the produced polymer, a known molecular weight controlling agent such as hydrogen can be present in the polymerization reaction system. The ethylene content in the copolymer is preferably from 0.1 to 10% by weight, more preferably from 0.1 to 8% by weight.

[0070]

The present invention will be described in more detail with reference to the following examples. The percentages are by weight unless otherwise specified. The physical properties were measured according to the following methods. (1) MFR: 230 according to ASTM D1238
The mass of the sample extruded for 10 minutes at a temperature of 2.degree. (2) Flexural modulus: Measured in accordance with JIS K7203-1982. (3) DuPont impact strength: JIS K7211-197
6 was measured. (4) Haze: Measured according to ASTM D1003.

A test piece for measuring the flexural modulus and the Dupont impact strength was prepared as follows. In the polymer,
2,6-di-t-butyl-4-methylphenol (BH
T) 0.18% by weight, distearyl thiodipropionate (DSTDP) 0.08% by weight, tetrakis-methylene- (3,5-di-t-butylhydroxyhydrocinnamate) methane (IRGANOX1010: trademark, Ciba-Geigy) 0.04% by weight) and 0.06% by weight of calcium stearate were added and dry-blended, then melt-kneaded and formed into pellets. Next, a test piece was prepared by injection molding using the pellet. Also,
A test piece for measuring haze was prepared as follows. 0.1% by weight of 2,6-di-t-butyl-4-methylphenol (BHT) was added to the polymer, and these were dry-blended, melt-kneaded and pelletized. Next, a test piece having a thickness of 1.0 mm was prepared by injection molding using the pellets.

Example 1 (1) Preparation of solid catalyst component (A1) Chip-like metallic magnesium (purity 99.1) was placed in a 1-liter reaction vessel equipped with a reflux condenser under a nitrogen gas atmosphere.
8.3 g of 5%, average particle size of 1.6 mm) and 250 ml of n-hexane were added, and the mixture was stirred at 68 ° C. for 1 hour. The metallic magnesium was taken out and dried at 65 ° C. under reduced pressure. Obtained.

Next, a suspension obtained by adding 140 ml of n-butyl ether and 0.5 ml of an n-butyl ether solution of n-butylmagnesium chloride (1.75 mol / l) to the metallic magnesium was maintained at 55 ° C. 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 performing the reaction at 70 ° C. for 4 hours with stirring, the reaction solution was kept at 25 ° C. Then, HC (OC ₂ H ₅₎ To the reaction solution ₃ 5
5.7 ml was added dropwise over 1 hour. After dropping, 60
The reaction was carried out at 15 ° C. for 15 minutes, and the resulting reaction solid was washed with n-hexane (300 ml each) six times and dried under reduced pressure at room temperature for 1 hour. 31.6 g of a solid were recovered.

In a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, under a nitrogen gas atmosphere,
6.3 g of magnesium-containing solid and 50 n-heptane
into a suspension and stirred at room temperature while stirring.
A mixed solution of 20 ml (0.02 mmol) of 2-trichloroethanol and 11 ml of n-heptane was dropped from the dropping funnel over 30 minutes, and further stirred at 80 ° C. for 1 hour. The obtained solid was filtered, and n-hexane at room temperature for 10
Wash 4 times with 0 ml, then add 2 ml with 100 ml each of toluene.
Washing twice gave a solid.

To the above solid, 40 ml of toluene was added, and titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene was 3/2, and the temperature was raised to 90 ° C. Under stirring,
After a mixed solution of 2 ml of dibutyl phthalate and 5 ml of toluene was added dropwise over 5 minutes, the mixture was stirred at 120 ° C. for 2 hours.
In addition, a new titanium tetrachloride / toluene volume ratio of 3
/ 2 and add titanium tetrachloride at 120 ° C.
Stirred for hours. The solid material obtained is filtered off at 110 ° C.
The plate was washed seven times with 100 ml of n-hexane at room temperature.
Thus, 5.5 g of a solid component (A1) was obtained.

(2) Propylene-ethylene block copolymerization (a) Polymerization of propylene (step a) In a 1.5 liter stainless steel autoclave equipped with a stirrer under a nitrogen atmosphere, the solid obtained in the above (1) 4.5 mg of catalyst component (A1), 1.6 mmol of triethylaluminum, 0.08 mmol of t-amyloxycyclopentyldimethoxysilane and 7 ml of n-heptane
Were mixed and the one kept for 5 minutes was added. Then, 0.04 mmol of aluminum bromide was added, 6000 ml of hydrogen as a molecular weight controlling agent (normal temperature, normal pressure) and 1 liter of liquid propylene were injected, and then the temperature of the reaction system was increased to 70 ° C., and propylene was added for 1 hour. Was polymerized. After completion of the polymerization, unreacted propylene and hydrogen were purged, and a part of the first-stage polymer (polypropylene) was collected.

(B) Copolymerization of Propylene and Ethylene (Step b) Following the first stage polymerization, a mixed gas having a molar ratio of propylene and ethylene of 1.5 was supplied to carry out the copolymerization of propylene and ethylene. went. The pressure in the container is 6 kg / cm ² G
And copolymerized at 75 ° C. for 2 hours. After polymerization,
Unreacted gas was purged to remove the polymer and dried. The MFR of the polymer finally obtained is 56 g / 1.
It was 0 minutes. As a result of the analysis, the amount of the polymer obtained by the copolymerization in the step (b) was 20% by weight, and the ethylene content in the copolymer was 50% by weight. Further, the M of the polymer sampled after the end of the step (a)
FR was 151 g / 10 minutes. When the physical properties of the final polymer were measured, the flexural modulus was 10.5 kg / cm.
^2. DuPont impact strength was 66.2 kg · cm.

Example 2 In Example 1 (2), triethyl aluminum
A propylene copolymer was produced in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of t-amyloxycyclopentyldimethoxysilane. Table 1 shows the results.

Examples 3 to 10 In Example 1 (2), instead of t-amyloxycyclopentyldimethoxysilane and aluminum bromide,
A propylene copolymer was produced in the same manner as in Example 1 except that the compounds shown in Table 1 were used in specified amounts. Table 1 shows the results.

Example 11 (1) Preparation of Catalyst Solid Component (A2) A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. In this flask, 5 g of silicon oxide (trade name: G-952, manufactured by DAVISON) and 40 ml of n-heptane, which were calcined at 200 ° C. for 2 hours and further at 700 ° C. for 5 hours in a nitrogen stream, were put. Further, n-butylethylmagnesium (hereinafter, referred to as n-butylethylmagnesium)
BEM) 20% -n-heptane solution (manufactured by Texas Alkyls, trade name: MAGALA BEM) 20
Then, the mixture was stirred at 90 ° C. for 1 hour.

After the obtained suspension was cooled to 0 ° C., 11.2 g of tetraethoxysilane was added to 20 ml of n-
The solution dissolved in heptane was dropped from the dropping funnel over 30 minutes. After completion of the dropwise addition, the temperature was raised to 50 ° C. over 2 hours, and stirring was continued at 50 ° C. for 1 hour. After the completion of the stirring, the supernatant was removed by decantation, and the generated solid was washed with 60
Washing at room temperature with ml of n-heptane, and the supernatant was removed by decantation. This washing treatment with n-heptane was further performed four 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 from a dropping funnel for 25 minutes. The mixture was added dropwise at 15 ° C over 15 minutes. After completion of the dropwise addition, stirring was continued at 25 ° C. for 30 minutes. After completion of the stirring, 2 ml of n-heptane was added at room temperature.
Washing was performed three times each with 60 ml of toluene. When the obtained solid (referred to as solid component I) was analyzed, SiO2: 36.6%, Mg: 5.1%, Cl:
It contained 38.5%.

To the solid component I obtained above, 10 ml of n-heptane and 40 ml of titanium tetrachloride were added.
Then, 0.6 g of di-n-butyl phthalate dissolved in 5 ml of n-heptane was added over 5 minutes. afterwards,
The temperature was raised to 115 ° C., and the reaction was performed for 2 hours. After the temperature was lowered to 90 ° C., the supernatant was removed by decantation, and the mixture was washed twice with 70 ml of n-heptane. Further 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 obtained solid substance is
Washing was performed 8 times at room temperature with 1 n-hexane. Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a solid component (A2). As a result of analysis, this component A contained T
i is contained at 3.1% by weight, and Si, Mg,
It was confirmed that Cl and di-n-butyl phthalate were contained.

(2) Propylene-ethylene block copolymerization (a) Polymerization of propylene (step a) In a 1.5 liter stainless steel autoclave equipped with a stirrer, under nitrogen atmosphere, the solid obtained in the above (1) 8.8 mg of catalyst component (A2), 1.6 mmol of triethylaluminum, 0.08 mmol of t-amyloxycyclopentyldimethoxysilane and 7 ml of n-heptane
Were mixed and the one kept for 5 minutes was added. Then, 0.04 mmol of aluminum bromide was added, 6000 ml of hydrogen as a molecular weight controlling agent (normal temperature, normal pressure) and 1 liter of liquid propylene were injected, and then the temperature of the reaction system was increased to 70 ° C., and propylene was added for 1 hour. Was polymerized. After completion of the polymerization, unreacted propylene and hydrogen were purged, and a part of the first-stage polymer (polypropylene) was collected.

(B) Copolymerization of Propylene and Ethylene (Step b) Following the first stage polymerization, a mixed gas having a molar ratio of propylene and ethylene of 1.5 was supplied to carry out the copolymerization of propylene and ethylene. went. The pressure in the container is 6 kg / cm ² G
And copolymerized at 75 ° C. for 2 hours. After polymerization,
Unreacted gas was purged to remove the polymer and dried. The MFR of the finally obtained polymer is 57 g / 1.
It was 0 minutes. As a result of the analysis, the amount of the polymer obtained by the copolymerization in the step (b) was 19% by weight, and the ethylene content in the copolymer was 50% by weight. Further, the M of the polymer sampled after the end of the step (a)
FR was 162 g / 10 min. When the physical properties of the final polymer were measured, the flexural modulus was 8.7 kg / c.
m ² , and DuPont impact strength was 62.9 kg · cm.

Example 12 Example 1 (2) was repeated except that the compounds shown in Table 1 were added in place of aluminum bromide in the specified amount in (2) of Example 11.
A propylene copolymer was produced in the same manner as described above. Table 1 shows the results.

Example 13 A propylene copolymer was produced in the same manner as in Example 1 except that 1.6 mmol of diethylzinc was added in (2) of Example 1. Table 2 shows the results.

Example 14 In Example 1, (a) polymerization of propylene (step a)
Was carried out in the same manner as in Example 1 except that the propylene copolymer was prepared as follows. Table 2 shows the results. (A) Polymerization of propylene (step a) A solid catalyst component (A1) was placed in a 1.5-liter stainless steel autoclave equipped with a stirrer under a nitrogen atmosphere.
4.2 mg, 1.6 mmol of triethylaluminum,
t-amyloxycyclopentyldimethoxysilane 0.0
8 mmol and 7 ml of n-heptane were mixed and kept for 5 minutes. Then, aluminum bromide 0.
04 mmol, diethylaluminum hydride 0.
4 mmol, and hydrogen as a molecular weight controlling agent was 700
After pressurizing 0 ml (normal temperature, normal pressure) and 1 liter of liquid propylene, the temperature of the reaction system was raised to 70 ° C., and polymerization of propylene was performed for 59 minutes. At this point, 2.5 × 10 ^-4 of bis (cyclopentadienyl) titanium dichloride
1 ml of a mol / l toluene solution was injected under pressure. After one minute, stirring of the autoclave was stopped, and at the same time, hydrogen and unreacted propylene were purged, and a part of the first-stage polymer (polypropylene) was collected.

Examples 15 to 16 A propylene copolymer was produced in the same manner as in Example 14 except that 1.6 mmol of dimethylzinc or diethylzinc was added in (2) of Example 14. Table 2 shows the results
Shown in

Comparative Example 1 A propylene copolymer was prepared in the same manner as in Example 1 except that aluminum bromide was not used and the amount of hydrogen added was 80000 ml (normal temperature, normal pressure). Was manufactured. Table 3 shows the results.

Comparative Example 2 In Example 1 (2), triethyl aluminum
The compounds shown in Table 2 were used in place of t-amyloxycyclopentyldimethoxysilane, aluminum bromide was not used, and the amount of hydrogen added was 80,000 ml (normal temperature, normal pressure).
A propylene copolymer was produced in the same manner as in Example 1 except that the above was used. Table 3 shows the results.

Comparative Example 3 In Example 1 (2), tetraethoxysilane was used in place of t-amyloxycyclopentyldimethoxysilane, aluminum bromide was not used, and the amount of hydrogen added was 1400 ml (normal temperature, normal temperature). Pressure), and a propylene copolymer was produced in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 4 In Example 1 (2), cyclohexylmethyldimethoxysilane was used in place of t-amyloxycyclopentyldimethoxysilane, aluminum bromide was not used, and the amount of hydrogen added was 8000 ml (normal temperature, A propylene copolymer was produced in the same manner as in Example 1 except that the pressure was changed to normal pressure. Table 3 shows the results.

Comparative Example 5 A propylene copolymer was produced in the same manner as in Example 11, except that aluminum bromide was not used in the propylene polymerization of Example 11 (step a). Table 3 shows the results
Shown in

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

Example 17 In a 1.5-liter stainless steel autoclave equipped with a stirrer, under a nitrogen atmosphere, 4.7 mg of the solid catalyst component (A1) obtained in (1) of Example 1 was added. 6 mmol, 0.08 mmol of t-amyloxycyclopentyldimethoxysilane and 7 ml of n-heptane were mixed, and the mixture kept for 5 minutes was added. Then, 0.04 mmol of aluminum bromide was added, 2000 ml of hydrogen (normal temperature, normal pressure) and 1 liter of liquid propylene were injected under pressure as a molecular weight controlling agent.
The temperature was raised to 0 ° C., and ethylene was continuously supplied to polymerize propylene for 1 hour. After completion of the polymerization, unreacted propylene, ethylene and hydrogen were purged, and the polymer was taken out and dried. The MFR of the obtained polymer was 31.5 g /
After 10 minutes, the ethylene content was 4.0% by weight. When the physical properties were measured, the flexural modulus was 11.3 kg / cm ² ,
The haze was 18%.

Example 18 A propylene copolymer was produced in the same manner as in Example 17 except that the compounds shown in Table 3 were used instead of triethylaluminum and aluminum bromide. Table 4 shows the results.

Examples 19 to 20 The procedure of Example 17 was repeated, except that the specified amounts of the compounds shown in Table 3 were used instead of t-amyloxycyclopentyldimethoxysilane and aluminum bromide. A polymer was produced. Table 4 shows the results.

Example 21 In a 1.5-liter stainless steel autoclave equipped with a stirrer, 9.2 mg of the solid catalyst component (A2) obtained in (1) of Example 11 and triethylaluminum in a nitrogen atmosphere were added. 6 mmol, 0.08 mmol of t-amyloxycyclopentyldimethoxysilane and 7 ml of n-heptane were mixed, and the mixture kept for 5 minutes was added. Then, 0.04 mmol of aluminum bromide was added, 2000 ml of hydrogen (normal temperature, normal pressure) and 1 liter of liquid propylene were injected under pressure as a molecular weight controlling agent.
The temperature was raised to 0 ° C., and ethylene was continuously supplied to polymerize propylene for 1 hour. After completion of the polymerization, unreacted propylene, ethylene and hydrogen were purged, and the polymer was taken out and dried. The MFR of the obtained polymer was 33.7 g /
After 10 minutes, the ethylene content was 3.9% by weight. When the physical properties were measured, the flexural modulus was 10.3 kg / cm ² ,
The haze was 20%.

Example 22 A propylene copolymer was produced in the same manner as in Example 22, except that the compounds shown in Table 3 were added in place of aluminum bromide. Table 4 shows the results
Shown in

Example 23 The procedure of Example 17 was repeated, except that trimethylaluminum was used instead of triethylaluminum.
6 mmol, diethyl aluminum hydride 0.4
Mmol and the amount of hydrogen added was 1500 ml (normal temperature,
A propylene copolymer was produced in the same manner as in Example 17 except that the pressure was changed to normal pressure. Table 4 shows the results.

Comparative Example 6 A propylene copolymer was produced in the same manner as in Example 17 except that aluminum bromide was not used. Table 4 shows the results.

Comparative Example 7 A propylene copolymer was produced in the same manner as in Example 21, except that aluminum bromide was not used. Table 4 shows the results.

Comparative Example 8 In the same manner as in Example 17, except that cyclohexylmethyldimethoxysilane was used instead of t-amyloxycyclopentyldimethoxysilane, and the amount of hydrogen added was 3,200 ml (normal temperature, normal pressure). To produce a propylene copolymer. Table 4 shows the results.

[0107]

[Table 4]

[0108]

According to the method of the present invention, a propylene-ethylene block copolymer having an excellent balance between rigidity and impact resistance and an excellent balance between transparency and rigidity in a high MFR region suitable as a molding material. It has become possible to produce a propylene-ethylene random copolymer.

[Brief description of the drawings]

FIG. 1 is a flowchart of a catalyst component and a polymerization method according to the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Satoshi Shimizu 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Inside the Tonen Co., Ltd. 1-3-1 Oka, Tonen Co., Ltd. (72) Inventor Issei Akira 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama

Claims (3)

[Claims] 1. A solid component comprising (A) magnesium, titanium, a halogen and an electron donating compound as essential components,
(B) a general formula (R ^k ) _r Al (Y) _3-r (where R ^k is each independently an alkyl group or an aryl group;
Y is each independently a group selected from an alkoxy group and an aryloxy group, and r is an arbitrary number in the range of 0 ≦ r ≦ 3. Or an organic aluminum compound selected from at least one selected from organic aluminum compounds in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom,
(C) an alkylalkoxysilane compound and (D) a general formula MetR _x (where Met is Mg, B, Al, G
a, Ge, In, Sn, Sb or a transition metal element;
R represents a halogen atom or a hydrocarbon-containing group, at least one of which is a halogen atom, and x represents the valency of Met. A method for producing a propylene-ethylene copolymer, comprising copolymerizing propylene and ethylene in the presence of a polymerization catalyst comprising a compound represented by the formula (1). 2. A copolymer of propylene and ethylene,
The propylene-ethylene copolymer according to claim 1, wherein (a) a step of polymerizing propylene and (b) a step of copolymerizing propylene and ethylene are performed to produce a propylene-ethylene block copolymer. Production method. 3. A propylene-ethylene random copolymer according to claim 1, wherein the copolymerization of propylene and ethylene is carried out under conditions containing an ethylene content of 0.01 to 10% by weight. A method for producing an ethylene copolymer.