JP2978287B2 - Method for producing propylene block copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a propylene block copolymer, and more particularly to a method for producing a propylene block copolymer having an excellent balance between impact resistance and rigidity.

[0002]

2. Description of the Related Art In recent years, the demand for highly crystalline polypropylene produced by using various kinds of highly stereoregular catalysts has been rapidly increasing because of its excellent rigidity and heat resistance. However, these properties are still inadequate depending on the purpose of use, and various methods for improving rigidity have been proposed, but most of them are methods in which post-treatment such as adding a nucleating agent to polypropylene is performed. is there. Therefore, the cost of the process is high, and some additives impair the appearance of the molded article. A method of improving rigidity by a polymerization method without treatment with an additive has also been proposed, but none of these methods has insufficient rigidity.

[0003] Furthermore, since polypropylene originally has a drawback of low impact strength, a method of improving impact resistance by copolymerizing with other olefins such as ethylene has been widely used. Although the impact resistance is improved by this method, the rigidity is reduced accordingly. Therefore, various methods have been proposed in which polymerization is performed stepwise while changing the polymerization ratio of other olefins of propylene, that is, multistage polymerization is performed to improve the rigidity and impact resistance of the copolymer. However, even with these methods, a sufficiently good balance of physical properties cannot be obtained.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for more effectively producing a propylene block copolymer having an excellent balance between impact resistance and rigidity.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the object of the present invention by copolymerizing using a polymerization catalyst containing a specific organosilicon compound as an essential component. The inventors have found that the present invention has been completed and completed the present invention.

The gist of the invention, that is, the gist of the present invention is as follows: (A) a solid catalyst component containing metal oxide, magnesium, titanium, halogen and an electron donating compound as essential components; (B) an organometallic compound; General formula

Embedded image [However, R ¹ , R ⁴ and R ⁵ are the same or different and have 1 carbon atom.
10 to 10 hydrocarbon groups, R ² is a hydrocarbon group having 1 to 10 carbon atoms or R ⁶ O, R ³ is a hydrocarbon group having 1 to 10 carbon atoms or R ⁷ O, and x is 2 or 3, R ⁶
And R ⁷ are the same or different hydrocarbon groups having 1 to 10 carbon atoms. (A) in the presence of a polymerization catalyst comprising an organosilicon compound represented by the following formula (1): (a) a step of polymerizing propylene to produce a highly crystalline polypropylene; and (2) a step (b) of copolymerizing propylene with ethylene. )) To produce a propylene block copolymer.

Solid catalyst component A solid catalyst component (hereinafter referred to as component A), which is one component of the catalyst used in the present invention (hereinafter referred to as the catalyst of the present invention), comprises:
Metal oxides, magnesium, titanium, halogens and electron donating compounds are essential components. Such components are usually metal oxides, magnesium compounds, titanium compounds and electron donating compounds, and each of the above compounds has a halogen. In the case of a compound that is not used, it is prepared by contacting a halogen-containing compound with each other.

(1) Metal Oxide The metal oxide used in the present invention is selected from Group II of the periodic table of elements.
~ An oxide of an element selected from the group of group IV elements,
To illustrate them, B_TwoO_Three, MgO, Al _TwoO_Three,
SiO_Two, CaO, TiO_Two, ZnO, ZrO_Two, Sn
O_Two, BaO, ThO_TwoAnd the like. Among these
Also B_TwoO_Three, MgO, Al_TwoO_Three, SiO_Two, Ti
O_Two, ZrO_TwoIs preferable, especially SiO._TwoIs desirable.
Further, composite oxides containing these metal oxides, for example, Si
O_Two-MgO, SiO_Two-Al_TwoO_Three, SiO_Two−Ti
O_Two, SiO_Two-V_TwoO_Five, SiO_Two−Cr_TwoO_Three, S
iO_Two-TiO_Two-MgO or the like may be used. These metals
The oxide is usually in the form of a powder. Powdered
The shape, such as size and shape, depends on the olefin polymer obtained.
It may affect the shape of the
Is desirable. Metal oxides reduce poisons during use.
For the purpose of removal, bake at the highest possible temperature.
It is desirable to handle it so that it does not come into direct contact with air.

(2) 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, as the hydrocarbon group of R ¹ and R ² , an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group is used. 12 alkyl groups, cycloalkyl group, aryl group, aralkyl group is chlorine as a halogen atom,
Bromine, iodine, fluorine and the like.

Specific examples of these compounds are shown below. In the chemical formula, Me: methyl, Et: ethyl, Pr: propyl, Bu: butyl, He: hexyl, Oct: octyl, Ph: phenyl, and cyHe: cyclohexyl Show. MgMe ₂ , MgEt ₂ , Mgi-P
r ₂ , MgBu ₂ , MgHe ₂ , MgOct ₂ , MgE
tBu, MgPh ₂ , MgcyHe ₂ , Mg (OMe)
₂ , Mg (OEt) ₂ , Mg (OBu) ₂ , Mg (OH
e) ₂ , Mg (OOct) ₂ , Mg (OPh) ₂ , Mg
(OcyHe) ₂ , EtMgCl, BuMgCl, He
MgCl, i-BuMgCl, t-BuMgCl, Ph
MgCl, PhCH ₂ MgCl, EtMgBr, BuM
gBr, PhMgBr, BuMgI, EtOMgCl,
BuOMgCl, HeOMgCl, PhOMgCl, E
tOMgBr, BuOMgBr, EtOMgI, MgC
l ₂ , MgBr ₂ , MgI ₂ .

The above magnesium compound can be prepared from metallic magnesium or other magnesium compounds when 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 carbon atom having 1 to 2 carbon atoms.
0 hydrocarbon groups, 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. X of the general formula of the alkoxy group-containing compound
And the hydrocarbon group of R include methyl (Me), ethyl (Et), propyl, (Pr), i-propyl (i-P
r), an alkyl group such as butyl (Bu), i-butyl (i-Bu), hexyl (He), octyl (Oct), a cycloalkyl group such as cyclohexyl (cyHe), methylcyclohexyl, allyl, propenyl, butenyl, etc. Phenyl (Ph), tolyl, aryl groups such as 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. Hereinafter, specific examples of the alkoxy group-containing compound will be described.

Compounds wherein M is carbon Formula C (OR)_Four(OMe) contained in_Four, C (OE
t)_Four, C (OPr) _Four, C (OBu)_Four, C (Oi-
Bu)_Four, C (OHe)_Four, C (OOct)_Four: Formula X
C (OR)_Three(OMe) contained in_Three, HC (OE
t)_Three, HC (OPr)_3,HC (OBu)_Three, HC
(OHe)_Three, HC (OPh)_ThreeMeC (OM
e)_Three, MeC (OEt)_Three, EtC (OMe)_Three , E
tC (OEt)_Three, CyHeC (OEt)_Three, PhC
(OMe)_Three, PhC (OEt)_Three, CH_TwoClC (O
Et)_Three, MeCHBrC (OEt)_Three, MeCHCl
C (OEt) _Three; ClC (OMe)_Three, ClC (OE
t)_Three, ClC (Oi-Bu)_Three, BrC (OE
t)_ThreeFormula X_TwoC (OR)_TwoMeCH (O
Me)_Two, MeCH (OEt)_Two, CH_Two(OM
e)_Two, CH_Two(OEt)_Two, CH_TwoClCH (OE
t)_Two, CHCl_TwoCH (OEt)_Two, CCl_ThreeCH
(OEt)_Two, CH _TwoBrCH (OEt)_Two, PhCH
(OEt)_Two.

Compound when M is silicon Si (OMe) ₄ , Si contained in formula Si (OR) ₄
(OEt) ₄ , Si (OBu) ₄ , Si (Oi-Bu)
₄ , Si (OHe) ₄ , Si (OOct) ₄ , Si (O
Ph) ₄ : HSi (O) contained in the formula XSi (OR) ₃
Et) ₃ , HSi (OBu) ₃ , HSi (OHe) ₃ ,
HSi (OPh) ₃ ; MeSi (OMe) ₃ , MeSi
(OEt) ₃ , MeSi (OBu) ₃ , EtSi (OE
t) ₃ , PhSi (OEt) ₃ , EtSi (OP
h) ₃ ; ClSi (OMe) ₃ , ClSi (OE
t) ₃ , ClSi (OBu) ₃ , ClSi (OP
h) ₃ , BrSi (OEt) ₃ ; Formula X ₂ Si (OR)
₂ contained in Me ₂ Si (OMe) ₂ , Me ₂ Si (O
Et) ₂ , Et ₂ Si (OEt) ₂ ; MeClSi (O
Et) ₂ ; CHCl ₂ SiH (OEt) ₂ ; CCl ₃ S
iH (OEt) ₂ ; MeBeSi (OEt) ₂ : X ₃ S
Me ₃ SiOMe, Me ₃ SiOE contained in iOR
t, Me ₃ SiOBu, Me ₃ SiOPh, Et ₃ Si
OEt, Ph ₃ SiOEt.

Compound where M is boron B (OEt) ₃ , B (OB) contained in formula B (OR) ₃
u) ₃ , B (OHe) ₃ , B (OPh) ₃ .

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

Compound when M is phosphorus Formula P (OR)_Three(OMe) contained in_Three, P (OE
t)_Three, P (OBu) _Three, P (OHe)_Three, P (OP
h)_Three.

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 ¹ R
² · n (MR ³ _m ). Examples of the metal include aluminum, zinc, and calcium, and R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. M represents the valence of the metal M, and n represents a number of 0.1 to 10. Specific examples of the compound represented by MR ³ _m include AlMe ₃ , AlEt ₃ ,
_{Ali-Bu 3, AlPh 3,} ZnMe 2, ZnE
t ₂ , ZnBu ₂ , ZnPh ₂ , CaEt ₂ , CaPh
_{And the} like.

(3) Titanium compound Titanium compounds are trivalent and tetravalent titanium compounds,
To illustrate them, titanium tetrachloride, titanium tetrabromide, trichloroethoxy titanium, trichlorobutoxy titanium,
Examples thereof include dichlorodiethoxytitanium, dichlorodibutoxytitanium, dichlordiphenoxytitanium, chlorotriethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium, and titanium trichloride. Among these, tetravalent titanium halides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium and dichlorodiphenoxytitanium are desirable, and titanium tetrachloride is particularly desirable.

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

Specific examples of the carboxylic acid 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, and malonic acid. Succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid, 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, p-tert-butyl benzoic acid, naphthoic acid, aromatic monocarboxylic acids such as cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
And aromatic polycarboxylic acids such as melitic acid. As the carboxylic acid anhydride, the acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, and 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
-Tert-butyl ethyl benzoate, ethyl p-anisate,
α-ethyl ethyl naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, tetraethyl pyromellitate And the like.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used.
Specific examples thereof include acetate chloride, acetate bromide, acetate iodide, propionate chloride, butyrate 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 chloride, succinic 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 include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride and phthalic acid butyl chloride can also be used.

Alcohols are represented by the general formula ROH. In the formula, R is alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms. Specific examples 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,
and n-octylphenol.

The ethers are represented by the general formula ROR ^1. In the formula, R and R ¹ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R and R ¹ 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 and the like.

As a method for preparing component A, a metal oxide (component 1), a magnesium compound (component 2), a titanium compound (component 3) and an electron donating compound (component 4) are brought into contact in that order. After contacting component 1 and component 3,
Contact component 4 and component 3 in that order. After the components 1 and 2 are brought into contact, the components 3 and 4 are simultaneously used to contact each other. After the components 2 and 3 are brought into contact, the components 4 and 1 are brought into contact in that order. After contacting 4, contact component 3 and component 1 in that order,
A method such as contacting the component 1, the component 3, and the component 4 at the same time and then contacting the component 1 can be adopted. It is also possible to contact with a halogen-containing compound before contacting with Component 3.

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

Halogenated hydrocarbons include those having 1 to 1 carbon atoms.
Mono- and poly-halogen substituents of 12 saturated or unsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons. 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 paraffins are chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentagen, and hexachlorocyclohexane for alicyclic compounds, and chlorobenzene, bromobenzene, o-
Examples thereof include dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. 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 a hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in one molecule are substituted with a halogen atom. Means a compound. 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-
Chlorbenzhydrol, (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
-Chlorthymol, 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)-
Bromphenol, 4-bromoresorcinol, (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-tribromo-4-hydroxytoluene,
2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetra Chlorbisphenol A, tetrabromobisphenol A, 2,2,2
3,3-tetrafluoro-1-propanol, 2,3
5,6-tetrafluorophenol, tetrafluororesorcin and the like.

Examples of the silicon halide compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , and H ₃ S.
iCl, HCH ₃ SiCl ₂ , HC ₂ H ₅ SiCl ₂ ,
_{H (t-C 4 H 9} ) SiCl 2, HC 6 H 5 SiCl
_2, H (CH ₃ ) ₂ SiCl, H (i-C ₃ H ₇ ) ₂ S
_{iCl, H 2 C 2 H 5} SiCl, H 2 (n-C 4 H 9)
SiCl, H ₂ (C ₆ H ₄ CH ₃ ) SiCl, HSiC
l (C ₆ H ₅ ) _{2 and the} like.

As metal halides, B, Al, Ga,
In, Tl, Si, Ge, Sn, Pb, As, Sb, B
and i) chlorides, fluorides, bromides, and iodides, especially BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , and AlBr.
₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TIC
l ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF ₅
Etc. are preferred.

The contact with the component 1, the component 2, the component 3 and the component 4, and the halogen-containing compound which can be brought into contact as required, is carried out by mixing and stirring in the presence or absence of an inert medium. This is done by mechanically co-milling. The contact can be performed under heating at 40 to 150 ° C.

As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used. .

Specific examples of the method for preparing Component A in the present invention include JP-A-58-162607 and JP-A-55-949.
No. 09, No. 55-115405, No. 57-10810
No. 7, No. 61-21109, No. 61-174204
Nos. 61-174205 and 61-174206
And the methods disclosed in JP-A-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-58-162).
607), a method in which a reaction product of an inorganic oxide and a magnesium hydrocarbyl halide compound is brought into contact with a Lewis base compound and titanium tetrachloride (Japanese Patent Application Laid-Open No. 55-94909), and a method in which a porous carrier such as silica and the like are used. A method in which a reaction product of a magnesium compound is brought into contact with an electron donating compound and a silicon halide compound before being brought into contact with a titanium compound (JP-A-55-115405 and JP-A-57-1081).
No. 07), a method of contacting a metal oxide, an alkoxy group-containing magnesium compound, an aromatic polycarboxylic acid having a carboxyl group at an ortho position or a derivative thereof, and a titanium compound (Japanese Patent Application Laid-Open No. 61-174204). A method of contacting an oxide, an alkoxy group-containing magnesium compound, a silicon compound having a hydrogen-silicon bond, an electron-donating compound and a titanium compound (Japanese Patent Application Laid-Open No. Sho 61-61).
174205), a method of contacting a metal oxide, a magnesium compound containing an alkoxy group, a halogen element or a compound containing a halogen, an electron-donating compound and a titanium compound (Japanese Patent Application Laid-Open No. 61-174206), a metal oxide, dihydrocarbyl A method of contacting a reaction product obtained by contacting magnesium and a halogen-containing alcohol with an electron-donating compound and a titanium compound (JP-A-61-21109), containing a metal oxide, hydrocarbylmagnesium and a hydrocarbyloxy group-containing compound; A method in which a solid obtained by contacting a compound (corresponding to the above-mentioned alkoxy group-containing compound) is contacted with a halogen-containing alcohol, and further contacted with an electron-donating compound and a titanium compound (Japanese Patent Laid-Open No.
2-7706). Among these, the method (1) is preferable, and the method (2) is particularly preferable.

Component A is prepared as described above,
Component A may be washed with the above-mentioned inert medium, if necessary, and further dried.

The component A may further contain an olefin polymer formed in the component A upon contact with an olefin in the presence of an organoaluminum compound. The organoaluminum compound is selected from the below-mentioned organometallic compounds which are one component of the catalyst of the present invention.

As the olefin, α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene can be used in addition to ethylene. The contact with the olefin is preferably carried out in the presence of the above-mentioned inert medium. Contact is usually 100 ° C. or less, preferably -10 to +
It is performed at a temperature of 50 ° C. The amount of the olefin polymer contained in the component A is usually 0.1 to 10 per gram of the component A.
0 g.

The contact between the component A and the olefin may be carried out in the presence of an electron donating compound together with the organoaluminum compound. The electron donating compound includes a compound used for preparing the component A and a Si—O—C bond or a Si—N
It is selected from organic silicon compounds having a -C bond. Component A, which has come into contact with the olefin, can be optionally washed with the above-mentioned inert medium and further dried.

Organometallic compounds Organometallic compounds (hereinafter referred to as component B) are listed in the Periodic Table I.
Organic compounds of Group III or Group III metals. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, an organoaluminum compound is particularly preferable. The organoaluminum compound may be used, the general formula R _n Al
X _3-n (where R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n represents 1
It is an arbitrary number in the range of ≦ n ≦ 3. And C1 to C18 such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride.
And preferably an alkylaluminum compound having 2 to 6 carbon atoms or a mixture or complex compound thereof. Specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trialkylaluminum such as trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide,
Monoalkylaluminum dihalides such as dialkylaluminum monohalide such as diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, and ethylaluminum sesquichloride Dialkyl aluminum monoalkoxides such as alkyl aluminum sesquihalide, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl Aluminum hydride, dipropyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride. Among these, trialkyl aluminum, particularly triethyl aluminum and triisobutyl aluminum are desirable. Further, these trialkylaluminums are other organic aluminum compounds, for example, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or mixtures or complex compounds thereof, which are easily available industrially. Etc. can be used in combination.

An organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example,

Embedded image Etc. can be exemplified.

Examples of organic compounds of metals other than aluminum metal include diethyl magnesium, ethyl magnesium chloride, diethyl zinc, and other LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) compounds such as _4.

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. In the formula, the hydrocarbon group of R ^{1 to} R ^{5 and} the hydrocarbon group of R ⁶ and R ⁷ in OR ⁶ and OR ⁷ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. No.

Examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, A decyl group or the like, as an alkenyl 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 aryl groups such as phenyl and tolyl , An xylyl group and the like and an aralkyl group include a benzyl, phenethyl and 3-phenylpropyl group. Among these, an aliphatic hydrocarbon group such as an alkyl group and an alkenyl group is desirable, and an alkyl group is particularly desirable. Further, among the hydrocarbon groups for R ⁴ , methyl and ethyl groups are most desirable.

Further, in the above general formula, OR ⁴ and R
^It is desirable that the total number of alkoxy groups in which ² is R ⁶ O and R ³ is R ⁷ O is 4 or less, and when the number is 4, at least one of the alkoxy groups is Particularly preferred is a methoxy group. It is particularly desirable that the number of alkoxy groups is at most three.

Component C is usually represented by the general formula R¹R^TwoR^ThreeSiO
H and a compound represented by the general formula (R ^FourO)_{x + 1}SiR^Five
_3-xReacts a compound represented by the formula with an amine compound
Can be synthesized.

Hereinafter, specific examples of the component C are listed. In addition,
In the following, Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Amy = amyl, Hex = hexyl, respectively.

○ R ¹ R ² R ³ SiOSi (OR ⁴ ) ₃
Wherein R ² and R ³ are hydrocarbon groups (R ¹ / R
Shows a ² / R ³ // OR ^4. Provided that when R ^1, R ² or R ³ are the same displays and _{^{R 1 3, R 1 2 /}} R 3 or the like. ) Me ₃ // OMe, Me ₃ // OEt, Et ₃ // OMe, E
t ₃ // OEt, Me ₂ / n-Pr // OMe, Me ₂ / n
_{-Pr // OEt, Me 2 / t} -Bu // OMe, Me 2 /
_{t-Bu // OEt, Et 2} / Me // OMe, Et 2 / M
e // OEt.

○ R¹R^TwoR^ThreeSiOSi (OR^Four)_Two
R^FiveAnd R^Two, R^ThreeIs a hydrocarbon group (R¹
/ R^Two/ R^Three// OR^Four/ R^FiveIs shown. Where R¹, R^Two
Or R ^ThreeAre the same, R¹ _Three, R¹ _Two/ R^ThreeEtc. and display
I do. ) Me_Three// OMe / Me, Me_Three// OEt / Me, Me_Three
// OMe / Et, Me _Three// OEt / Et, Me_Three// OM
e / i-Pr, Me_Three// OEt / i-Pr, Me_Three// O
Me / t-Bu, Me_Three// OEt / t-Bu, Me_Three//
OMe / n-Bu, Me_Three// OEt / n-Bu, Me_Three
// OMe / s-Bu, Me_Three// OEt / s-Bu, Et
_Three// OMe / Me, Et_Three// OEt / Me, Et_Three// O
Me / i-Pr, Et_Three// OEt / i-Pr, Me_Two/
n-Pr // OMe / Me, Me_Two/ N-Pr // OEt /
Me, Me_Two/ T-Bu // OMe / Et, Me_Two/ T-
Bu // OEt / Et, Me_Two/ N-Bu // OMe / M
e, Me_Two/ N-Bu // OEt / Me, Me_Two/ NH
ex // OMe / Me, Me_Two/ N-Hex // OEt / M
e, Me_Two/ S-Amy // OMe / Me, Me_Two/ S-
Amy // OEt / Me.

○ R ¹ R ² R ³ SiOSi (OR ⁴ ) ₃
Where R ² is a hydrocarbon group and R ³ is R ⁶ O (shown as R ¹ / R ² / R ⁶ O // OR ⁴ , provided that R ¹ , R
When ² are the same displays and R ¹ _2. ) Me ₂ / MeO // OMe, Me ₂ / MeO // OEt, M
_{e 2 / EtO // OMe, Me} 2 / EtO // OEt, Me
₂ / i-PrO // OMe, Me ₂ / i-PrO // OE
t, Me ₂ / t-BuO // OMe, Me ₂ / t-BuO
_{// OEt, Me 2 / n-} Hex // OMe, Me 2 / n-
_{HexO // OEt, Et 2 / MeO} // OMe, Et 2 /
MeO // OEt, Me / t-Bu / MeO // OMe, M
e / t-Bu / MeO // OEt, (i-Pr) ₂ / Me
O // OMe, (i-Pr) ₂ / MeO // OEt, Me /
s-Amy / MeO // OMe, Me / s-Amy / Me
O // OEt.

○ R¹R^TwoR^ThreeSiOSi (OR^Four)_Two
R^FiveAnd R^TwoIs a hydrocarbon group, R^ThreeIs R⁶Place of O
(R¹/ R^Two/ R⁶O // OR^Four/ R^FiveIs shown. However,
R¹And R^TwoAre the same, R¹ _TwoIs displayed. ) Me_Two/ MeO // OMe / Me, Me_Two/ MeO // OE
t / Me, Me_Two/ EtO // OMe / Me, Me_Two/ E
tO // OEt / Me, Me_Two/ I-PrO // OMe / M
e, Me_Two/ I-PrO // OEt / Me, Me_Two/ S-
BuO // OMe / Me, Me_Two/ S-BuO // OEt /
Me, Me_Two/ T-AmyO // OMe / Me, Me_Two/
t-AmyO // OEt / Me, Me_Two/ N-HexO //
OMe / Me, Me_Two/ N-HexO // OEt / Me,
Et_Two/ MeO // OMe / Me, Et_Two/ MeO // OE
t / Me, Me / n-Pr / MeO // OMe / Et, M
e / n-Pr / MeO // OEt / Et, Me / t-Bu
/ MeO // OMe / Me, Me / t-Bu / MeO // O
Et / Me, Me_Two/ MeO // OMe / Et, Me _Two/
MeO // OEt / Et, Me_Two/ MeO // OMe / i-
Pr, Me_Two/ MeO // OEt / i-Pr, Me_Two/ M
eO // OMe / t-Bu, Me_Two/ MeO // OEt / t
-Bu.

○ R¹R^TwoR^ThreeSiOSi (OR^Four)_Three
And R^TwoIs R⁶O, R^ThreeIs R ⁷In the case of O (R¹
/ R⁶O / R⁷O // OR^FourIs shown. Where R⁶, R⁷But
At the same time, (R⁶O)_TwoIs displayed. ) Me / (MeO)_Two// OMe, Me / (MeO)_Two// O
Et, Et / (MeO)_Two// OMe, Et / (MeO)
_Two// OEt, Me / (EtO)_Two// OMe, Me / (E
tO)_Two// OEt, Me / (n-PrO)_Two// OMe,
Me / (n-PrO) // OEt, Me / (MeO) /
(T-BuO) // OMe, Me / (MeO) / (t-B
uO) // OEt.

○ R¹R^TwoR^ThreeSiOSi (OR^Four)_Two
R^FiveAnd R^TwoIs R⁶O, R^ThreeIs R⁷In case of O
(R¹/ R⁶O / R⁷O // OR^Four/ R^FiveIs shown. However,
R⁶And R ⁷Are the same, (R⁶O)_TwoIs displayed. ) Me / (MeO)_Two// OMe / Me, Me / (MeO)
_Two// OEt / Me, Et / (MeO)_Two// OMe / M
e, Et / (EtO)_Two// OEt / Me, i-Pr /
(MeO)_Two// OMe / Me, i-Pr / (MeO)_Two
// OEt / Me, n-Bu / (MeO)_Two// OMe / M
e, n-Bu / (MeO)_Two// OEt / Me, Me /
(N-PrO)_Two// OMe / Me, Me / (n-Pr
O)_Two// OEt / Me, Me / (s-BuO)_Two// OM
e / Me, Me / (s-BuO)_Two// OEt / Me, M
e / MeO / n-HexO // OMe / Me, Me / Me
O / n-HexO // OEt / Me, Et / (MeO)_Two
// OMe / Et, Et / (MeO) _Two// OEt / Et,
Vinyl / (MeO)_Two// OMe / vinyl, vinyl / (E
tO)_Two// OEt / vinyl.

The catalyst of the present invention comprises Component A, Component B and Component C. The component ratio of Component B is 1 to 2,000 g mol per 1 g atom of titanium in Component A.
Desirably, 20 to 500 gmol, wherein component C is component B1
0.001 to 10 mol, preferably 0.0
It is used so as to be 1 to 1.0 mol.

Method for Producing Propylene-Ethylene Block Copolymer The method for producing the propylene-ethylene block copolymer includes a step of polymerizing propylene to obtain a highly crystalline polypropylene (step a), and a step of converting propylene and ethylene. And a step of copolymerizing (step b).

(1) Step a Step a) comprises polymerizing propylene in the presence of the polymerization catalyst. The polymerization reaction may be any of a gas phase and a liquid phase, and when polymerizing in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane,
It can be carried out in an inert hydrocarbon such as heptane, octane, cyclohexane, benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually from -80 ° C to +
It is in the range of 150C, preferably 40-120C. The polymerization pressure may be, for example, 1 to 60 atm. The molecular weight of the resulting polymer is adjusted by the presence of hydrogen or other known molecular weight regulators. In step a,
It is desirable that the obtained polypropylene accounts for 50 to 98% by weight, particularly 70 to 95% by weight of the block copolymer.

(2) Step b The copolymerization of propylene and ethylene is carried out in the presence of the above-mentioned polymerization catalyst. The copolymerization is carried out when the ethylene content in the copolymer obtained therefrom is 30 to 95% by weight, preferably 4% by weight.
The reaction is carried out by bringing propylene and ethylene into contact with each other so as to be 0 to 80% by weight. The copolymerization reaction is
It can be appropriately selected from the range of polymerization conditions performed in step a, and the use of a molecular weight regulator such as hydrogen is the same as in step a. The amount of the copolymer obtained in the step b is usually 50 to 2% by weight of the block copolymer, but preferably 30 to 5% by weight.

The method of the present invention comprises a step a and a step b. In the step a and the step b, the step a and the step b are performed in parallel, in addition to the series method in which the steps are performed or vice versa. A method of combining the polymers obtained in the above can be adopted, and among these, a method in which step a and step b are performed in that order is particularly advantageous and desirable in terms of the apparatus.

[0058]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. The physical properties of the polymer were measured by adding BHT (2,6-di-tert-butyl-4) to the polymer powder.
0.18% by weight of DSTDP
0.08% by weight (disterial thiodipropionate), 0.04% by weight of IRGANOX1010 [tetrakis- {methylene- (3,5-ditert-butyl-4-hydroxyhydro-cinnamate) methane]], calcium stearate After adding 0.06% by weight of each rate and pelletizing by melt kneading, test pieces were prepared by injection molding. Flexural modulus: JIS K
7203-1982: Dupont impact strength: JIS K
7211-1976. The MFR of the polymer was measured according to ASTM D-1238.

Example 1 Preparation of Component A A 200 ml flask equipped with a dropping funnel and a stirrer was replaced with nitrogen gas. In this flask, silicon oxide (D
5g of n-heptane and 40 ml of n-heptane were placed in a nitrogen stream at 200 ° C for 2 hours and then at 700 ° C for 5 hours. And n
-Butylethylmagnesium (hereinafter referred to as BEM)
20% n-heptane solution (manufactured by Texas Alkyls,
20 ml (trade name: MAGALA BEM) was added and stirred at 90 ° C. for 1 hour. After the suspension was cooled to 0 ° C., a solution of 11.2 g of tetraethoxysilane dissolved in 20 ml of n-heptane was dropped from the dropping funnel over 30 minutes. After completion of dropping, the temperature was raised to 50 ° C. over 2 hours,
Stirring was continued for 1 hour at ° C. After completion of the reaction, the supernatant was removed by decantation, and the resulting solid was reconstituted in 60 ml of n-
After washing with heptane at room temperature, 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 make a suspension, and a solution of 8.0 g of 2,2,2-trichloroethanol dissolved in 10 ml of n-heptane was added to the suspension at 25 ° C from a dropping funnel at 15 ° C. It was dropped over a period of minutes. After completion of the dropwise addition, stirring was continued at 25 ° C. for 30 minutes. After completion of the reaction, washing was performed twice at room temperature with 60 ml of n-heptane and three times with 60 ml of toluene. When the obtained solid (solid component I) was analyzed,
SiO ₂ 36.6%, magnesium 5.1%, chlorine 3
8.5%. In the solid component I obtained above,
10 ml of n-heptane and 40 ml of titanium tetrachloride were added, and 9
The temperature was raised to 0 ° C., and 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. At the end of the reaction, the solid material obtained is
Washing was carried out eight times with hexane at room temperature. Next, drying was performed at room temperature under reduced pressure for 1 hour to obtain 8.3 g of a catalyst component (component A). Component A contained 3.1% titanium, as well as silicon oxide, chlorine and di-n-butyl phthalate.

[0060]polymerization 5 liters of autoclaved with nitrogen replacement
In a reave, 39.5 mg of the component A obtained above, n-hept
0.6 mol of triethylaluminum per liter of tan
In 4 ml of a solution containing the solution and 1 liter of n-heptane
0.08 mol of 1,1,1-trimethoxy-3,3,3
3 ml of a solution containing trimethyldisiloxane are mixed and 5
What was held for a minute was put in. Then 7.0 liters of hydrogen
Pressure and 3 liters of liquid propylene
The internal temperature of the clave was raised to 70 ° C., and the first-stage polymerization was performed.
Was. After one hour, unreacted propylene and hydrogen are purged.
And the internal pressure is 0.2kg / cm^Two・ G First stage
After collecting a small amount of eye polymer, introduce hydrogen into the system
Was. Subsequently, the molar ratio of propylene to ethylene is 1.5
To supply propylene-ethylene copolymer
went. 6kg / cm internal pressure^Two・ Keep at G, 75 ℃
For 2 hours. After the polymerization, unreacted gas is purged.
And the polymer was removed and dried. In unreacted gas
Contained 0.5 mol% of hydrogen. The resulting polymer
-Had an MFR of 11.8 g / 10 min. Analysis results
As a result, the amount of polymer produced by copolymerization was 21
% And the ethylene content was 51% by weight. Ma
MFR of polymer sampled after the first stage
Was 29.1 g / 10 minutes. Physical properties of final polymer
Upon measurement, the flexural modulus was 8.72 × 10 ^Threekg /
cm^Two, DuPont impact strength is 60.7kgcm
Was.

Examples 2 to 5 and Comparative Examples 1 and 2 In Example 1, 1 was used as one component of the polymerization catalyst.
An organic silicon compound as shown in Table 1 was used in place of 1,1-trimethoxy-3,3,3-trimethyldisiloxane, and the amount of hydrogen was adjusted so as to obtain an MFR as shown in Table 1. In the same manner as in Example 1, propylene was copolymerized. Table 1 shows the physical properties of the final polymer obtained.
It was shown to. This indicates that the block copolymer according to the present invention is excellent in elastic modulus and impact strength in a well-balanced manner.

[Table 1]

[0062]

According to the method of the present invention, a block copolymer of propylene having an excellent balance between impact resistance and rigidity can be produced.

[Brief description of the drawings]

FIG. 1 is a flow chart illustrating the method of the present invention.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Satoshi Ueki 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. (72) Inventor Hiroo Saito Nishi-Tsurugaoka, Oi-machi, Iruma-gun, Saitama chome third No. 1 Tonen Sogo the laboratory (72) inventor Noriyuki Taki Saitama Prefecture Iruma-gun Oi-cho, Nishitsurugaoka chome third No. 1 Tonen Sogo the laboratory (58) investigated the field (Int.Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (1)

(57) [Claims] 1. A solid catalyst component comprising (A) a metal oxide, magnesium, titanium, a halogen and an electron donating compound as essential components, (B) an organometallic compound, and (C) a general formula: [However, R ¹ , R ⁴ and R ⁵ are the same or different and have 1 carbon atom.
10 to 10 hydrocarbon groups, R ² is a hydrocarbon group having 1 to 10 carbon atoms or R ⁶ O, R ³ is a hydrocarbon group having 1 to 10 carbon atoms or R ⁷ O, and x is 2 or 3, R ⁶
And R ⁷ are the same or different hydrocarbon groups having 1 to 10 carbon atoms. (A) in the presence of a polymerization catalyst comprising an organosilicon compound represented by the following formula (1): (a) a step of polymerizing propylene to produce a highly crystalline polypropylene; and (2) a step (b) of copolymerizing propylene with ethylene. A method for producing a propylene block copolymer comprising: