JPH07102028A - Production of propylene block copolymer - Google Patents

Abstract

PURPOSE:To produce a propylene block copolymer improved in rigidity, heat resistance and impact resistance by polymerizing propylene in the presence of a specified olefin polymerization catalyst and copolymerizing ethylene and an alpha-olefin in the presence of the obtained polypropylene. CONSTITUTION:A pretreated polymerization catalyst prepared by prepolymerizing 0.01-2000g of a 2 C or higher olefin per 1g of a solid titanium catalyst component (A) containing Mg, Ti, halogen and an electron donor with a catalyst component comprising component (A), an organometallic compound catalyst component (B) and an organosilicon compound (C) of formula I (wherein R and R' are each a hydrocarbon group; and 0<n<4) is combined with an organosilicon compound (D) of formula II and optionally an organometallic compound (E) to obtain an olefin polymerization catalyst. Propylene is polymerized in the presence of this catalyst to obtain a PP, and ethylene and a 3-20 C alpha-olefin are copolymerized in the presence of the formed PP to obtain a propylene block copolymer having a stereoregularity index [H5] of 0.97 or above as determined according to equation III from the <13>C-NMR spectrum data on boiling heptane-insolubles.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a propylene-based block copolymer, and more particularly to a method for producing a propylene-based block copolymer having excellent rigidity and heat resistance as well as impact resistance.

[0002]

BACKGROUND OF THE INVENTION Polypropylene is a so-called Ziegler compound composed of a group IV-VI transition metal compound of the periodic table and an organometallic compound containing a group I-III metal.
It is manufactured using a Natta catalyst and is used in a wide range of applications.

The polypropylene obtained by using the above Ziegler type catalyst has a problem that it is excellent in rigidity and heat resistance but inferior in impact resistance. Methods for improving the impact resistance of such polypropylene have been studied in the past. For example, a method of compounding a rubber such as ethylene / propylene copolymer (EPR) with polypropylene, or polymerization of propylene to form a polypropylene component. Then, multi-stage polymerization, that is, block copolymerization such as copolymerization of ethylene and propylene to form a rubber component, is performed to obtain a propylene-based block copolymer having a polypropylene component and an ethylene / propylene rubber component in the same polymer. A method for obtaining a polymer is known. In particular, the propylene block copolymer obtained by the latter method generally has good dispersibility of the rubber component in the copolymer and excellent impact resistance, and is widely used in various applications.

Further, since propylene-based copolymers have characteristics such as low specific gravity and easy recycling, they are attracting attention from the viewpoint of environmental protection, and their use in a wider range of applications is desired. .

However, the propylene-based block copolymer obtained by the prior art may not always have sufficient rigidity and heat resistance depending on the application, and its use is sometimes limited.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional techniques, and it is possible to obtain a propylene-based block copolymer having extremely excellent rigidity, heat resistance and impact resistance. It is an object of the present invention to provide a method for producing such a propylene-based block copolymer.

[0007]

SUMMARY OF THE INVENTION A method for producing a propylene-based block copolymer according to the present invention comprises: [I] [A] a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor; and [B] an organometal. A compound catalyst component and [C] an organosilicon compound represented by the following formula (c); R _n Si (OR ′) _4-n (c) (wherein R and R ′ are hydrocarbon groups, 0 <n <
It is 4. ), A olefin having 2 or more carbon atoms is prepolymerized in an amount of 0.01 to 2000 g per 1 g of the [A] solid titanium catalyst component, and [II] the following formula: (Ci); R ^a _n Si (OR ^b ) _4-n ... (ci) (wherein n is 1, 2 or 3, and when n is 1, R ^a is a secondary or tertiary carbonization) Is a hydrogen group and n is 2
Or 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a may be the same or different, and R ^b is a hydrocarbon having 1 to 4 carbon atoms. When the group is 4-n and 2 or 3, OR ^b may be the same or different. In the presence of an olefin polymerization catalyst formed from an organosilicon compound represented by the formula (3) and, if necessary, an organometallic compound catalyst component [III], the formation of a polypropylene component by the polymerization of propylene and the formation of ethylene and carbon atoms of 3 ~ 2
It is characterized by producing an ethylene / α-olefin copolymerization component by copolymerization with 0-α-olefin in any order to produce a propylene-based block copolymer having the following characteristics.

(I-1) From the ¹³ C-NMR spectrum of the boiling heptane-insoluble component of the propylene block copolymer,
The value of the stereoregularity index [M ₅ ] obtained by the following formula (1) is 0.97 or more;

[0009]

[Equation 3]

(In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit at the site where five propylene units are continuously isotactically bonded, and [Pw]: derived from the methyl group of the propylene unit. [Sαγ]: a secondary carbon in the main chain, one of the two tertiary carbons closest to the secondary carbon being in the α-position,
The other is the absorption intensity derived from the secondary carbon in the γ-position, and [Sαδ ⁺ ]: the secondary carbon in the main chain, of the two tertiary carbons closest to the secondary carbon. , One of which is at the α-position and the other of which is the absorption intensity derived from the secondary carbon located at the δ-position or at a position distant from the δ-position, and [Tδ ⁺ δ ⁺ ]: tertiary carbon in the main chain Of the two tertiary carbons closest to the tertiary carbon, one of them is at the δ position or a position away from the δ position, and the other is at a position of the δ position or away from the δ position. Is the absorption intensity derived from. ), (I-2) The boiling heptane-insoluble component has a stereoregularity index [M ₃ ] determined by the following formula (2) of 0.0020-
0.0050;

[0011]

[Equation 4]

(Ii-1) The 23 ° C. n-decane-soluble component of the propylene block copolymer has an intrinsic viscosity [η] of 4 dl / g.
That is all.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a propylene block copolymer according to the present invention will be specifically described below.

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may refer to not only homopolymer but also copolymer. It may be used in a meaning including a polymer.

The method for producing a propylene block copolymer according to the present invention comprises: [I] [A] a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor, and [B] an organometallic compound catalyst. Component and [C] an organosilicon compound represented by the following formula (c): R _n Si (OR ′) _4-n (c) (wherein R and R ′ are hydrocarbon groups, and 0 < n <
It is 4. ), A olefin having 2 or more carbon atoms is prepolymerized in an amount of 0.01 to 2000 g per 1 g of the [A] solid titanium catalyst component, and [II] the following formula: (Ci); R ^a _n Si (OR ^b ) _4-n ... (ci) (wherein n is 1, 2 or 3, and when n is 1, R ^a is a secondary or tertiary carbonization) Is a hydrogen group and n is 2
Or 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a may be the same or different, and R ^b is a hydrocarbon having 1 to 4 carbon atoms. When the group is 4-n and 2 or 3, OR ^b may be the same or different. In the presence of an olefin polymerization catalyst formed from an organosilicon compound represented by the formula (3) and, if necessary, an organometallic compound catalyst component [III], the formation of a polypropylene component by the polymerization of propylene and the formation of ethylene and carbon atoms of 3 ~ 2
The formation of the ethylene / α-olefin copolymerization component by copolymerization with 0-α-olefin is carried out in any order to produce a specific propylene block copolymer as described below.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst and the steps for producing the propylene block copolymer used in the present invention. First, the prepolymerization catalyst [I] used in the present invention and each component forming the olefin polymerization catalyst will be specifically described below.

The solid titanium catalyst component [A] used in the present invention can be prepared by bringing the following magnesium compound, titanium compound and electron donor (a) into contact with each other.

[A] Used for preparing solid titanium catalyst component
Specific examples of the titanium compound include
The tetravalent titanium compound represented by Ti (OR)_gX_4-g (In the formula, R is a hydrocarbon group, and X is a halogen atom.
And g is 0 ≦ g ≦ 4. As such a titanium compound, specifically, TiC
l_Four, TiBr_Four, TiI_Four Tetrahalogenated titanium such as;
Ti (OCH₃) Cl₃, Ti (OC₂H_Five) Cl₃, Ti (O-n-C_Four
H₉) Cl₃, Ti (OC₂H _Five) Br₃, Ti (O-iso-C_FourH₉) Br
₃ Trihalogenated alkoxy titanium such as; Ti (OCH
₃)₂Cl₂, Ti (OC₂H_Five)₂Cl₂, Ti (O-n-C_FourH₉)₂C
l₂, Ti (OC ₂H_Five)₂Br₂Dihalogenated dialkoxy such as
Si Titanium; Ti (OCH₃)₃Cl, Ti (OC₂H_Five)₃Cl, Ti
(O-n-C_FourH₉)₃Cl, Ti (OC₂H _Five)₃Monoha such as Br
Trialkoxy titanium rogenate; Ti (OCH₃)_Four, Ti
(OC₂H_Five)_Four, Ti (O-n-C_FourH₉)_Four, Ti (O-iso-C_FourH₉)
_Four, Ti (O-2-ethylhexyl)_Four Such as Tetraalkoki
Examples thereof include titanium.

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include a magnesium compound having a reducing property and a magnesium compound having no reducing property.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a magnesium compound having a reducing property include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
Examples include dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride. it can. These magnesium compounds may be used alone or may form a complex compound with an organic metal compound described later. Further, these magnesium compounds may be liquid or solid, or may be derived by reacting metallic magnesium with a corresponding compound. It can also be derived from metallic magnesium during catalyst preparation using the methods described above.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride;
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxy magnesium halides such as phenoxy magnesium chloride, methylphenoxy magnesium chloride;
Ethoxymagnesium, isopropoxymagnesium,
Butoxy magnesium, n-octoxy magnesium, 2-
Examples thereof include alkoxy magnesium such as ethylhexoxy magnesium; phenoxy magnesium, allyloxy magnesium such as dimethylphenoxy magnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during the preparation of the catalyst component.

A magnesium compound having no reducing property is
To derive from a reducing magnesium compound,
For example, a reducing magnesium compound, halogen, halogen-containing organosilicon compounds, halogen-containing aluminum compounds and other halogen compounds, alcohols,
It may be brought into contact with a compound having an active carbon-oxygen bond such as an ester, a ketone or an aldehyde, or a polysiloxane compound.

In the present invention, in addition to the above-mentioned reducing magnesium compound and non-reducing magnesium compound, the magnesium compound may be a complex compound, a complex compound or another metal of the above-mentioned magnesium compound and another metal. It may be a mixture with a compound. further,
You may use the said compound in combination of 2 or more type.

As the magnesium compound used for the preparation of the solid titanium catalyst component [A], many magnesium compounds other than those mentioned above can be used, but in the finally obtained solid titanium catalyst component [A]. , Preferably in the form of a halogen-containing magnesium compound,
Therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

Among the above-mentioned magnesium compounds, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are particularly preferable.

The solid titanium catalyst component [A] used in the present invention is formed by contacting the above magnesium compound with the above titanium compound and the electron donor (a).

Specific examples of the electron donor (a) used in the preparation of the solid titanium catalyst component [A] include the following compounds. Methanol, ethanol,
C1-C18 alcohols such as propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol. And halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol, and trichlorohexanol, and lower alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol. Optionally having 6 to 20 carbon atoms, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophene C3 to C15 ketones such as benzene, benzophenone and benzoquinone, C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde, methyl formate, methyl acetate, ethyl acetate. , Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl Organic acid esters having 2 to 30 carbon atoms such as ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, acetyl chloride, benzoyl chloride C2 to C15 acid halides such as toluic acid chloride, anisic acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc. Ethers prime 2-20, acetate N, N-dimethylamide, benzoic acid N, N-diethylamide,
Toluic acid N, N-dimethylamide and other acid amides, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine and other amines, acetonitrile, benzo Nitriles such as nitrile and trinitrile, acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride, pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole, pyrroline; pyrrolidine; indole;
Pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine,
Pyridines such as trimethylpyridine, phenylpyridine, benzylpyridine and pyridine chloride, piperidines,
Nitrogen-containing cyclic compounds such as quinolines and isoquinolines,
Tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran,
Examples thereof include cyclic oxygen-containing compounds such as diphenylfuran, benzofuran, coumarane, phthalane, tetrahydropyran, pyran and ditedropyran.

In addition to these, water, anionic, cationic and nonionic surfactants can also be used.
Further, as the organic acid ester, a polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferable example.

[0031]

[Chemical 1]

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted group. Alternatively, it is an unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a ring structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent includes a hetero atom such as N, O and S, and is, for example, C—O—C, COOR, COOH, OH, SO.
_It has groups such as ₃ H, —C—N—C—, and NH ₂ .

Specific examples of such polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, diethyl methyl malonate, diethyl ethyl malonate, isopropyl malonate. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Acid diisopropyl, ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, aliphatic polycarboxylic acid esters such as dioctyl citracone, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclyl Hexanecarboxylic acid diisobutyl, tetrahydrophthalic acid diethyl, adicyclic polycarboxylic acid ester such as diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, Di-isopropyl phthalate, Di-n-butyl phthalate, Diisobutyl phthalate, Di-n-heptyl phthalate, Di-2-ethylhexyl phthalate, Di-n-octyl phthalate, Dineopentyl phthalate, Phthalic acid Aromatic polycarboxylic acid esters such as didecyl, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, 3,4-furandicarboxylic acid, etc. Examples thereof include cyclic polycarboxylic acid esters.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate,
Examples thereof include esters of long-chain dicarboxylic acids such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate.

In the present invention, among these, as the electron donor (a), it is preferable to use a carboxylic acid ester, and it is particularly preferable to use a polyvalent carboxylic acid ester, especially a phthalic acid ester.

Two or more of these compounds can be used in combination. Further, as the electron donor (a), an organosilicon compound represented by the general formula (c) described below can also be used.

When the titanium compound, the magnesium compound and the electron donor (a) as described above are brought into contact with each other, a carrier-supporting solid titanium catalyst component [A] is prepared by using the following particulate carrier. You can also do it.

Examples of such a carrier include Al ₂ O ₃ and Si.
O ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, Zn
Examples thereof include resins such as ₂ O, SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer. Of these carriers, SiO ₂ and Al ₂ O are preferable.
₃ , MgO, ZnO, Zn ₂ O and the like can be mentioned.

The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum. The solid titanium catalyst component [A] can be produced by bringing the above titanium compound, magnesium compound and electron donor (a) into contact with each other,
It can be produced by any method including known methods.

The specific production method of the solid titanium catalyst component [A] will be briefly described below by giving some examples. (1) A method in which a solution of a magnesium compound, an electron donor and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, a titanium compound is contact-reacted.

(2) A method in which a complex consisting of a magnesium compound and an electron donor is brought into contact with an organometallic compound to cause a reaction, and then a titanium compound is allowed to undergo a catalytic reaction. (3) For the contact product between the inorganic carrier and the organic magnesium compound,
A method of catalytically reacting a titanium compound and preferably an electron donor. At this time, the contact product may be previously contact-reacted with a halogen-containing compound and / or an organometallic compound.

(4) A magnesium compound-supported inorganic or organic carrier is obtained from a mixture of a solution containing a magnesium compound, an electron donor, and optionally a hydrocarbon solvent, and an inorganic or organic carrier. How to contact.

(5) magnesium compound, titanium compound,
A method for obtaining a solid titanium catalyst component carrying magnesium and titanium by contacting a solution containing an electron donor, and optionally a hydrocarbon solvent, with an inorganic or organic carrier.

(6) A method of reacting an organomagnesium compound in a liquid state with a halogen-containing titanium compound in a catalytic reaction. At this time, the electron donor is used once. (7) A method of contacting a titanium compound after a liquid reaction of an organomagnesium compound with a halogen-containing compound.
At this time, the electron donor is used once.

(8) A method of catalytically reacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used once. (9) A method of reacting a complex of an alkoxy group-containing magnesium compound and an electron donor with a titanium compound.

(10) A method of bringing a complex consisting of an alkoxy group-containing magnesium compound and an electron donor into contact with an organometallic compound and then contacting with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in any order. In this reaction, each component may be pretreated with an electron donor and / or a reaction aid such as an organometallic compound or a halogen-containing silicon compound. In this method, it is preferable to use the electron donor at least once.

(12) A method of reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor, to precipitate a solid magnesium-titanium complex.

(13) A method of further reacting the reaction product obtained in (12) with a titanium compound. (14) A method of further reacting the reaction product obtained in (11) or (12) with an electron donor and a titanium compound.

(15) A method of treating a solid substance obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound with any of halogen, a halogen compound and an aromatic hydrocarbon. In this method,
It may include a step of pulverizing only the magnesium compound, the complex compound consisting of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after pulverization, pretreatment with a reaction auxiliary agent and then treatment with halogen or the like may be performed. Examples of the reaction aid include organic metal compounds and halogen-containing silicon compounds.

(16) A method of pulverizing a magnesium compound and then contacting and reacting with the titanium compound. At this time, it is preferable to use an electron donor or a reaction aid during pulverization and / or contact / reaction.

(17) A method of treating the compound obtained in (11) to (16) above with halogen or a halogen compound or an aromatic hydrocarbon. (18) A method of bringing a contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound into contact with an electron donor and a titanium compound.

(19) A method of reacting a magnesium salt of an organic acid, a magnesium compound such as alkoxy magnesium or aryloxy magnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor.

(20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium into contact with a titanium compound and / or an electron donor. At this time, it is preferable to coexist with a halogen-containing compound such as a halogen-containing silicon compound.

(21) A liquid magnesium compound having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex,
Then, a method of reacting an electron donor and a titanium compound.

The amount of each of the above components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. For example, the electron donor (a) is added per mol of the magnesium compound. 0.01-5 moles,
It is preferably used in an amount of 0.1 to 1 mol, and the titanium compound is 0.01 to 1000 mol, preferably 0.1 to 200 mol.
Used in molar amounts.

The solid titanium catalyst component [A] thus obtained contains magnesium, titanium, halogen and an electron donor. In this solid titanium catalyst component [A], the halogen / titanium (atomic ratio) is about 2 to
200, preferably about 4-100, the electron donor / titanium (molar ratio) is about 0.01-100, preferably about 0.2-10, and magnesium / titanium (atomic ratio) is about 1 It is desirable to be -100, preferably about 2-50.

Examples of the organometallic compound catalyst component [B] used in the present invention include organometallic compounds of Group I to Group III metals of the Periodic Table, specifically the following compounds. To be

[B-1] General formula R ¹ _m Al (OR ² ) _n H _p X _q (In the formula, R ¹ and R ² are carbonized containing usually 1 to 15, preferably 1 to 4 carbon atoms. Hydrogen groups, which may be the same or different, X represents a halogen atom,
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0
≦ q <3, and m + n + p + q = 3)
An organoaluminum compound represented by.

[0059] [B-2] Formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, a K, R ¹ is same as that defined above) and a group I metal and aluminum represented by Complex alkylated product.

[B-3] General formula R ¹ R ² M ² (wherein R ¹ and R ² are the same as above, and M ² is M
g, Zn or Cd) represented by Group II or
Group III dialkyl compounds.

The following compounds can be exemplified as the organoaluminum compound belonging to the above [B-1]. A compound represented by the general formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as defined above, and m is preferably a number of 1.5 ≦ m ≦ 3). A compound represented by the general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as defined above, X is halogen, and m is preferably 0 <m <3); ¹ _m AlH _3-m (wherein R ¹ is as defined above, and m is preferably 2 ≦
m <3), a general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as defined above, X is halogen, and 0 <m ≦ 3. , 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

The aluminum compound belonging to [B-1] is more specifically a trialkylaluminum such as triethylaluminum or tributylaluminum;
Trialkenylaluminums such as triisoprenylaluminum; Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; R ¹ _2.5 Al (OR
² ) Partially alkoxylated alkylaluminum having an average composition represented by _0.5, etc .; Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethyl Alkyl aluminum sesquihalides such as aluminum sesquibromide; Partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; Dialkyls such as diethyl aluminum hydride and dibutyl aluminum hydride Aluminum hydride; ethyl aluminum dihydride, propyla Other partially hydrogenated alkylaluminum such as alkylaluminum dihydride such as mini-um dihydride; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride,
Mention may be made of partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy bromide.

Further, as a compound similar to [B-1],
An organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can be given.
Examples of such a compound include (C ₂ H ₅ ) ₂ Al
_{OAl (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
_{In addition to 2} H ₅ ) _{2 and the} like, aluminoxanes such as methylaluminoxane can also be mentioned.

The compounds belonging to the above [B-2] include L
Examples thereof include iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Of these, organoaluminum compounds are preferably used. The [C] organosilicon compound used in the present invention is represented by the following formula (c).

R _n Si (OR ′) _4-n (c) (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Is. ) Specific examples of the organosilicon compound represented by the general formula (c) include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, and phenylmethyl. Dimethoxysilane, diphenyldiethoxysilane, bis o-
Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane , Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy silane, vinyl tris (β-methoxyethoxysilane),
Examples thereof include vinyltriacetoxysilane and dimethyltetraethoxydisiloxane.

Further, as the [C] organosilicon compound, a compound represented by the following formula (ci) can also be mentioned. R ^a _n Si (OR ^b ) _4-n ... (ci) (wherein n is 1, 2 or 3, and when n is 1, R ^a is a secondary or tertiary hydrocarbon group. , N is 2
Or 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a may be the same or different, and R ^b is a hydrocarbon having 1 to 4 carbon atoms. When the group is 4-n and 2 or 3, OR ^b may be the same or different. ) In the organosilicon compound represented by the formula (ci), 2
Examples of the primary or tertiary hydrocarbon group include a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, these groups having a substituent and a carbon atom adjacent to Si.
Included are hydrocarbon groups that are primary or tertiary. More specifically, the substituted cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethyl Cyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,
Examples thereof include a cyclopentyl group having an alkyl group such as a 3,5-trimethylcyclopentyl group, a 2,3,4-triethylcyclopentyl group, a tetramethylcyclopentyl group, and a tetraethylcyclopentyl group.

As the substituted cyclopentenyl group, a 2-methylcyclopentenyl group, a 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl Examples include cyclopentenyl group, cyclopentenyl group having an alkyl group such as 2,3,5-trimethylcyclopentenyl group, 2,3,4-triethylcyclopentenyl group, tetramethylcyclopentenyl group, and tetraethylcyclopentenyl group. it can.

The substituted cyclopentadienyl group is 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentadienyl group, 2,3-dimethylcyclopentadienyl group, 2,4 -Dimethylcyclopentadienyl group,
2,5-dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group, 2, 3,4-triethylcyclopentadienyl group, 2,3,4,
5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4,5-pentamethylcyclopentadienyl group, 1,2,3,4 Examples thereof include cyclopentadienyl groups having an alkyl group such as a 5,5-pentaethylcyclopentadienyl group.

Examples of the hydrocarbon group in which the carbon adjacent to Si is secondary carbon include i-propyl group, s-butyl group, s-amyl group and α-methylbenzyl group. Examples of the hydrocarbon group whose carbon adjacent to is a tertiary carbon include a t-butyl group, a t-amyl group, an α, α′-dimethylbenzyl group, and an admantyl group.

Such an organosilicon compound represented by the formula (ci) has cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, when n is 1. Cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-
Examples are trialkoxysilanes such as norbornanetriethoxysilane.

When n is 2, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane,
Examples of dialkoxysilanes include t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

When n is 2, the organosilicon compound represented by the formula (ci) is represented by the following formula (c-ii)
The dimethoxy compound represented by

[0074]

[Chemical 2]

In the formula, R ^a and R ^c are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or
A hydrocarbon group in which the carbon adjacent to Si is secondary carbon or tertiary carbon is shown.

Examples of the organosilicon compound represented by the formula (c-ii) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane and dicyclopentadienyldimethoxysilane. (2-Methylcyclopentyl) dimethoxysilane, Di (3-methylcyclopentyl) dimethoxysilane, Di (2-ethylcyclopentyl) dimethoxysilane, Di (2,3-dimethylcyclopentyl) dimethoxysilane, Di (2,4-dimethylcyclopentyl) Dimethoxysilane, di (2,5-dimethylcyclopentyl) dimethoxysilane, di (2,3-diethylcyclopentyl) dimethoxysilane, di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethyl Cyclopentyl) dimethoxysilane, di (2,3,4-triethylsilane) Lopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclo) Pentenyl) dimethoxysilane, di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5- Dimethylcyclopentenyl) dimethoxysilane, di (2,3,4-trimethylcyclopentenyl) dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxy Silane, di (tetramethylcyclopenteni ) Dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxy Silane, di (2-
n-Butylcyclopentenyl) dimethoxysilane, di (2,
3-dimethylcyclopentadienyl) dimethoxysilane,
Di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl)
Dimethoxysilane, di (2,3,4-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,4-triethylcyclopentadienyl) ) Dimethoxysilane, di (2,3,4,5-tetramethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3 , 4,5-Pentamethylcyclopentadienyl) dimethoxysilane, di (1,2,
3,4,5-Pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (admantyl) dimethoxysilane, admantyl-t-butyldimethoxy Examples thereof include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, dis-butyldimethoxysilane, dis-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

When n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, Examples include monoalkoxysilanes such as cyclopentyldimethylethoxysilane.

In the present invention, as the [C] organosilicon compound, among the compounds represented by the formula (ci), an organosilicon compound having a lower alkyl group or a lower alkoxy group and a compound represented by the formula (ci) are exemplified. preferable.
As the compound represented by the formula (ci), dimethoxysilanes, particularly dimethoxysilane represented by the formula (c-ii) are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2 -Methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane and di-t-amyldimethoxysilane are preferred.

The above compounds may be used in combination of two or more kinds. In the present invention, in producing a propylene-based block copolymer, first, the above-mentioned [A] solid titanium catalyst component and [B] organometallic compound catalyst component,
A catalyst component composed of a specific [C] organosilicon compound,
An olefin having 2 or more carbon atoms is prepolymerized in an amount of 0.01 to 2000 g per 1 g of the [A] solid titanium catalyst component to form a prepolymerized catalyst.

Specific examples of the olefin having 2 or more carbon atoms to be prepolymerized include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,
Linear α-olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene,
Cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octa Cycloolefin such as hydronaphthalene, and further the following formula (i)
And the olefin represented by (ii).

[0081]

[Chemical 3]

In the above formulas (i) and (ii), examples of the cycloalkyl group represented by X include a cyclopentyl group, a cyclohexyl group and a cycloheptyl group, and examples of the aryl group include a phenyl group, a tolyl group and a xylyl group. Group, naphthyl group and the like.

The hydrocarbon group represented by R ¹ , R ² and R ³ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an aryl group such as a phenyl group or a naphthyl group, or a norbornyl group. And so on. Further, the hydrocarbon group represented by R ¹ , R ² and R ³ may contain silicon or halogen.

Specific examples of the compound represented by the formula (i) or (ii) include 3-methyl-1-butene and 3-methyl-1-butene.
Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc. α-olefin, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalene, allyltoluenes, allylbenzene, vinylcyclohexane,
Examples thereof include vinyl compounds such as vinylcyclopentane, vinylcycloheptane, and allyltrialkylsilanes.

Of these, propylene, 1-butene, 1-
Pentene, 3-methyl-1-butene, 3-methyl-1-pentene,
3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene and the like are preferable,
More preferred are propylene, 3-methyl-1-butene, vinylcyclohexane and allyltrimethylsilane. These may be a combination of two or more kinds.

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. The concentration of the solid titanium catalyst component [A] in the prepolymerization is usually about 0.0 in terms of titanium atom per liter of polymerization volume.
It is desirable that the concentration is 1 to 200 mmol, preferably about 0.05 to 100 mmol.

The organometallic compound catalyst component [B] is generally used in an amount of 0.1 to 100 mmol, preferably 0.5 to 50 mmol, per mol of titanium atom in the solid titanium catalyst component [A]. The [C] organosilicon compound is usually 0.1 to 50 mol, preferably 0.1, per mol of titanium atom.
It is used in an amount of 5 to 30 mol, more preferably 1 to 10 mol.

In the present invention, as the [C] organosilicon compound, when the above-mentioned prepolymerized monomer is a linear olefin, among the organosilicon compounds represented by the formula (c), the compound represented by the formula (ci ) Is preferably used, more preferably dimethoxysilane represented by the formula (c-ii), when the prepolymerized monomer is a branched olefin, in the formula (c) Among the organic silicon compounds shown, it is preferable to use an organic silicon compound having a lower alkyl group or a lower alkoxy group.

In the prepolymerization, other electron donor (b) may be used, if necessary, together with the specific [C] organosilicon compound as described above. Specific examples of the electron donor (b) include the electron donor (a) shown when the solid titanium catalyst component [A] is used, a nitrogen-containing compound as described below, and other oxygen-containing compounds: A phosphorus-containing compound or the like can also be used in combination.

Specific examples of such nitrogen-containing compounds include 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ′, N′-tetramethylmethylenediamine, N, N,
Substituted methylenediamines such as N ′, N′-tetraethylmethylenediamine, 1,3-dibenzylimidazolidine, 1,3-dibenzyl-2-phenylimidazolidine and the like can be mentioned.

Specific examples of the phosphorus-containing compound include triethylphosphite, tri-n-propylphosphite, triisopropylphosphite, tri-n-butylphosphite, triisobutylphosphite, diethyl n-butylphosphite and diethyl. Examples thereof include phosphite esters such as phenylphosphite. As the oxygen-containing compound, specifically, 2,6-substituted tetrahydropyrans, 2,
Examples include 5-substituted tetrahydropyrans.

The prepolymerization can be carried out under mild conditions, for example, in the presence of a polymerization-inert hydrocarbon medium, with the above-mentioned α-olefin and the above-mentioned catalyst component added.
Examples of the inert hydrocarbon medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or a combination thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon.

The reaction temperature in the prepolymerization is preferably a temperature at which the resulting prepolymer does not substantially dissolve in the inert hydrocarbon medium, usually about -20 to +10.
Desirably, it is 0 ° C, preferably about -20 to + 80 ° C, more preferably 0 to + 40 ° C.

In the prepolymerization, a molecular weight modifier such as hydrogen can be used. In the present invention, the prepolymerization is
0.1 g per 1 g of the solid titanium catalyst component [A] as described above.
It is desirable to carry out so that 01 to 2000 g, preferably 0.1 to 500 g of a prepolymer is produced. The prepolymerization may be carried out by a batch system, a semi-continuous system or a continuous system.

In the method for producing a propylene-based block copolymer according to the present invention, the above-mentioned [I] prepolymerization catalyst, [II] the organosilicon compound represented by the formula (ci) and, if necessary, III] In the presence of an olefin polymerization catalyst formed from an organometallic compound catalyst component, the formation of a polypropylene component by the polymerization of propylene and the formation of ethylene and a carbon number of 3 to 2
The formation of an ethylene / α-olefin copolymerization component by copolymerization with 0-α-olefin is carried out in an arbitrary order to produce a propylene block copolymer having the properties described below.

As the method for producing the propylene block copolymer according to the present invention, specifically, propylene is first polymerized to form a polypropylene component in the presence of an olefin polymerization catalyst, and then ethylene and the number of carbon atoms are added. 3 to 20
The method of forming an ethylene / α-olefin copolymerization component by copolymerizing the α-olefin with the above α-olefin can be exemplified. It is also possible to exemplify a method of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms to form an ethylene / α-olefin copolymerization component, and then polymerizing propylene to form a polypropylene component.

The case of producing a propylene-based block copolymer by forming a polypropylene component and then an ethylene / α-olefin copolymerization component will be mainly described below.

Production of Polypropylene Component In the present invention, the above [I] prepolymerization catalyst and [I]
First, propylene is polymerized in the presence of an olefin polymerization catalyst formed from [I] an organosilicon compound and, if necessary, a [III] organometallic compound catalyst component.

Specific examples of the [II] organosilicon compound include the organosilicon compounds represented by the formula (ci) shown in the preparation of the prepolymerization catalyst. Include [B] organometallic compound catalyst components. When forming this olefin polymerization catalyst, the [III] organometallic compound catalyst component may or may not be used, and can be used as necessary. The organosilicon compound [II] is preferably a dimethoxysilane represented by the formula (c-ii) among the organosilicon compounds represented by the formula (ci),
Specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane and the like are preferable.

The organosilicon compound [II] and the organometallic compound catalyst component [III] used in the main polymerization are the organosilicon compound represented by the formula (ci) used in preparing the prepolymerization catalyst, [B] organic. They may be the same as or different from the metal compound catalyst component.

This polymerization is carried out by a solvent suspension polymerization method, a suspension polymerization method using liquid propylene as a solvent, a gas phase polymerization method or the like. When carrying out the solvent suspension polymerization, a polymerization-inert hydrocarbon can be used as a polymerization solvent. As such an inert hydrocarbon, specifically,
The hydrocarbons shown in the prepolymerization are mentioned, and aliphatic hydrocarbons are preferable.

In the polymerization system, the prepolymerization catalyst [I] is used.
Is usually about 0.0001 to 2 mmol, preferably about 0.0, in terms of titanium atom per liter of polymerization volume.
01 to 1 mmol, more preferably 0.005 to 0.5
Used in millimolar amounts. The [II] organosilicon compound is usually used in an amount of 0.001 to 50 per mol of the titanium atom.
It is used in an amount of 00 mol, preferably 0.01 to 1000 mol. In addition, the organometallic compound catalyst component [B] is used in an amount of usually 1 to 2000 mol, preferably 2 to 1000 mol, per 1 mol of titanium atom in the polymerization system, if necessary.

Further, hydrogen (chain transfer agent) can be used to control the molecular weight of polypropylene. The polymerization temperature is usually about -50 to 200 ° C, preferably about 50 to 1
00 ° C., the pressure is usually from atmospheric pressure to 100 kg / cm ² ,
It is preferably set to about ² to 50 kg / cm ² .

Polymerization can be carried out by any of batch, semi-continuous and continuous methods. In the propylene polymerization step as described above, it is preferable to homopolymerize propylene, but it is also possible to add a small amount of an olefin other than propylene to propylene for copolymerization.

Specific examples of the olefin other than propylene include ethylene, 1-butene, 1-pentene,
1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-
Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1
-Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1
Α-olefins such as -pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4 , 5,8-Dimethano-1,2,3,
Cycloolefins such as 4,4a, 5,8,8a-octahydronaphthalene, vinyl compounds such as styrene and vinylcyclohexane, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene , 1,4-hexadiene, 1,5-
Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene,
6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9- Examples thereof include diene compounds such as decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene.

These may be a combination of two or more kinds. It is preferable that such a constitutional unit derived from an olefin other than propylene is used so as to be finally present in the polypropylene component in an amount of 5 mol% or less, preferably 4 mol% or less.

In the present invention, the polymerization of propylene can be carried out in two or more stages by changing the reaction conditions. The polypropylene component thus obtained has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.1 to 2
0 dl / g, preferably 0.5 to 15 dl / g, and particularly preferably 0.7 to 12 dl / g.

With this polypropylene component, 23 ° C.
It is desirable that the content of the n-decane-soluble component is 5% by weight or less, preferably 3% by weight or less, more preferably 2% by weight or less.

Preparation of ethylene / α-olefin copolymerization component
Concrete in the present invention, after producing the polypropylene component as described above, without performing the catalyst deactivation treatment of the resulting polypropylene, and then ethylene and having 3 to 20 carbon atoms α-
Copolymerize with olefin.

After the polypropylene component is produced as described above, when ethylene is copolymerized with the α-olefin having 3 to 20 carbon atoms, the solid titanium catalyst component [A] and the organosilicon are further added to the copolymerization system. A compound [II], an organometallic compound catalyst component [III] and the like can be added.

Examples of the α-olefin copolymerized with ethylene include the α-olefin having 3 to 20 carbon atoms as shown in the production of the polypropylene component.

Of these, propylene, 1-butene, 1-
Pentene is preferred. These may be a combination of two or more kinds. Further, the ethylene / other α-olefin copolymerization component may contain a constitutional unit derived from another olefin, and specifically, the olefin, vinyl compound, diene and the like as shown in the propylene polymerization. And so on.

These may be a combination of two or more kinds. The copolymerization is usually performed in the gas phase or the liquid phase. When the copolymerization is carried out by solvent suspension polymerization, the above-mentioned inert hydrocarbon can be used as the polymerization solvent.

In the copolymer system, the amount of polypropylene is 10 to 1000 g, preferably 10 to 800 g, and particularly preferably 30 to 500 g per liter of the polymerization volume.
Used in an amount of. The solid catalyst component [A] contained in the polypropylene is present in an amount of usually 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol, per 1 liter of polymerization volume, when converted to titanium atoms. ..

When a solid titanium catalyst component [A], an organosilicon compound [II], an organometallic compound catalyst component [III], etc. are added to the copolymerization system, the solid titanium catalyst component [A] is , Per 1 liter of polymerization volume, 0.00
The amount of the organosilicon compound [II] in an amount of 01 to 20 mmol, preferably 0.001 to 10 mmol, is 0.001 to 5000 mol, preferably 0.01 to 1000 mol, per 1 mol of the titanium atom in the polymerization system. The organometallic compound catalyst component [III] is appropriately used in an amount of 1 to 2000 mol, preferably about 2 to 1000 mol, per 1 mol of titanium atom in the polymerization system.

At the time of copolymerization, hydrogen (chain transfer agent) may be added to adjust the molecular weight, if necessary. In the above copolymerization, the polymerization temperature is usually about -50 to 20.
The temperature is 0 ° C, preferably about 20 to 100 ° C, and the polymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably about 2 to 5 ° C.
It is 0 kg / cm ² .

Polymerization can be carried out by any of batch, semi-continuous and continuous methods. Further, the copolymerization can be carried out in two or more stages by changing the reaction conditions. According to the present invention using the above olefin polymerization catalyst, a polymer having a high molecular weight can be easily obtained, and a boiling heptane-insoluble component and / or a high-molecular weight ethylene / α-olefin copolymerization component are contained. A propylene block copolymer can be easily produced.

Further, in the present invention, since the yield of the propylene block copolymer based on the unit amount of the solid titanium catalyst component [A] is high, it is possible to relatively reduce the content of the catalyst residue in the product, particularly the halogen content. it can. Therefore, it is possible to omit the operation of removing the catalyst in the product, and it is possible to effectively prevent rusting of the mold when molding a molded product using the obtained propylene block copolymer.

The propylene block copolymer obtained in the present invention is a propylene polymerization catalyst containing the above-described specific prepolymerization catalyst, to form a polypropylene component by polymerization of propylene, and ethylene and a carbon number of 3 ~ 20
It is produced by multistage polymerization in which the formation of the ethylene / α-olefin copolymerization component by copolymerization with α-olefin is carried out in any order, and has the following characteristics.

The propylene-based block copolymer obtained in the present invention is (i) its boiling heptane-insoluble component and (i)
i) The 23 ° C n-decane soluble component will be explained.
The boiling heptane insoluble component is the predominantly crystalline part of the copolymer, and (ii) the 23 ° C n-decane soluble component is the predominantly amorphous or low crystalline part of the copolymer.

The boiling heptane-insoluble component amount of the propylene block copolymer obtained in the present invention largely depends on the 23 ° C. n-decane-soluble component amount and cannot be unconditionally specified, but it is 23 ° C. n-decane. The n-decane-insoluble component, which is the remaining amount of the soluble component, is a boiling heptane-insoluble component, usually 80% by weight or more,
Preferably 85% by weight or more, more preferably 90% by weight
The above content is more preferably 93% by weight or more, and particularly preferably 94% by weight or more. When determining the content of the above boiling heptane-insoluble component,
The n-decane soluble component is calculated assuming that it is also soluble in boiling heptane.

The boiling heptane-insoluble component of the propylene-based block copolymer is substantially composed of structural units derived from propylene, but is composed of olefins other than propylene used for polymerizing propylene. It also contains a unit and a part of an ethylene / α-olefin copolymerization component.

At 23 ° C, the n-decane-soluble component is a rubber component, but even if it is usually homopolypropylene,
It contains a small amount of n-decane soluble component. In the present invention, in the homopolypropylene component formed by the polymerization of propylene as described below, the content of the 23 ° C. n-decane-soluble component is 5% by weight or less, preferably 3% by weight, more preferably 2% by weight. It is the following.

(I) Boiling Heptane-Insoluble Component The propylene block copolymer according to the present invention contains (i) a boiling heptane-insoluble component in an amount of 50 to 95% by weight, preferably 70 to 93% by weight, particularly preferably 75 to It is desirable to contain 90% by weight

The boiling heptane-insoluble component of the propylene block copolymer is obtained as follows. In a 1 liter flask equipped with a stirrer, 3 g of polymer sample, 2,6-di-t
ert-Butyl-4-methylphenol 20mg, n-decane 5
Add 00 ml and heat to dissolve on an oil bath at 145 ° C.
After the polymer sample has dissolved, it is cooled to room temperature over about 8 hours and then held on a 23 ° C. water bath for 8 hours. The n-decane suspension containing the precipitated polymer (23 ° C. n-decane insoluble component) is separated by filtration with a G4 (or G2) glass filter and dried under reduced pressure. Soxhlet extraction of 1.5 g of the dried polymer with heptane for 6 hours or more gives a boiling heptane-insoluble component as an extraction residue.

The boiling heptane-insoluble component of the propylene block copolymer according to the present invention satisfies the following conditions. (i-1) This boiling heptane-insoluble component has a stereoregularity index [M ₅ ] of 0.97 or more, preferably 0.97, which is determined by the following formula (1) by ¹³ C-NMR spectrum.
0 to 0.995, more preferably 0.980 to 0.99
5, particularly preferably 0.982 to 0.995.

[0127]

[Equation 5]

(In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit in the site where 5 units of propylene units are continuously isotactically bonded, and [Pw]: derived from the methyl group of propylene unit. [Sαγ]: a secondary carbon in the main chain, one of the two tertiary carbons closest to the secondary carbon being in the α-position,
The other is the absorption intensity derived from the secondary carbon in the γ-position, and [Sαδ ⁺ ]: the secondary carbon in the main chain, of the two tertiary carbons closest to the secondary carbon. , One of which is at the α-position and the other of which is the absorption intensity derived from the secondary carbon located at the δ-position or at a position distant from the δ-position, and [Tδ ⁺ δ ⁺ ]: tertiary carbon in the main chain Of the two tertiary carbons closest to the tertiary carbon, one of them is at the δ position or a position away from the δ position, and the other is at a position of the δ position or away from the δ position. Is the absorption intensity derived from. ) The stereoregularity index [M ₅ ] as described above will be described more specifically.

When the boiling heptane-insoluble component of the propylene-based block copolymer is homopolypropylene (propylene polymer unit), the boiling heptane-insoluble component is represented by, for example, the following structural formula (A).

[0130]

[Chemical 4]

¹³ C derived from the methyl group at the third unit in the propylene unit 5 chain represented by (for example, Me ³ , Me ⁴ ).
-The absorption intensity in the NMR spectrum is defined as [Pmmmm], and all methyl groups (Me ¹ , Me ² ,
Me ³ ...) As the absorption intensity derived from [Pw], the stereoregularity of the propylene polymer unit represented by the structural formula (A) is determined by the following formula (1A) [M ₅ ']
It can be evaluated by the value of.

[0132]

[Equation 6]

(In the formula, [Pmmmm] and [Pw] are the same as those in the above formula (1).) Further, the boiling heptane-insoluble component of the propylene block copolymer is a structural unit derived from an olefin other than propylene. For example, when a small amount of ethylene units are contained, the structure of the boiling heptane-insoluble component can be represented by the following formula (B-1) or (B-2). The formula (B-
1) shows the case where the propylene unit chain contains one ethylene unit, and the formula (B-2) shows the case where the propylene unit chain contains an ethylene unit chain consisting of two or more ethylene units. Is shown.

[0134]

[Chemical 5]

In the case of the structure represented by the formula (B-1) or (B-2), a methyl group other than the methyl group at the third unit in the propylene unit 5 chain (the above formula (B- 1), (B
In -2), the absorption intensities derived from Me ⁴ , Me ⁵ , Me ⁶ and Me ⁷ ) should be excluded in principle when evaluating stereoregularity. However, the absorption of these methyl groups is observed to overlap with the absorption of other methyl groups, so it is difficult to quantify.

Therefore, when the stereoregularity of the boiling heptane-insoluble component having the structure represented by the formula (B-1) is evaluated, the secondary carbon in the ethylene unit and the tertiary carbon in the propylene unit are to be evaluated. Absorption intensity (Sαγ) in ¹³ C-NMR spectrum derived from the secondary carbon (C ¹ ) bonded to (C ^a ), and the secondary carbon in the propylene unit, which is the secondary carbon in the ethylene unit. Absorption intensity (Sαγ) derived from secondary carbon (C ³ ) bonded to (C ² ).
Use to exclude this.

That is, a secondary carbon in the main chain,
Secondary carbon (C¹Or C³) The closest two tertiary coals
One of the primes (C^aOr C^b) Is in alpha position, while
(C ^bOr C^a) Is derived from secondary carbon such as γ position
The absorption intensity (Sαγ) doubled is subtracted from Pw
As a result, the 3rd unit of the propylene unit 5 chain
Methyl groups other than^Four, Me^Five, Me⁶And Me⁷) To
Exclude the derived absorption intensity.

When the stereoregularity of the boiling heptane-insoluble component having the structure represented by the formula (B-2) is evaluated, it is a secondary carbon in the ethylene unit chain consisting of two or more ethylene units. From the secondary carbon (C ⁴ ) bonded to the tertiary carbon (C ^d ) in the propylene unit ¹³
Absorption intensity in C-NMR spectrum (Sαδ ⁺ ),
And the absorption intensity (Sαδ ⁺ ) derived from the secondary carbon in the propylene unit and the secondary carbon (C ⁶ ) bonded to the secondary carbon (C ⁵ ) in the chain of two or more ethylene units. Exclude this.

That is, a secondary carbon in the main chain,
Of the two tertiary carbons closest to the primary carbon (C ⁴ or C ⁶ ), one (C ^d or C ^e ) is at the α position and the other (C ^e or C ^d ) is at the δ position or the δ position. By subtracting from Pw a value obtained by doubling the absorption intensity (Sαδ ⁺ ) derived from secondary carbon at a distant position, a methyl group other than the third methyl group (M
Exclude absorption intensities from e ⁴ , Me ⁵ , Me ⁶ and Me ⁷ ).

Therefore, the stereoregularity of the boiling heptane-insoluble component having the structure represented by the above formulas (B-1) and (B-2) is evaluated by the value of [M ₅ "] obtained from the following formula (1B). can do.

[0141]

[Equation 7]

(In the formula, [Pmmmm], [Pw], [Sα
γ] and [Sαδ ⁺ ] are the same as in the above equation (1). ) Furthermore, when the boiling heptane-insoluble component of the propylene-based block copolymer contains a small amount of ethylene units and one propylene unit is contained in the ethylene unit chain,
The structure of the boiling heptane-insoluble component has, for example, the following formula (C):
Can be expressed as

[0143]

[Chemical 6]

When the stereoregularity of the boiling heptane-insoluble component having the structure represented by the formula (C) is evaluated as described above, if the above formula (1B) is applied as it is, five methyl groups to be excluded ( Me ⁴ , Me ⁵ , Me ⁶ , Me ⁷ and Me ⁸ ), but since there are four methyl groups corresponding to Sαγ or Sαδ ⁺ , methyl other than the central methyl group in the 5-chain propylene unit is present. Since three more groups will be excluded, further correction is necessary.

Therefore, the units included in the ethylene unit chain are
Derived from the tertiary carbon in the ropylene unit¹³C-NMR spectrum
This is corrected by using the absorption intensity in Koutor. sand
A tertiary carbon in the main chain, which is the closest to the tertiary carbon
Two tertiary carbons (C^f, C ^g), One (C^f)
Is at the δ position or at a position distant from the δ position, while the other (C^g)
Is a tertiary carbon such that is at or at a position distant from the δ position
(C⁷) -Derived absorption intensity (Tδ⁺δ⁺) Is also tripled
This is corrected by adding to Pw.

Therefore, the stereoregularity of the boiling heptane-insoluble component of the propylene block copolymer can be evaluated by the value obtained by the above-mentioned formula (1). The above formulas (1B) and (1C) are represented by the general formula (1)
It can be said that it is a special case included in. Even if the boiling heptane-insoluble component contains a constitutional unit other than a propylene unit, the stereoregularity should be evaluated according to the formula (1A) ([M ₅ ']) applied to the above homopolypropylene depending on the type. You may be able to

(I-2) The boiling heptane-insoluble component is
The value of the stereoregularity index [M ₃ ] determined by the following formula (2) is 0.0020 to 0.0050, preferably 0.00
23-0.0045, more preferably 0.0025-
It is 0.0040.

[0148]

[Equation 8]

In the above formula (2), [Pmmrm], [Pmrmr],
[Pmrrr], [Prmrr], [Prmmr], and [Prrrr] are
5 consecutive polypropylenes in a propylene unit chain
3 methyl groups in the same direction, 2 in opposite directions
A structure oriented in the direction (such a structure will be referred to as “M₃Structure
It is sometimes called "building". ) Having 5 propylene units
Showing the absorption intensity derived from the chain, [Pw], [Sαγ],
[Sαδ⁺], [Tδ⁺δ ⁺] Is the constant in the above equation (1).
Same as righteousness. That is, the standing required by (2) above.
Body regularity index [M₃The value of] is in the propylene unit chain
M in₃The percentage of structure is shown.

As described above, when the boiling heptane-insoluble component of the propylene block copolymer is composed of only propylene polymer units, the stereoregularity index [M ₃ '] represented by the following formula (2A) is used. To be evaluated.

[0151]

[Equation 9]

(In the formula, [Pmmrm], [Pmrmr], [Pmr]
rr], [Prmrr], [Prmmr], [Prrrr], [Pw]
Is similar to the above equation (2). The stereoregular indices [M ₅ ] and [M ₃ ] of the boiling heptane-insoluble component will be described in more detail below.

As described above, the propylene block copolymer according to the present invention has a stereoregularity index [M ₅ ] of 0.97 or more for the boiling heptane-insoluble component, which is determined by the above formula (1). And the value of the stereoregularity index [M ₃ ] obtained by the above formula (2) is 0.0020 to
It is 0.0050. Such a boiling heptane-insoluble component has an extremely long meso chain (a propylene unit chain in which α-methyl carbon points in the same direction).

Generally, in polypropylene, the smaller the value of the stereoregularity index [M ₃ ] is, the longer the mesochain is. However, when the value of the stereoregularity index [M ₅ ] is extremely large and the value of the stereoregularity index [M ₃ ] is very small, if the values of the stereoregularity index [M ₅ ] are almost the same, The larger the regularity index [M ₃ ] is, the longer the meso chain is.

[0155] For example a polypropylene having a structure (I) shown below, when compared with polypropylene having the structure (b), the polypropylene represented by the structure (a) having the M ₃ structure, the M ₃ structure It has a longer meso chain than the polypropylene represented by the structure (b) which does not have it (however, the following structure (a) and structure (b) are each composed of 1003 propylene units).

[0156]

[Chemical 7]

Polypropylene represented by the above structure (a)
Stereoregularity index [M_Five] Is 0.986, and
Stereoregularity index of polypropylene represented by structure (b)
[M _Five] Is 0.985 and is represented by structure (a)
Polypropylene and polypropylene represented by the structure (b)
Ren's stereoregularity index [M_Five] Values are almost equal
is there. However, M₃Table with structure (a) with structure
In the case of polypropylene, the propylene contained in the meso chain
The average len unit is 497 units, and M₃Contains structure
In the polypropylene represented by the non-structure (b),
The average number of propylene units in the chain is 250 units.
It That is, the stereoregularity index [M_Five] Is extremely large
In polypropylene, it is included in the propylene unit chain.
The ratio of the structure shown by r (rasemo) is extremely small.
Therefore, the structure indicated by r (rasemo) is concentrated.
Polypropylene (M₃Polypropylene with structure)
Is a port where the structure indicated by r (rasemo) exists in a distributed manner.
Lipropylene (M₃Polypropylene without structure)
Will have a longer meso chain.

The boiling heptane-insoluble component forming the propylene-based block copolymer according to the present invention is a highly stereoregular polypropylene having an M ₃ structure as shown in the above structure (a), The value of the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component is 0.97 or more, and the value of the stereoregularity index [M ₃ ] is 0.0020 to 0.005.
It is 0. The propylene-based block copolymer containing such a boiling heptane-insoluble component has higher rigidity and heat resistance than conventional polypropylene.

When the value of the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component deviates from the range of 0.0020 to 0.0050, the rigidity and heat resistance of the propylene block copolymer may be lowered. is there.

In the present invention, the boiling heptane-insoluble component ¹³
C-NMR measurement is performed as follows, for example.
That is, 0.35 g of the insoluble component is dissolved in 2.0 ml of hexachlorobutadiene. After filtering this solution through a glass filter (G2), deuterated benzene 0.5m
1 is added and charged into an NMR tube having an inner diameter of 10 mm.
Using a GX-500 type NMR measuring device manufactured by JEOL Ltd., 1
The ¹³ C-NMR measurement spectrum is measured at 20 ° C. The total number of times is 10,000 or more. Stereoregularity index [M ₅ ]
The values of [M ₃ ] and [M ₃ ] can be obtained from the peak intensity or the sum of peak intensities based on the respective structures obtained by the above measurement.

In the propylene block copolymer according to the present invention, the boiling heptane-insoluble component has a crystallinity of usually 60% or more, preferably 65% or more, as measured by an X-ray diffraction method. Preferably 65-95%
It is particularly preferably 65 to 90% or more.

For X-ray diffraction, a press sheet obtained by molding the above-mentioned boiling heptane-insoluble component as a sample into a rectangular plate having a thickness of 1 mm by a pressure molding machine at 180 ° C. and immediately cooling with water was used. , Rigaku Denki KK Rotorflex RU300 measuring device (output 50k
V, 250 mA). At this time, the measurement is performed by the transmission method while rotating the sample.

(Ii) 23 ° C. n-decane-soluble component The propylene block copolymer according to the present invention is (ii) 2
It is desirable that the 3 ° C n-decane-soluble component is contained in an amount of 60 to 3% by weight, preferably 50 to 3% by weight, more preferably 40 to 3% by weight, and particularly preferably 30 to 3% by weight.

In the propylene block copolymer according to the present invention, (ii-1) this 23 ° C. n-decane-soluble component has an intrinsic viscosity [η]
Is 4 dl / g or more, preferably 4 to 20 dl / g, more preferably 5 to 15 dl / g, particularly preferably 6 to 12 dl / g.
Is.

(Ii-2) 23 ° C. The n-decane-soluble component preferably contains a structural unit derived from ethylene in an amount of 30 to 60 mol%, preferably 35 to 50 mol%.

23 of the propylene-based block copolymer
The amount of the ° C n-decane-soluble component (rubber component) is measured as follows. That is, a 1 liter flask equipped with a stirrer was charged with 3 g of the polymer sample, 20 mg of 2,6-ditert-butyl-4-methylphenol and 500 ml of n-decane, and
Heat and dissolve on an oil bath at 5 ° C. After the polymer sample has dissolved, it is cooled to room temperature over about 8 hours and then held on a 23 ° C. water bath for 8 hours. The precipitated polymer and the n-decane solution containing the dissolved polymer are separated by filtration with a G-4 (or G-2) glass filter. The obtained solution is 10 mmH
g, dried at 150 ° C. until a constant weight is obtained, and the weight thereof is measured to obtain the amount of the soluble component of the polymer in the mixed solvent,
Calculated as a percentage of the weight of sample polymer.

The propylene-based block copolymer obtained in the present invention satisfies the specific conditions as described above, contains a boiling heptane-insoluble component having a high stereoregularity, and is superior to conventional catalysts. High intrinsic viscosity [η] 2
Contains 3 ° C n-decane soluble component.

Such a propylene block copolymer is produced by using a specific prepolymerization catalyst as described above. As the prepolymerization catalyst (prepolymer), an α-olefin having 2 or more carbon atoms is used. The derived structural unit is contained in the propylene block copolymer in an amount of 0.001 to 3% by weight, preferably 0.005 to 2% by weight, more preferably 0.008 to 1% by weight. Is desirable.

The propylene block copolymer obtained in the present invention has a melt flow rate (MFR: 230 ° C., 2.16 kg, measured according to ASTM D1238).
Under load) is 0.01 to 500 g / 10 minutes, preferably 0.05 to 300 g / 10 minutes, more preferably 0.08 to
It is preferably 200 g / 10 minutes.

The propylene block copolymer obtained in the present invention contains, if necessary, a nucleating agent, a rubber component, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent. , Lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers and the like can be added.

[0171]

INDUSTRIAL APPLICABILITY In the method for producing a propylene-based block copolymer according to the present invention, a propylene-based block copolymer is produced using an olefin polymerization catalyst containing a specific prepolymerization catalyst. A propylene block copolymer having a high stereoregular polypropylene component and a high molecular weight rubber component is obtained.

The propylene block copolymer obtained according to the present invention is extremely excellent in rigidity, heat resistance and impact resistance.

[0173]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

In the following examples, the physical properties of polymers were measured as follows. Flexural modulus (FM): Measured according to ASTM-D790. Test piece 12.7 cm × 12.7 mm × 3.0 mm Heat distortion temperature (HDT): Measured in accordance with ASTM-D648.

Test piece 12.7 cm × 12.7 mm ×
6.0 mm Izod impact strength (IZ): Measured according to ASTM-D256. Test piece 12.7 cm x 12.7 mm x 6.0 mm (rear notch)

[Measurement of Physical Properties] Polymer 1 obtained below
Tetrakis (methylene (3,5-di-t-
Butyl-4-hydroxy) hydrocinnamate) methane (0.05 parts by weight), tris (mixed mono & dinonylphenyl phosphite) (0.05 parts by weight) and calcium stearate (0.1 parts by weight) are mixed, and the mixture is heated to 250 ° C.
Granulation was carried out using an extrusion granulator with a screw diameter of 20 mm manufactured by Thermoplastics.

From the obtained granules, each ASTM standard test piece as described above was prepared at 200 ° C. using an injection molding machine manufactured by Toshiba Machine Co., Ltd., and the bending elastic modulus ( FM), heat distortion temperature (HDT), and Izod impact strength (IZ) were measured.

[0178]

Example 1 [Preparation of Solid Titanium Catalyst Component (A)] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to form a uniform solution. Then, 21.3 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve the phthalic anhydride.

The homogeneous solution thus obtained was cooled to room temperature and then 200 ml of titanium tetrachloride kept at -20 ° C.
75 ml of this homogeneous solution were added dropwise therein over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held

After the completion of the reaction for 2 hours, a solid portion was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration and washed sufficiently with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

The solid titanium catalyst component (A) prepared as described above was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained is
2.3% by weight titanium, 61% by weight chlorine, 1 magnesium
It was 9% by weight and 12.5% by weight of DIBP. [Preparation of prepolymerization catalyst [I]] In a 400 ml four-necked glass reactor equipped with a stirrer, purified hexane 1 was added under a nitrogen atmosphere.
2. After adding 00 ml, triethylaluminum 10 mmol, dicyclopentyldimethoxysilane (DCPMS) 2.0 mmol and 1.0 mmol of the solid titanium catalyst component (A) obtained as described above in terms of titanium atom. Propylene was fed to the reactor for 1 hour at a rate of 2 liters / hour. The polymerization temperature was kept at 20 ° C.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant liquid and addition of purified hexane was carried out twice, and then resuspended in purified hexane to prepare a catalyst bottle. Preliminary polymerization catalyst [I]
Got [Polymerization] An autoclave having an internal volume of 17 liters was charged with 3 kg of propylene and 120 liters of hydrogen and heated to 60 ° C., then 15 mmol of triethylaluminum, 15 mmol of dicyclopentyldimethoxysilane (DCPMS) and a prepolymerization catalyst [I]. 0.0 in terms of titanium atoms
Charged 5 mmol Ti. After raising the temperature to 70 ° C, set this to 3
It was kept for 5 minutes to carry out homopolymerization of propylene.

After the homopolymerization of propylene was completed, the vent valve was opened and the pressure inside the polymerization vessel was released until it became normal pressure. After completion of depressurization, copolymerization of ethylene and propylene was subsequently carried out. That is, ethylene was supplied to the polymerization vessel at a rate of 240 Nl / hour and propylene was supplied to the polymerization vessel at a rate of 960 Nl / hour.
The vent opening of the polymerization vessel was adjusted so that the pressure in the polymerization vessel was 10 kg / cm ² G. The temperature was kept at 70 ° C. and polymerization was carried out for 80 minutes. The polymerization reaction was stopped by adding a small amount of ethanol, and the unreacted gas in the polymerization vessel was purged.

The results are shown in Table 1.

[0185]

Example 2 Polymerization was carried out in the same manner as in Example 1 except that ethylene was fed at a rate of 480 Nl / hr and propylene was fed at a rate of 720 Nl / hr when copolymerizing ethylene and propylene. The results are shown in Table 1.

[0186]

Example 3 Polymerization was carried out in the same manner as in Example 1 except that 50 liters of hydrogen was added at the homopolymerization of propylene and the polymerization time was 40 minutes. The results are shown in Table 1.

[0187]

Example 4 Polymerization was carried out in the same manner as in Example 1 except that 20 liters of hydrogen was added at the homopolymerization of propylene and the polymerization time was 40 minutes. The results are shown in Table 1.

[0188]

Example 5 [Preparation of Prepolymerization [I-2]] 400 ml of a four-necked glass reactor equipped with a stirrer and 100 m of purified hexane under nitrogen atmosphere
1, 10 mmol of triethylaluminum, 2.0 mmol of diphenyldimethoxysilane and 1.0 mmol of the solid titanium catalyst component (A) in terms of titanium atom were added, and then propylene was added at a rate of 3.2 liters / hour for 1 hour. Feed to the reactor. The polymerization temperature was kept at 20 ° C.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was carried out twice, and then resuspended in purified hexane to prepare a catalyst bottle. Transfer the entire amount to the prepolymerization catalyst [I-
2] was obtained. [Polymerization] An autoclave having an internal volume of 17 liters was charged with 3 kg of propylene and 40 liters of hydrogen and heated to 60 ° C., then 15 mmol of triethylaluminum, 15 mmol of dicyclopentyldimethoxysilane (DCPMS) and a prepolymerization catalyst [I -2] is converted to titanium atom.
05 mmol Ti was charged. After the temperature was raised to 70 ° C., this was kept for 35 minutes to carry out propylene homopolymerization.

After completion of the homopolymerization, the vent valve was opened and the pressure inside the polymerization vessel was released until it became normal pressure. After completion of depressurization, ethylene and propylene were subsequently copolymerized. That is, 240 Nl / hr of ethylene and 960 of propylene
It was fed to the polymerizer at a rate of Nl / hr. The vent opening of the polymerization vessel was adjusted so that the pressure inside the polymerization vessel was 10 kg / cm ² · G. The temperature was kept at 70 ° C. and polymerization was carried out for 50 minutes. The polymerization reaction was stopped by adding a small amount of ethanol, unreacted gas in the polymerization vessel was purged, and the produced white powder was dried under reduced pressure at 80 ° C. The results are shown in Table 1.

[0191]

Comparative Example 1 [Preparation of Prepolymerized Catalyst [I _ref ]] In a 400 ml four-necked glass reactor equipped with a stirrer, 100 ml of purified hexane, 3.0 mmol of triethylaluminum and the product of Example 1 were prepared under a nitrogen atmosphere. After adding 1.0 mmol of the solid titanium catalyst component (A) in terms of titanium atom, propylene was fed to this reactor at a rate of 3.2 liter / hour for 1 hour. The polymerization temperature was kept at 20 ° C.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant liquid and addition of purified hexane was carried out twice, and then resuspended in purified hexane to prepare a catalyst bottle. The whole amount is transferred to the prepolymerization catalyst [I
_ref ] [Polymerization] An autoclave having an internal volume of 17 liters was charged with 3 kg of propylene and 40 liters of hydrogen and heated to 60 ° C., then 15 mmol of triethylaluminum, 5 mmol of diphenyldimethoxysilane (DPMS) and a prepolymerization catalyst [I _ref ]. Was added in an amount of 0.05 mmol Ti in terms of titanium atom. After the temperature was raised to 70 ° C., this was kept for 25 minutes to carry out homopolymerization of propylene.

After completion of the homopolymerization of propylene, the vent valve was opened and the pressure inside the polymerization vessel was released until it became normal pressure. After completion of depressurization, copolymerization of ethylene and propylene was subsequently carried out. That is, 240 Nl / hour of ethylene, 960 Nl / hour of propylene, and 5 Nl / hour of hydrogen were supplied to the polymerization vessel at a rate. Pressure in the polymerization vessel is 10kg / cm ² G
The vent opening of the polymerization vessel was adjusted so that The temperature is 7
The temperature was maintained at 0 ° C. and polymerization was performed for 50 minutes. A small amount of ethanol was added to stop the polymerization reaction, unreacted gas in the polymerization vessel was purged, and the produced white powder was dried at 80 ° C. under reduced pressure to obtain a polymer. The results are shown in Table 1.

[0194]

Comparative Example 2 Polymerization was carried out in the same manner as in Comparative Example 1 except that the copolymerization of ethylene and propylene in Comparative Example 1 was carried out for 40 minutes. The results are shown in Table 1.

[0195]

Comparative Example 3 [Polymerization] An autoclave having an internal volume of 17 liters was charged with 3 kg of propylene and 45 liters of hydrogen and heated to 60 ° C., then 15 mmol of triethylaluminum, DPMS
5 mmol and a prepolymerization catalyst [I _ref ] of 0.05 mmol Ti in terms of titanium atom were charged. After the temperature was raised to 70 ° C., this was kept for 25 minutes to carry out homopolymerization of propylene.

After completion of the homopolymerization of propylene, the vent valve was opened and the pressure in the polymerization vessel was released until it became normal pressure. After completion of depressurization, copolymerization of ethylene and propylene was subsequently carried out. That is, ethylene was supplied to the polymerization vessel at a rate of 240 Nl / hour and propylene was supplied to the polymerization vessel at a rate of 960 Nl / hour.
The vent opening of the polymerization vessel was adjusted so that the pressure in the polymerization vessel was 10 kg / cm ² G. The temperature was kept at 70 ° C. and polymerization was carried out for 50 minutes. Table 1 shows the results of obtaining a polymer by adding a small amount of ethanol to stop the polymerization reaction, purging the unreacted gas in the polymerization vessel, and drying the produced white powder at 80 ° C. under reduced pressure.

[0197]

Comparative Example 4 Polymerization was carried out in the same manner as in Comparative Example 3 except that the copolymerization of ethylene and propylene was carried out for 40 minutes in Comparative Example 3. The results are shown in Table 1.

[0198]

[Table 1]

Example 6 [Preparation of Prepolymerized Catalyst [I-3]] Nitrogen-substituted 400
After charging 200 ml of purified hexane to a ml reactor made of glass, 20 mmol of triethylaluminum, 4 mmol of dicyclopentyldimethoxysilane and 2 parts of the solid titanium catalyst component (A) prepared in Example 1 in terms of titanium atom. After charging millimole, propylene was added at 7.3 Nl / h.
Polymerization was carried out by feeding at a rate of r for 1 hour. The amount of propylene prepolymerized is 3 per 1 g of the solid titanium catalyst component (A).
It was g. After the prepolymerization, the liquid part was removed by filtration to separate the solid part, and then the solid part was reslurried in decane to prepare a decane suspension of the prepolymerization catalyst [I-3].

[Polymerization] To an autoclave having an internal volume of 2 liters, 800 ml of purified decane was charged, and at room temperature in a propylene atmosphere, 0.75 mmol of triethylaluminum,
Dicyclopentyldimethoxysilane (DCPMS) 0.
15 mmol and prepolymerization catalyst [I
-3] was charged in an amount of 0.015 mmol in terms of titanium atom.
After introducing 1.8 Nl of hydrogen, the temperature was raised to 80 ° C. while introducing propylene. The polymerization pressure was kept at 7 kg / cm ² G by supplementing with propylene. After propylene was polymerized for 30 minutes, it was cooled to 60 ° C. and depressurized, and then unreacted propylene was purged with nitrogen for 20 minutes.

The polypropylene component produced by the above polymerization had a content of n-decane-soluble component at 23 ° C. of 1.0% by weight, and [M ₅ ] measured for the component insoluble in n-decane at 23 ° C. of 0. It was 980. Then, after adding 20 Nml of hydrogen all at once under a nitrogen atmosphere at 60 ° C., a mixed gas of 68 mol% propylene / 32 mol% ethylene was introduced, and the polymerization temperature was 60 ° C. and the polymerization pressure was 5 kg / cm ² G under constant conditions. Polymerized down for 40 minutes. After the completion of the polymerization, the slurry containing the produced polymer was filtered at a temperature of 60 ° C. to separate the liquid phase portion to obtain a white powdery polymer. The obtained white powdery polymer was washed twice with 1 liter of hexane at room temperature.

The yield of the propylene block copolymer after drying was 210 g, and the polymerization activity was 14000 g / mmol-Ti. The MFR was 2.2 dg / min. When this propylene block copolymer was subjected to solvent fractionation with n-decane at 23 ° C., the amount of soluble components was 31% by weight and the amount of insoluble components was 69% by weight. The soluble component had an ethylene content of 37 mol% and an intrinsic viscosity [η] of 7.3 dl.
/ G. The insoluble component has an MFR of 130 dg.
/ Min, and the pentad isotacticity [M ₅ ] was 0.985.

[Brief description of drawings]

FIG. 1 is a diagram showing a process for producing a propylene-based block copolymer by a method for producing a propylene-based block copolymer according to the present invention.

Claims (1)

[Claims] 1. A solid titanium catalyst component containing [I] [A] magnesium, titanium, halogen, and an electron donor, [B] an organometallic compound catalyst component, and [C] the following formula:
An organic silicon compound represented by (c); R _n Si (OR ′) _4-n (c) (In the formula, R and R ′ are hydrocarbon groups, and 0 <n <
It is 4. ), A olefin having 2 or more carbon atoms is prepolymerized in an amount of 0.01 to 2000 g per 1 g of the [A] solid titanium catalyst component, and [II] the following formula: (ci); R ^a _n Si (OR ^b ) _4-n ... (ci) (wherein n is 1, 2 or 3, and when n is 1, R ^a is a secondary or tertiary carbonization Is a hydrogen group and n is 2
Or 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a may be the same or different, and R ^b is a hydrocarbon having 1 to 4 carbon atoms. When the group is 4-n and 2 or 3, OR ^b may be the same or different. In the presence of an olefin polymerization catalyst formed from an organosilicon compound represented by the formula (3) and, if necessary, an organometallic compound catalyst component [III], the formation of a polypropylene component by the polymerization of propylene and the formation of ethylene and carbon atoms of 3 ~ 2
A propylene-based block copolymer having the following properties is produced by forming an ethylene / α-olefin copolymerization component by copolymerization with 0-α-olefin in any order. Method for producing copolymer: (i-1) From the ¹³ C-NMR spectrum of the boiling heptane-insoluble component of the propylene-based block copolymer, the value of the stereoregularity index [M ₅ ] determined by the following formula (1) is , 0.97
That is all; (In the formula, [Pmmmm]: Absorption intensity derived from the methyl group of the third unit in the site where five propylene units are continuously isotactically bonded, and [Pw]: Absorption intensity derived from the methyl group of the propylene unit. [Sαγ]: a secondary carbon in the main chain, one of the two tertiary carbons closest to the secondary carbon being in the α-position,
The other is the absorption intensity derived from the secondary carbon in the γ-position, and [Sαδ ⁺ ]: the secondary carbon in the main chain, of the two tertiary carbons closest to the secondary carbon. , One of which is at the α-position and the other of which is the absorption intensity derived from the secondary carbon located at the δ-position or at a position distant from the δ-position, and [Tδ ⁺ δ ⁺ ]: tertiary carbon in the main chain Of the two tertiary carbons closest to the tertiary carbon, one of them is at the δ position or a position away from the δ position, and the other is at a position of the δ position or away from the δ position. Is the absorption intensity derived from. ), (I-2) The boiling heptane-insoluble component has a stereoregularity index [M ₃ ] determined by the following formula (2) of 0.0020-
0.0050; [Equation 2] (ii-1) The 23 ° C. n-decane-soluble component of the propylene-based block copolymer has an intrinsic viscosity [η] of 4 dl / g or more.