JPH07286022A - Propylene block copolymer - Google Patents

Abstract

(57) [Summary] [Object] The present invention provides a propylene-based block copolymer which is excellent in rigidity and impact resistance, and is capable of forming a molded product without producing a lump in the appearance, and a propylene-based block copolymer thereof. A manufacturing method is provided. [Structure] The propylene block copolymer according to the present invention comprises [A] I ₅ of 0.98 or more at 23 ° C. n-decane insoluble component: 40 to 85% by weight, and [B] intrinsic viscosity [η]. 23 ° C n-decane soluble component: 15 to 15 dl / g: 15 to 15
60% by weight. This propylene-based block copolymer has an average particle size of 250 to 8000 μm, an apparent bulk specific gravity of 0.25 to 0.80 g / ml, and a fall time of 5 to 15 seconds / 100 m.
It is preferably l-polymer particles. The propylene block copolymer as described above is preferably produced using a Ziegler catalyst composed of a particulate catalyst component having an average particle size of 5 μm and a particle content of 20% by weight or less.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene-based block copolymer capable of forming a molded article having excellent rigidity, impact resistance and appearance, and a method for producing the same.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Crystalline polypropylene has rigidity,
Although it is excellent in heat resistance and surface gloss, it has a problem that it is inferior in impact resistance.

Therefore, various methods for improving the impact resistance of polypropylene have hitherto been proposed. For example, a crystalline polypropylene is blended with a modifier such as an ethylene polymer or a rubber-like substance to form a polypropylene composition. Methods of forming are known. As the rubber-like substance, an amorphous or low crystalline ethylene / propylene random copolymer, polyisobutylene, polybutadiene, etc. are generally used.

Further, such a polypropylene composition is
When the above rubber-like substance is a block copolymer composed of an ethylene / propylene random copolymer (EPR rubber) component and a polypropylene component, the polypropylene composition has impact resistance and crystalline polypropylene It is known to be remarkably superior to a mere blend with a crystalline ethylene / propylene random copolymer.

In a composition comprising polypropylene and an amorphous ethylene / propylene random copolymer as described above, if the ethylene / propylene random copolymer has a high molecular weight, the resulting polypropylene composition will have a high impact resistance. It is known to be excellent.

By the way, the block copolymer of polypropylene and ethylene / propylene random copolymer as described above is a propylene polymerization tank for producing polypropylene or a rubber polymerization tank for producing ethylene / propylene random copolymer. It is manufactured by a continuous polymerization method using a continuous polymerization apparatus consisting of.

However, polypropylene and ethylene
When producing a block copolymer with a propylene random copolymer by a continuous polymerization method, if an attempt is made to increase the molecular weight of the ethylene / propylene random copolymer component, the high molecular weight rubber component is inferior in dispersibility. A block copolymer in which the ethylene / propylene random copolymer is not evenly dispersed may be obtained, and such a block copolymer is inferior in impact resistance, and the molded product has a poor appearance. There were occasions when it happened.

Therefore, it has been desired to develop a propylene-based block copolymer which has excellent rigidity and impact resistance and is capable of forming a molded article which is free from the appearance of scratches.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is capable of forming a molded article having excellent rigidity and impact resistance, and having no external appearance. It is an object of the present invention to provide a propylene-based block copolymer capable of achieving the above and a method for producing the same.

[0010]

SUMMARY OF THE INVENTION The propylene block copolymer according to the present invention comprises [A] 23 ° C. n-decane insoluble component: 40 to 85 wt%, and [B] 23 ° C. n-decane soluble component: 15 to 60 The [A] 23 ° C. n-decane-insoluble component is composed of (1) a propylene-derived structural unit in an amount of 85 to 100 mol%, and an α-containing 2 to 10 carbon atoms other than propylene. Containing a structural unit derived from an olefin in an amount of 0 to 15 mol%, (2)
The intrinsic viscosity [η] is 0.1 to 20 dl / g, (3) the pentad isotacticity I ₅ measured for the 60 ° C. n-decane insoluble component is 0.98 or more, and [B] The 23 ° C n-decane-soluble component has (1) an ethylene-derived structural unit in an amount of 20 to 80 mol% and a carbon number of 3
10 to 20 constituent units derived from α-olefins
Contained in an amount of ˜80 mol%, and (2) the intrinsic viscosity [η] is 5 to
It is characterized in that it is 15 dl / g.

The propylene block copolymer as described above has an average particle size of 250 to 8000 .mu.m, an apparent bulk specific gravity of 0.25 to 0.80 g / ml, and a fall time of 5 to 15 seconds / 100 m.
It is preferably l-polymer particles.

The propylene-based block copolymer as described above is (i) propylene 95% in the presence of a Ziegler catalyst.
~ 100 mol% and 0 to 5 mol% of an α-olefin having 2 to 10 carbon atoms other than propylene are polymerized to obtain 23 ° C n-
Decane-soluble component is 2% by weight or less, and the temperature is 23 ° C.
A polypropylene component having a pentad isotacticity I ₅ of 0.97 or more for the n-decane-insoluble component is formed, and then (ii) ethylene is copolymerized with an α-olefin having 3 to 10 carbon atoms to give ethylene / It is produced by forming an α-olefin random copolymerization component.

The above Ziegler catalyst has an average particle size of 5 μm.
It is preferable that the particle content of m is 20 wt% or less and the particulate catalyst component is used.

[0014]

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

The propylene-based block copolymer according to the present invention is subjected to solvent fractionation with n-decane at 23 ° C.
[A] 23 ° C n-decane-insoluble component is separated into [B] 23 ° C n-decane-insoluble component, and [A] 23 ° C n-decane-insoluble component is 40 to 85% by weight, preferably 50 to 80% by weight. %, More preferably 60-80% by weight, [B] 23 ° C.
15-60% by weight of n-decane-soluble component, preferably 20-
It is contained in an amount of 50% by weight, more preferably 20 to 40% by weight.

23 ° C. n-of propylene-based block copolymer
Solvent fractionation with decane is performed as follows. In a 1 liter flask equipped with a stirrer, 3 g of the polymer sample,
20 mg of 2,6-tert-butyl-4-methylphenol and 500 ml of n-decane were put and dissolved by heating on an oil bath at 145 ° C. After the polymer sample is dissolved, it takes 3 hours to 80 ° C, 3 hours to 46 ° C, and 2 hours to 23 ° C.
Gradually cool to 0 ° C followed by 20 hours on a 23 ° C water bath. The n-decane suspension containing the precipitated polymer was added to G
4 (or G2) glass filter. The separated solid part was dried under reduced pressure and used as an insoluble component of n-decane at 23 ° C. On the other hand, from the separated solution part, 10 mmH
g, 23 ° C by evaporating n-decane at 150 ° C
An n-decane soluble component was obtained.

[A] 23 ° C n-decane insoluble component and [B] 23 ° C n-decane of the propylene block copolymer according to the present invention obtained by solvent fractionation with 23 ° C n-decane as described above. The soluble component has the following characteristics.

[A] 23 ° C. n-Decane-insoluble component 23 ° C. n-of the propylene block copolymer according to the present invention
The decane-insoluble component is (1) a structural unit derived from propylene in an amount of 85 to 100 mol%, preferably 95 to 100 mol%, and a structural unit derived from an α-olefin having 2 to 10 carbon atoms other than propylene. In an amount of 0 to 15 mol%, preferably 0 to 5 mol%.

Carbon numbers other than propylene such as 2 to 1
Examples of the α-olefin of 0 include ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene. , 1-octene, 1-decene and combinations thereof.

(2) At 23 ° C. n-decane-insoluble component [A] is 1
Intrinsic viscosity [η] measured in decalin at 35 ° C is 0.1
-20 dl / g, preferably 0.5-15 dl / g, particularly preferably 0.7-12 dl / g.

(3) The 23 ° C. n-decane insoluble component [A] has a pentad isotacticity I ₅ of 0.98 or more, which is measured for the 60 ° C. n-decane insoluble component. The 60 ° C. n-decane-insoluble component is a solid part obtained when filtration separation is carried out at 60 ° C. according to the above-mentioned n-decane solvent fractionation method.

This pentad isotacticity I ₅
The propylene-based block copolymer having a ratio of 0.98 or more has excellent rigidity. The pentad isotacticity I ₅ is measured by the method proposed by A. Zambelli et al. In Macromolecules 6, 925 (1973), that is, the ¹³ C-NMR method (nuclear magnetic resonance method). It is an isotactic fraction in a pentad unit in a polypropylene molecular chain, and is a fraction of a propylene monomer unit in which five propylene units are isotactically bonded in succession.

Assignment of peaks in ¹³ C-NMR spectrum is carried out based on the description in Macromolecules 8, 687 (1975). Also, ¹³ C-NMR is Fourier transform NMR.
By using a [500 MHz (at the time of hydrogen nucleus measurement)] device and performing integrated measurement at a frequency of 125 MHz for 20000 times, it is possible to perform measurement while improving the zynal detection limit to 0.001.

The above-mentioned 23 ° C. n-decane-insoluble component [A] is 230% in accordance with ASTM D1238.
The melt flow rate (MFR) measured under a load of 2.16 kg at 10 ° C. is 10 to 200 g / 10 minutes, preferably 20.
It is desirable to be 150 g / 10 minutes.

[B] 23 ° C. n-decane-soluble component 23 ° C. n-of the propylene block copolymer according to the present invention
The decane-soluble component [B] is substantially an amorphous part (rubber component) of the propylene-based block copolymer, and mainly ethylene / other α-in the propylene-based block copolymer.
It is an olefin copolymerization moiety.

The 23 ° C. n-decane-soluble component [B] of the propylene-based block copolymer according to the present invention comprises (1) 20 to 80 mol% of a structural unit derived from ethylene, preferably 3
It contains a structural unit derived from an α-olefin having 3 to 10 carbon atoms in an amount of 0 to 50 mol% and an amount of 20 to 80 mol%, preferably 50 to 70 mol%.

Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and combinations thereof.

(2) The 23 ° C. n-decane-soluble component [B] has an intrinsic viscosity [η] measured in 135 ° C. decalin of 5 to 15 dl / g, preferably 6 to 11 dl / g. The propylene-based block copolymer of the present invention contains the above-mentioned 23 ° C. n-decane-soluble component [B] in a specific amount together with the above-mentioned highly crystalline 23 ° C. n-decane-insoluble component [A]. It has excellent rigidity and impact resistance.

Such propylene block copolymers include propylene, 3-methyl-1-butene and 3,3-dimethyl-1.
-Butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3,5,5-trimethyl-1-hexene, vinylcyclopentane, vinylcyclohexane etc. When it is contained as a prepolymer formed by polymerization, it has a high crystallization rate and high rigidity.

The propylene block copolymer according to the present invention is preferably in the form of particles, and specifically has an average particle size of 250 to 8000 μm, preferably 300 to 1000 μm.
The apparent bulk specific gravity is 0.25 to 0.80 g / ml, preferably 0.30 to 0.50 g / ml, and the fall seconds is 5 to 15 seconds / 100 ml-polymer, preferably 5 to 10 seconds /
100 ml-polymer particles are preferred.

The number of seconds that the polymer particles fall is measured as follows. 86m diameter equipped with a vibrator
m, length 168 mm, outlet diameter 10.5 mm cylindrical funnel is charged with 100 ml of polymer. The time (seconds) for dropping 100 ml of the polymer is measured while vibrating the funnel with a vibrator.

Further, in the propylene block copolymer according to the present invention, it is desirable that the number of rubber lumps having a diameter of 0.1 mm or more contained in the T-die forming film is 5 pieces / 100 cm ² or less.

The propylene block copolymer according to the present invention as described above has a melt flow rate (MFR) of
0.02 to 150 g / 10 minutes, preferably 0.1 to 100 g /
10 minutes is desirable.

The propylene-based block copolymer having an MFR as described above has excellent fluidity and moldability and can be molded into a large product. The propylene-based block copolymer according to the present invention, if necessary, a nucleating agent, a rubber component, a heat stabilizer, a weathering stabilizer, a power failure preventive agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye. , Content, natural oil, synthetic oil, wax, filler and the like can be blended.

Method for producing propylene block copolymer The propylene block copolymer as described above is prepared by polymerizing (i) propylene to form a polypropylene component in the presence of a Ziegler catalyst, and then (ii) ethylene. Ethylene with an α-olefin having 3 to 10 carbon atoms
It is produced by forming an α-olefin random copolymerization component.

First, the Ziegler catalyst used in the present invention will be described below. Ziegler Catalyst The Ziegler catalyst used in the present invention is a Ziegler catalyst exhibiting isospecificity and is composed of, for example, a transition metal catalyst component and an organometallic catalyst component. As the transition metal catalyst component, a titanium trichloride catalyst component, a MgCl ₂ -supported titanium catalyst component composed of magnesium, halogen, titanium and an electron donor, and _two crosslinked cyclopentadienyl groups as ligands are used. Examples of the metallocene catalyst component having, also as the organometallic catalyst component, trialkylaluminum, alkylaluminum halide,
Examples thereof include alkyl aluminum oxide.

Of these, a catalyst composed of a MgCl ₂ -supported titanium catalyst component (solid titanium catalyst component) and an organometallic catalyst component will be described below. The Ziegler catalyst containing the MgCl ₂ -supported catalyst component used in the present invention is (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor, (b) an organometallic compound catalyst component, c) an organosilicon compound represented by 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, ^Ra is a secondary or tertiary hydrocarbon 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. ) And.

Solid titanium catalyst component (a) as described above
Can be prepared by bringing the following magnesium compound, titanium compound and electron donor (d) into contact with each other.

Specific examples of the titanium compound used for preparing the solid titanium catalyst component (a) include a tetravalent titanium compound represented by the following formula. Ti (OR) _g X _4-g (wherein R is a hydrocarbon group, X is a halogen atom, and g is 0 ≦ g ≦ 4). As such a titanium compound, specifically, TiC
Tetrahalogenated titanium such as l ₄ , TiBr ₄ and TiI ₄ ;
Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H
₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄ H ₉ ) Br ₃
Trihalogenated alkoxy titanium such as; Ti (OCH ₃ )
₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ ,
Ti (OC ₂ H ₅₎ dihalogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On
_{-C 4 H 9) 3 Cl,} Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br; Ti (OCH 3) 4} , Ti (OC 2 H
_{5) 4, Ti (On-} C 4 H 9) 4, Ti (O-iso-C 4 H 9) 4, Ti (O
Examples thereof include tetraalkoxy titanium such as -2-ethylhexyl) ₄ .

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 magnesium metal using the above method during catalyst preparation.

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; allyoxy magnesium such as phenoxy magnesium and 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 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), In the case of using a halogen-free magnesium compound, it is preferable to react with the 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.

Solid titanium catalyst component used in the present invention
(a) is formed by contacting the above-mentioned magnesium compound with the above-mentioned titanium compound and electron donor (d).

Specific examples of the electron donor (d) used in the preparation of the solid titanium catalyst component (a) include the following compounds. Carbon number such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol ~ 18 alcohols, halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol, trichlorohexanol, etc., lower alkyls such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol. C6-C20 phenols which may have a group, acetone, methyl ethyl ketone, methyl iso Cyl ketone having 3 to 15 carbon atoms such as chill ketone, acetophenone, benzophenone and benzoquinone, aldehyde having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octyl aldehyde, 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 18 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, nitriles such as trinitrile, acetic anhydride, phthalic anhydride, acid anhydrides such as benzoic anhydride, pyrrole, methylpyrrole, pyrroles such as 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.

[0052]

[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 methylsuccinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate and isopropylmalon. 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 Hexacarboxylic 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 (d), 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 (d), it is also possible to use the organosilicon compounds represented by the general formulas (ci), (c-ii) and (c-iii) described below.

When the titanium compound, the magnesium compound and the electron donor (d) 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 contacting the titanium compound, magnesium compound and electron donor (d) as described above, and can be produced by any method including known methods. .

A few specific examples of the method for producing the solid titanium catalyst component (a) will be briefly described below. (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 subjected to 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 in which an organomagnesium compound in a liquid state is subjected to a catalytic reaction with a halogen-containing titanium compound. 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 in which a complex consisting of a magnesium compound containing an alkoxy group and an electron donor is contacted with an organometallic compound and then reacted 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 compound such as a magnesium salt of an organic acid, 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) composite,
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 (d) is added per mol of the magnesium compound. The titanium compound is used in an amount of 0.01 to 5 mol, preferably 0.1 to 1 mol, and the titanium compound is used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol.

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

Examples of the (b) organometallic compound catalyst component 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.

(B-2) Group I metal represented by the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, K and R ¹ is the same as above) and aluminum; Complex alkylated product.

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

Examples of the organoaluminum compound belonging to the above [B-1] include the following compounds. 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).

Specific examples of the aluminum compound belonging to (b-1) include trialkyl aluminum such as triethyl aluminum and tributyl aluminum, trialkenyl aluminum such as triisoprenyl aluminum, diethyl aluminum ethoxide and dibutyl aluminum butoxide. Dialkyl aluminum alkoxide, ethyl aluminum sesquiethoxide,
Butyl aluminum sesquibutoxide and other alkyl aluminum sesquialkoxides, R ¹ _2.5 Al (OR ² )
Partially alkoxylated alkylaluminum having an average composition represented by _0.5 , diethyl aluminum chloride, dibutyl aluminum chloride, dialkyl aluminum halides such as diethyl aluminum bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesqui Alkyl aluminum sesquihalide such as bromide,
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride, propylaluminum Alkyl aluminum such as dihydrido Other partially hydrogenated alkyl aluminum such as dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy bromide and other partially alkoxylated and halogenated alkyl aluminum Can be mentioned.

As a compound similar to (b-1), an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can be mentioned. Examples of such a compound include (C ₂ H ₅ ) ₂ AlO
Al (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C
_{4 H 9) 2, (C} 2 H 5) 2 AlN (C 2 H 5) Al (C 2 H 5)
_In addition to _2, etc., aluminoxanes such as methylaluminoxane can also be mentioned.

Compounds belonging to the above (b-2) include Li
Examples thereof include Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

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

The substituted cyclopentenyl group includes 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.

Examples of the substituted cyclopentadienyl group include 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethyl Cyclopentadienyl 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, Examples thereof include a cyclopentadienyl group having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-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.

The organosilicon compound represented by the formula (ci) has a 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

[0093]

[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.

Of these, dimethoxysilanes, particularly dimethoxysilanes represented by the formula (c-ii), are preferred, 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. The Ziegler catalyst used in the present invention is formed from a solid catalyst component such as the solid titanium catalyst component (a) as described above, and this solid catalyst component has an average particle size of 10 to 50 μm, preferably 15 to 30 is desirable, and the content of particles having an average particle size of 5 μm or less is 2
It is desirable that the content is 0% by weight or less, preferably 10% by weight or less.

The particle size of the catalyst is measured by a centrifugal sedimentation type automatic particle size distribution measuring device based on the liquid phase sedimentation method. This is a measurement method that combines the Stokes settling equation and the proportional relationship between the absorbance and the particle concentration.A catalyst existing in a solvent having a constant density and viscosity will settle at a constant rate according to the Stokes settling equation. . The sedimentation rate differs depending on the size of the catalyst particle size, and the size of the particle size can be determined by this difference.

Preliminary Polymerization In the present invention, it is preferable to preliminarily polymerize an olefin with the catalyst component forming the above Ziegler catalyst to form a prepolymerized catalyst component for use.

The prepolymerization is carried out in the presence of the above catalyst component, for example, in the presence of an inert hydrocarbon medium, with 2 to 1 carbon atoms.
It is carried out by polymerizing or copolymerizing 0 olefins.

Examples of the olefin having 2 to 10 carbon atoms include ethylene, propylene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-
Examples include pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 3,5,5-methyl-1-hexene, vinylcyclopentane, vinylcyclohexane, and among these, propylene and 3-methyl- 1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3,
5,5-trimethyl-1-hexene, vinylcyclopentane,
Vinylcyclohexane and the like are preferably used.

Specific examples of the inert hydrocarbon medium used for the prepolymerization include propane, butane, pentane,
Hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclopentane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; ethylene chloride, chloro Examples thereof include halogenated hydrocarbons such as benzene, and combinations thereof. Of these, aliphatic hydrocarbons are preferably used, and aliphatic hydrocarbons having a boiling point of 180 ° C. or less are particularly preferably used.

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
0.0 per 1 g of the solid titanium catalyst component (a) as described above
It is desirable to carry out so as to produce 1 to 2000 g, preferably 1 to 500 g, preferably 2 to 200 g of the prepolymer.

The prepolymerization may be carried out by any of batch method, semi-continuous method and continuous method. When a Ziegler catalyst or a prepolymerization catalyst component composed of the solid titanium catalyst component (a), the organometallic compound catalyst component (b) and the specific organosilicon compound (c) as described above is used, a polymer having a high molecular weight is obtained. A high-molecular weight polypropylene component and a propylene-based block copolymer containing a high-molecular weight ethylene / α-olefin copolymerization component are easily obtained.

Production of Propylene-Based Block Copolymer In the present invention, in the presence of the above Ziegler catalyst,
First, (i) propylene is polymerized to form a polypropylene component, and then (ii) ethylene is copolymerized with an α-olefin having 3 to 10 carbon atoms to form an ethylene / α-olefin copolymerization component, thereby producing propylene. A system block copolymer is produced.

In the present invention, the propylene block copolymer can be produced by any of a batch type polymerization method, a semi-continuous type polymerization method and a continuous type polymerization method, but it is a batch type. Preferably, specifically, (i) propylene polymerization is carried out batchwise, and further (i) propylene polymerization and (ii) ethylene / α-
It is preferable to perform all of the olefin copolymerizations in a batch system.

(I) Polymerization of Propylene In the propylene polymerization step, the content of n-decane-soluble component at 23 ° C. is 2% by weight or less, preferably 1.5% by weight or less, more preferably 1.0% by weight or less, and Pentad isotacticity of n-decane insoluble component at 23 ℃ I
_A polypropylene component is formed in which ₅ is 0.97 or more, preferably 0.975 or more, more preferably 0.980 or more.

In the propylene polymerization step, as a Ziegler catalyst, for example, a solid titanium catalyst component as described above is used.
A catalyst formed from (a), an organometallic compound catalyst component (b), and an organosilicon compound (c) represented by the formula (ci) is used. The prepolymerization catalyst component obtained as described above When is used, the organometallic compound catalyst component (b) and / or the organosilicon compound (c) can be used together with the prepolymerization catalyst component.

Organometallic compound catalyst component (b) and organosilicon compound (c) used together with the prepolymerization catalyst component
May be the same as or different from the organometallic compound catalyst component (b) and the organosilicon compound (c) used when preparing the prepolymerization catalyst component.

In the polymerization system, the solid titanium catalyst component (a) or the prepolymerization catalyst component is usually converted to about 0.0001 to 2 in terms of titanium atom per liter of polymerization volume.
It is used in an amount of mmol, preferably about 0.001-1 mmol, more preferably 0.005-0.5 mmol. 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, and the organosilicon compound (c) is 1 mol of this titanium atom. It is usually used in an amount of 0.001 to 5000 mol, preferably 0.01 to 1000 mol.

Polymerization of propylene can be carried out by a solvent suspension method, a suspension polymerization method using liquid propylene as a solvent, a gas phase polymerization method or the like, but a solvent suspension method is preferable.

As the polymerization solvent used in the solvent suspension polymerization, a hydrocarbon inert to the polymerization can be used. Specific examples of such an inert hydrocarbon include hydrocarbons used in the prepolymerization. Of these, aliphatic hydrocarbons are preferable, and aliphatic hydrocarbons having a boiling point of 180 ° C. or less are particularly preferable.

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 200 ° C.
At 100 ° C., normal pressure to 100 kg / cm ^2, preferably about 2 to 5
It is carried out under a pressure of 0 kg / cm ² .

In the propylene polymerization step as described above, propylene is preferably homopolymerized.
It is also possible to copolymerize by adding a small amount of an olefin other than propylene having 2 to 10 carbon atoms to propylene.

Examples of the α-olefin having 2 to 10 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and 3-methyl-1. -Butene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like can be used, and these may be used in combination. The constituent unit derived from such other α-olefin 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, more preferably 3 mol% or less. .

The polypropylene component thus formed has an MFR (230 ° C., 2.16 kg) of 10 to 500 g /
10 minutes, preferably 10 to 300 g / 10 minutes.

(Ii) Ethylene / α-Olefin Copolymerization In the present invention, after the polypropylene component is produced as described above, the resulting polypropylene is treated with ethylene and the above-mentioned carbon without deactivating the catalyst. Ethylene / copolymerized with α-olefin of several 3 to 10
An α-olefin random copolymerization component is formed.

After producing the polypropylene component as described above, when the ethylene and the α-olefin having 3 to 10 carbon atoms are copolymerized, the solid titanium catalyst component (a) and the organometallic compound are added to the copolymerization system. Compound catalyst component (b),
It is also possible to add an organosilicon compound (c) or the like.

As the α-olefin copolymerized with ethylene, an α-olefin having 3 to 10 carbon atoms as used in the production of the polypropylene component is used. Of these, propylene, 1-butene, 1-pentene and the like are preferably used. These may be used in combination of two or more.

When ethylene and α-olefin are copolymerized, other olefins copolymerizable with them, such as cycloolefins, vinyl compounds and dienes, can be used.

The copolymerization can be carried out in a gas phase or a liquid phase, but is preferably carried out in a liquid phase, particularly in a solvent suspension polymerization. At this time, as the polymerization solvent, the above-mentioned inert hydrocarbons are used, and among these, aliphatic hydrocarbons having a boiling point of 180 ° C. or less are preferably used.

In the copolymerization system, the polypropylene (i) is added in an amount of 10 to 1000 g per liter of the polymerization volume,
Preferably 10 to 800 g, particularly preferably 30 to 50
Used in an amount of 0 g. Further, the solid catalyst component (a) contained in the polypropylene, when converted to titanium atoms,
It is usually present in an amount of 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol, per liter of polymerization volume.

The solid titanium catalyst component (a),
When an organometallic compound catalyst component (b) or an organosilicon compound (c) is added, a solid titanium catalyst component (a)
Is an amount of 0.0001 to 20 mol, preferably 0.001 to 10 mol, per 1 liter of polymerization volume, and the organometallic compound catalyst component (b) is 1 to 1 mol of titanium atom in the polymerization system. The amount of the organosilicon compound (c) in an amount of 2000 moles, preferably about 2 to 1000 moles, is 0.001 to 2000 moles, preferably 0.01 to 1000 moles, per 1 mole of the titanium atom of the polymerization system, Each is used appropriately.

At the time of copolymerization, hydrogen (chain transfer agent) may be added as necessary to adjust the molecular weight. The above copolymerization is usually carried out at a polymerization temperature of about −50 to 200 ° C., preferably about 20 to 100 ° C. and a normal pressure to 100 kg / cm ^{2 and} preferably about ² to 50 kg / cm ² .

In the present invention, this copolymerization can be carried out in two or more stages by changing the reaction conditions. The propylene block copolymer produced as described above is washed with a hydrocarbon inert to the copolymer,
It is preferable since propylene-based block copolymer particles having excellent particle properties can be obtained. As this reaction-inactive hydrocarbon, the hydrocarbon shown as a polymerization solvent in the polymerization step can be used. In particular, the above copolymerization has a boiling point of 180 ° C.
When not carried out in the presence of the following hydrocarbon medium or in the presence of a medium having a boiling point of 180 ° C. or higher, the propylene-based block copolymer obtained by the copolymerization is treated with an inert gas. It is preferable to wash with a hydrocarbon, especially an aliphatic hydrocarbon having a boiling point of 180 ° C. or lower.

The method for producing a propylene-based block copolymer according to the present invention has a high yield per unit amount of the solid titanium catalyst component (a) of the propylene-based block copolymer.
According to the method of the present invention, the content of catalyst residues, particularly halogen, in the product can be relatively reduced. 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.

[0129]

The propylene block copolymer according to the present invention has excellent rigidity and heat resistance, as well as impact resistance and toughness.

Further, the film formed by T-die molding from the propylene block copolymer according to the present invention has a small number of rubber lumps of 0.1 mm or more and is excellent in appearance. Such a propylene-based block copolymer according to the present invention can be used in a wide range of applications, and is particularly preferably used for applications such as automobile interior and exterior materials and electric component housings.

[0131]

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 and comparative examples, each physical property was measured as follows. (1) MFR: Measured according to ASTM D1238. (230 ° C., under 2.16 kg load) (2) Flexural modulus (FM): Measured in accordance with ASTM D790.

Test piece 12.7 mm (width) × 6.4 mm (thickness)
× 127 mm (length) Span span 100 mm Bending speed 2 mm / min (3) Izod impact strength (IZ): ASTM D256
It was measured according to.

Temperature 23 ° C or -30 ° C Test piece 12.7mm (width) x 6.4mm (thickness) x 64mm (length) Notch is machined (4) Heat distortion temperature (HDT) Measured according to ASTM D648 did.

Load 4.6 kg / cm ² (5) Low temperature embrittlement temperature (BTc) Measured in accordance with ASTM D746.

A test piece was punched out from a 2 mm thick square plate. 4.0 mm (width) x 2.0 mm (thickness) x 38.0 mm (length) (6) Number of rubber lumps A polymer is loaded into a 30 mmφ uniaxial extruder equipped with a T die, the cooling roll temperature is 25 ° C, and the resin is Temperature 230
Width of 30 cm x thickness of 50μ at a take-off speed of 3 m / min.
m into a film.

The number of rubber blocks in the film thus T-die formed was counted.

[0138]

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.

The solid titanium catalyst component (a) is
The average particle size was 18.2 μm, and the content of particles having a particle size of 5 μm or less was 5% by weight. [Preparation of prepolymerization catalyst component-1] 400 substituted with nitrogen
A 200 ml glass reactor was charged with 200 ml of purified hexane, and 20 mmol of triethylaluminum, 4 mmol of dicyclopentyldimethoxysilane and the solid titanium catalyst component (a) prepared as described above were converted into titanium atoms in an amount of 2 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 g per 1 g of the solid titanium catalyst component (a).
Met.

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 prepolymerization catalyst component-1. [Polymerization] An autoclave having an internal volume of 2 liters was charged with 800 ml of purified decane, and at room temperature in a propylene atmosphere, 0.75 mmol of triethylaluminum, 0.15 mmol of dicyclopentyldimethoxysilane and the preliminary polymerization obtained by the above-mentioned preliminary polymerization. Polymerization catalyst component-1 was charged in an amount of 0.015 mmol in terms of titanium atom. After introducing 1.8 N liter of hydrogen, the temperature was raised to 80 ° C. while introducing propylene. The polymerization pressure was increased to 7 by replenishing propylene.
It was kept at kg / cm ² G.

After polymerizing propylene for 30 minutes, 60
After cooling to ℃ and depressurizing, unreacted propylene was purged with nitrogen.
Purge for 20 minutes. The porosity produced by the above polymerization
The content of soluble component of n-decane at 23 ℃ is
1.0% by weight, and at 23 ° C insoluble in n-decane.
I measured_Five Was 0.980.

Then, at 60 ° C. under a nitrogen atmosphere, 20 Nml
After adding all the hydrogen at once, a mixed gas of 68 mol% of propylene / 32 mol% of ethylene was introduced, and a polymerization temperature of 60
Polymerization was carried out for 40 minutes under constant conditions of ℃ and polymerization pressure of 5 kg / cm ² G.

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,
It was washed twice with 1 liter of hexane at room temperature.

The yield of the polymer after drying was 210 g,
The polymerization activity was 14000 g / mmol-Ti. The MFR was 2.2 dg / min. The powdery polymer had an apparent bulk specific gravity of 0.43 g / ml, an average particle size of 430 μm, and a falling seconds after heating at 110 ° C. for 1 hour of 7.0 seconds / 100 ml, The fluidity was good.

When this polymer 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 a pentad isotacticity I ₅ of 0.985.
Met.

[0149]

Example 2 The procedure of Example 1 was repeated, except that the hydrogenation amount was changed to 30 Nml when polymerizing the propylene / ethylene mixed gas. The results are shown in Table 1.

[0150]

Example 3 The procedure of Example 1 was repeated, except that hydrogen was not added when the propylene / ethylene mixed gas was polymerized. The results are shown in Table 1.

[0151]

COMPARATIVE EXAMPLE 1 In Example 1, propylene was polymerized for 55 minutes, and then propylene 75 mol% / ethylene 25
Example 1 except that the mol% mixed gas was polymerized for 15 minutes.
I went the same way. The results are shown in Table 1.

[0152]

Comparative Example 2 The procedure of Example 1 was repeated except that the hydrogenation amount was changed to 40 Nml when polymerizing the propylene / ethylene mixed gas. The results are shown in Table 1.

[0153]

Comparative Example 3 [Preparation of Prepolymerization Catalyst Component-2] Nitrogen-substituted 100
After charging 40 liters of purified hexane to a reactor of 1 liter, 5 mol of triethylaluminum, 1 mol of dicyclopentyldimethoxysilane and the solid titanium catalyst component (a) prepared in Example 1 were converted into titanium atom in terms of titanium atom. 5
After charging in a molar amount, propylene was fed at a rate of 7.3 kg / hr for 1 hour to carry out polymerization while maintaining stirring at 20 ° C.
The amount of propylene prepolymerized is the solid titanium catalyst component (a)
It was 3 g per 1 g.

After the prepolymerization, the liquid part was removed by decantation to separate the solid part, and the solid part was reslurried in n-hexane to prepare an n-hexane suspension of prepolymerization catalyst component-2. .

[Continuous Polymerization] Propylene polymerizer A having an internal volume of 200 liters, depressurizing drum B of 200 liters, 200
Polymerization was carried out using a continuous device consisting of a liter propylene / ethylene polymerizer C and a 60 liter depressurizing drum.

In a polymerization vessel A having a liquid level of 130 liters, 33 liters of hexane and 17 kg / hr of propylene were added.
Was continuously supplied, and hydrogen was supplied so that the hydrogen / propylene mole fraction in the gas phase part was 0.4 mole / mole. Furthermore, triethylaluminum 55 mmol / h
r, dicyclopentyldimethoxysilane 11 mmol / hr and the prepolymerization catalyst component-2 obtained above in Ti
It was supplied in an amount of 1.1 mmol / hr in terms of atom, and propylene was polymerized under constant conditions of a polymerization temperature of 80 ° C. and a polymerization pressure of 7 kg / cm ² G. The slurry concentration at this time is 30
It was 0 g / liter.

A depressurizing drum B having a liquid level of 30 liters
Then, under constant conditions of a pressure of 0.3 kg / cm ² G and a temperature of 60 ° C., nitrogen was supplied to the liquid phase portion in an amount of 20 Nm ³ / hr to remove propylene and hydrogen. The depressurizing drum B has
Hexane was continuously fed at a rate of 20 l / hr.

In the polymerization vessel C having a liquid level of 130 liters,
Hexane 38 liters / hr, propylene 9 kg / h
r and ethylene were continuously supplied at a rate of 4.5 kg / hr, and hydrogen was added at a hydrogen / propylene molar ratio of 0 in the gas phase.
Polymerization temperature 60 by supplying 005 mol / mol
Copolymerization of propylene and ethylene was carried out under constant conditions of ℃ and polymerization pressure of 5 kg / cm ² G. The slurry concentration at this time was 200 g / liter.

In the depressurizing drum D having a liquid level of 30 liters, a constant temperature of 65 ° C. and a pressure of 0.3 kg / cm ² G were used.
Nitrogen was supplied to the liquid phase portion at 20 Nm ³ to remove propylene, ethylene and hydrogen.

The slurry extracted from the depressurizing drum D in the final step was separated into a wet cake and a mother liquor by a decanter. Wet cake with a dryer at temperature 90
It was dried at ° C to obtain a white powdery polymer. A part of the obtained white powdery polymer was collected and washed twice with 1 liter of hexane at room temperature.

The amount of the white powder polymer (after drying) extracted from the polymerization vessel D was 20 kg / hr, and the polymerization activity was 18,500 g / mmol-Ti. Also, MFR
Was 7.8 dg / min.

The powdery polymer had an apparent bulk specific gravity of 0.1.
40 g / ml, average particle size is 470 μm, and 110
The dropping time after heating for 1 hour at ℃ was 18 seconds / 100 ml, and the fluidity was poor.

When this polymer was subjected to solvent fractionation with n-decane at 23 ° C., the amount of soluble components was 26.6% by weight and the amount of insoluble components was 73.4% by weight. The soluble component had an ethylene content of 36 mol% and an intrinsic viscosity [η] of 6.9 dl.
/ G. The insoluble component has an MFR of 200 dg.
/ Min and the pentad isotacticity I ₅ was 0.983.

The results are shown in Table 1.

[0165]

[Table 1]

Claims (4)

[Claims] 1. [A] 23 ° C. n-decane insoluble component: 40 to 8
5% by weight and [B] 23 ° C n-decane-soluble component: 15 to 60% by weight, and the [A] 23 ° C n-decane-insoluble component is (1) a structural unit derived from propylene. 85 to 100 mol% in an amount of 0 to 15 mol% of a structural unit derived from an α-olefin having 2 to 10 carbon atoms other than propylene, (2)
The intrinsic viscosity [η] is 0.1 to 20 dl / g, (3) the pentad isotacticity I ₅ measured for the 60 ° C. n-decane insoluble component is 0.98 or more, and [B] The 23 ° C n-decane-soluble component has (1) an ethylene-derived structural unit in an amount of 20 to 80 mol% and a carbon number of 3
10 to 20 constituent units derived from α-olefins
Contained in an amount of ˜80 mol%, and (2) the intrinsic viscosity [η] is 5 to
A propylene-based block copolymer having a content of 15 dl / g. 2. A propylene block copolymer having an average particle size of 250 to 8000 μm and an apparent bulk specific gravity of 0.25 to 0.8.
The propylene-based block copolymer according to claim 1, wherein the propylene-based block copolymer is 0 g / ml and the number of falling seconds is 5 to 15 seconds / 100 ml-polymer particles. 3. In the presence of a Ziegler catalyst, (i) propylene (95 to 100 mol%) and an α-olefin having 2 to 10 carbon atoms other than propylene (0 to 5 mol%) are polymerized to obtain 23 ° C. n- A polypropylene component having a decane-soluble component of 2% by weight or less and a pentad isotacticity I _{5 of} the 23 ° C n-decane-insoluble component of 0.97 or more is formed, and then (ii) ethylene and carbon Number 3-10
The propylene-based block copolymer according to claim 1, wherein the propylene-based block copolymer is produced by copolymerizing the ethylene-α-olefin random copolymerization component with the above α-olefin. Manufacturing method. 4. The method for producing a propylene-based block copolymer according to claim 3, wherein the Ziegler catalyst comprises a particulate catalyst component having an average particle size of 5 μm and a particle content of 20% by weight or less. .