JPH0768294B2 - Process for producing olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer.

[Prior Art] Thermoplastic elastomers are widely used as energy-saving or resource-saving type elastomers, in particular, as substitutes for vulcanized rubber, for automobile parts, industrial machine parts, electronic / electric parts, building materials and the like.

The olefin-based thermoplastic elastomer (TPO) is generally produced by a method of kneading polypropylene and ethylene-propylene-diene rubber (EPDM) in the presence of a peroxide (for example, JP-A-61-217747). ). However, this method has a drawback that the operation is complicated and the manufacturing cost is high.

On the other hand, various attempts have been conventionally made to reduce the cost by directly producing a high molecular weight polymer having the same mechanical properties as TPO at the polymerization stage. For example, a propylene-hexene copolymer (see, for example, JP-A-
49-53983 and Japanese Patent Publication No. 62-19444) and elastic polypropylene (for example, JP-A-61-179247) are proposed.

However, all of these high molecular weight polymers have insufficient low temperature characteristics.

A propylene / ethylene-propylene two-stage polymerization method is well known as a method for improving the low temperature characteristics of polypropylene (for example, JP-A-57-50804).
With this method, it was difficult to produce a vulcanized rubber-like polymer having both flexibility and practical tensile strength.

[Problems to be Solved by the Invention] The present invention has a practical tensile strength even in an unvulcanized state, satisfies flexibility and low temperature characteristics, and has low surface tackiness.
Moreover, it is an object of the present invention to provide a method for producing an olefin polymer having a low production cost.

The present inventors have conducted extensive studies in order to achieve the above object, and as a result, by controlling the crystallinity of a polymer using a specific catalyst system, TPO (partially crosslinked It has been found that a vulcanized rubber-like olefin polymer having the same physical properties as described above can be easily obtained. The present invention is based on this finding.

[Means for Solving the Problems] That is, the method for producing an olefin polymer of the present invention is a method for producing an olefin polymer by a solventless polymerization method, and comprises (A) (a) a crystalline polyolefin and (b) A solid catalyst component composed of magnesium, titanium (tetravalent), a halogen atom and an electron donor, a solid component (B) an organoaluminum compound, and (C) a general formula [In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms; R ² is 1 carbon atom
To 10 hydrocarbon groups; m is an integer of 1 to 6; n is an integer of (6-m). ] An alkoxy group-containing aromatic compound represented by the following formula (D) and an electron-donating compound (D) are used.

Hereinafter, the present invention will be described in detail.

First, the catalyst system used in the present invention will be described.

The solid component (A) in the catalyst system used in the present invention is
It is composed of a crystalline polyolefin (a) and a solid catalyst component (b) composed of magnesium, titanium (tetravalent), a halogen atom and an electron donor.

The solid component (A) may be prepared by, for example, (1) adding an olefin in the presence of a combination of the solid catalyst component (B), an organoaluminum compound, and an electron donating compound used as necessary. Preliminary polymerization method (preliminary polymerization method), (2) In the crystalline powder such as crystalline polypropylene or polyethylene having a uniform particle size, the solid catalyst component (b), an organoaluminum compound optionally used and an electron donor A method of dispersing a reactive compound (melting point of 100 ° C. or higher) (dispersion method), (3) a method of combining the method (1) and the method (2), and the like can be used.

Examples of the crystalline polyolefin (a) in the solid component (A) include crystalline polyolefins obtained from α-olefins having 2 to 10 carbon atoms such as polyethylene, polypropylene, polybutene and poly-4-methylpentene. This crystalline polyolefin (ii)
Is an α having 2 to 10 carbon atoms as shown in the above-mentioned preparation method (1).
-Using olefin, usually 30 to 80 ° C, preferably 55 to 70
It can be produced by carrying out prepolymerization at a temperature in the range of ° C.

At this time, the aluminum / titanium atomic ratio of the catalyst system is usually 0.
It is selected in the range of 1 to 100, preferably 0.5 to 5, and the electron donating compound / titanium molar ratio is 0 to 50, preferably 0.
It is selected in the range of 1-2. In addition, as the crystalline polyolefin (a), as shown in the above-mentioned preparation method (2), it is possible to use one which is manufactured in advance as a powdery crystalline polyolefin.

The crystalline polyolefin (a) has a melting point of 100.
It is preferably at least ° C.

As the organoaluminum compound used for preparing the solid component (A), those exemplified later as the organoaluminum compound as the component (B) can be used. Further, as the electron donating compound used as necessary, those exemplified later as the electron donating compound of the component (D) can be used.

Solid catalyst component (b) constituting the above solid component (A)
Contains magnesium, titanium (tetravalent), a halogen atom and an electron donor as essential components, and can be prepared by bringing a magnesium compound, a titanium compound and an electron donor into contact with each other. In this case, the halogen atom is included as a halide in the magnesium compound and / or the titanium compound.

Examples of the magnesium compound include magnesium dihalides such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite, carboxylates of magnesium, alkoxy magnesium such as diethoxy magnesium, and aryloxy magnesium.
Alkoxy magnesium halides, allyloxy magnesium halides, alkyl magnesium such as ethyl butyl magnesium, alkyl magnesium halides, or reaction products of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, aluminum compounds and the like. However, among these, magnesium halide, alkoxy magnesium, alkyl magnesium, and alkyl magnesium halide are preferable. These magnesium compounds may be used alone or in combination of two or more.

The titanium compound has a general formula of Ti (OR ³ ) _p
Examples thereof include those represented by X _4-p (wherein R ³ is a hydrocarbon group having 1 to 10 carbon atoms, X is a halogen group, and p is an integer of 0 to 4). For example, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetracyclohexyloxy titanium, tetraphenoxy titanium and other tetraalkoxy titanium, tetrachloride. Titanium, titanium tetrabromide, titanium tetraiodide and other tetrahalogenated titanium, methoxytitanium trichloride, ethoxytitanium trichloride,
Trihalogenated alkoxy titanium such as propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium di Dihalogenated dialkoxytitanium such as bromide, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-
Examples include monohalogenated trialkoxy titanium such as n-butoxytitanium chloride, and among these, a high halogen content titanium compound, particularly titanium tetrachloride is preferable. These titanium compounds may be used alone or in combination of two or more.

Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and these halogen atoms are usually used as a halide contained in a magnesium compound and / or a titanium compound.

Further, as the electron donor, those exemplified later as the electron donating compound of the component (D) can be used.

The solid catalyst component (b) can be prepared by a known method (Japanese Patent Laid-Open No. Sho 53-53).
-43094, JP55-135102, JP55-1351
No. 03, JP-A-56-18606). For example, (1) a method of pulverizing a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence of an electron donor and a pulverization aid optionally used and reacting with a titanium compound, ( 2) A method of reacting a liquid material of a magnesium compound having no reducing ability with a liquid titanium compound in the presence of an electron donor to precipitate a solid titanium complex, (3) The above (1) or ( A method of reacting a titanium compound with the one obtained in 2), (4) a method of further reacting an electron donor and a titanium compound with the one obtained in (1) or (2) above, (5) a magnesium compound Alternatively, a complex compound of a magnesium compound and an electron donor is pulverized in the presence of an electron donor, a titanium compound, and optionally a pulverization aid. Then, it can be prepared by a method of treating with halogen or a halogen compound, (6) a method of treating the compound obtained in the above (1) to (4) with halogen or a halogen compound, and the like.

Furthermore, methods other than these methods (JP-A-56-166205, JP-A-57-63309, JP-A-57-190004, JP-A-57-300407, and JP-A-58-58) (47003 publication)
The solid catalyst component (b) can also be prepared by

Further, oxides of elements belonging to Groups II to IV of the periodic table, for example,
Oxides such as silicon oxide, magnesium oxide, and aluminum oxide, or composite oxides containing at least one of the oxides of the elements belonging to Groups II to IV of the periodic table, for example, a solid product obtained by supporting the magnesium compound on silica alumina or the like. And an electron donor and a titanium compound in a solvent
2 minutes to 2 at a temperature in the range of ℃, preferably 10 to 150 ℃
The solid catalyst component (b) can be prepared by contacting for 4 hours.

In preparing the solid catalyst component (b), an organic solvent inert to the magnesium compound, the electron donor and the titanium compound as a solvent, for example, an aliphatic hydrocarbon such as hexane and heptane, an aromatic solvent such as benzene and toluene, and the like. Group hydrocarbons or halogenated hydrocarbons such as mono- or polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms can be used.

The composition of the solid catalyst component (B) thus prepared is usually in the range of magnesium / titanium atomic ratio of 2 to 100, halogen / titanium atomic ratio of 5 to 200, and electron donor / titanium molar ratio of 0.1 to 10. It is in.

Regarding the ratio of the crystalline polyolefin (a) and the solid catalyst component (b) in the solid component (A),
The weight ratio of the component (a) to the component (b) is usually 0.33 to
It is selected to be in the range of 200, preferably 0.10 to 50.

The organoaluminum compound (B) in the catalyst system used in the present invention has the general formula AlR ⁴ _p X _3-p (1) (wherein R ⁴ is an alkyl group having 1 to 10 carbon atoms; X is chlorine or bromine). And a halogen atom; p is a number of 1 to 3). Examples of such an aluminum compound include, for example, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, and trioctyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum. Dialkylaluminum monohalides such as monochloride and alkylaluminum sesquihalides such as ethylaluminum sesquichloride can be preferably used. These aluminum compounds may be used alone or in combination of two or more.

The alkoxy group-containing aromatic compound (C) in the catalyst system used in the present invention has the general formula [In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms; R ² is 1 carbon atom
To 10 hydrocarbon groups; m is an integer of 1 to 6; n is an integer of (6-m). ] Specifically, for example, m-methoxytoluene, vinylanisole, p- (1-propenyl) anisole, p-allylanisole, 1,3-bis (p-methoxyphenyl)- Monoalkoxy compounds such as 1-pentene, dialkoxy compounds such as o-dimethoxybenzene, m-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene, 1-allyl-3,4-dimethoxybenzene and 1,3 , 5-Trimethoxybenzene, 5-allyl-1,2,3-trimethoxybenzene, 5-allyl-1,2,4-trimethoxybenzene, 1,2,3
-Trimethoxy-5- (1-propenyl) benzene, 1,
Examples thereof include trialkoxy compounds such as 2,4-trimethoxy-5- (1-propenyl) benzene, 1,2,3-trimethoxybenzene, and 1,2,4-trimethoxybenzene. Alkoxy compounds and trialkoxy compounds are preferred. These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more.

The electron-donating compound (D) in the catalyst system used in the present invention is a compound containing oxygen, nitrogen, phosphorus, sulfur, silicon, etc., and basically has the ability to improve regularity in the polymerization of propylene. It is possible to have one.

Examples of such electron-donating compounds include organosilicon compounds, esters, thioesters, amines,
Ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides,
Examples thereof include aldehydes and organic acids. Furthermore, for example, diphenyldimethoxysilane, diphenyldiethoxysilane, dibenzyldimethoxylane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane. , Phenyltriethoxysilane,
Organosilicon compounds such as benzyltrimethoxysilane,
Aromatic dicarboxylic acid esters such as n-butyl phthalate and diisobutyl phthalate, benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and alkyl monocarboxylic acids such as toluic acid having 1 to 4 carbon atoms. ester,
Isopropyl methyl ether, isopropyl ethyl ether, t-butyl methyl ether, t-butyl ethyl ether, t-butyl-n-propyl ether, t-butyl-n-butyl ether, t-amyl methyl ether,
asymmetric ethers such as t-amyl ethyl ether, 2,
2'-azobis (2-methylpropane), 2,2'-azobis (2-ethylpropane), 2,2'-azobis (2-methylpentane), α, α'-azobisisobutyronitrile, 1 A sterically hindering substituent is attached to the azo bond of 1,1'-azobis (1-cyclohexanecarboxylic acid), (1-phenylmethyl) -azodiphenylmethane, phenylazo-2,4-dimethyl-4-trixoxypentanenitrile, etc. The azo compound and the like may be used, and one kind may be used, or two or more kinds may be used in combination. Specifically, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl Terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl isobutyl terephthalate, ethyl propyl terephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, diisobutyl isophthalate, methyl ethyl iso Aromatic dicarboxylic acid diesters such as talate, methyl propyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and propyl isobutyl isophthalate, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, acetic acid Cyclohexyl, ethyl propionate, ethyl acetate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoate Acid phenyl, benzyl benzoate, ethyl toluate, amyl toluate, ethyl anisate, ethyl ethoxybenzoate,
Monoesters such as ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate, γ-valerolactone, coumarin, phthalide, esters having 2 to 18 carbon atoms such as ethylene carbonate, benzoic acid, p-oxy Organic acids such as benzoic acid, succinic anhydride, benzoic anhydride,
Acid anhydrides such as anhydrous p-toluic acid, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, etc.
C2 to C15 aldehydes such as 15 ketones, acetaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde and naphthyl aldehyde, and C2 to C15 acids such as acetyl chloride, benzyl chloride, toluic acid chloride and anisic acid chloride. Halides, methyl ether, ethyl ether, isopropyl ether,
C2-C20 ethers such as n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, tributylamine, N, N ' -Dimethylpiperazine, 2,2,6,6-tetramethylpiperidine, tribenzylamine, aniline, pyridine, picoline, amines such as tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, tolunitrile, etc. .

Among these, organic silicon compounds, esters, ethers, ketones and acid anhydrides are preferable, and particularly, organic silicon compounds such as diphenyldimethoxysilane and phenyltriethoxysilane, di-n-butyl phthalate and phthalic acid. Aromatic dicarboxylic acid diesters such as diisobutyl, benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid and alkyl esters of aromatic monocarboxylic acids such as toluic acid having 1 to 4 carbon atoms are preferable. Aromatic dicarboxylic acid diesters are particularly preferred because they improve catalyst activity and activity persistence.

As for the amount of each component of the catalyst system used in the present invention, the solid component (A) is used in such an amount that it is usually in the range of 0.0005 to 1 mol per reaction volume in terms of titanium atom. The organoaluminum compound (B) has an atomic ratio of aluminum / titanium of usually 1 to 3000, preferably
An amount of 40 to 800 is used, and if the amount deviates from the above range, the catalytic activity may be insufficient. Further, the alkoxy group-containing aromatic compound (C) has a molar ratio to the titanium atom in the solid component (A) of usually 0.01 to
It is used at a ratio of 500, preferably 1 to 300,
If this amount is less than 0.01, the physical properties of the polymer produced may deteriorate, and if it exceeds 500, the catalytic activity tends to decrease. The electron donating compound (D) has a molar ratio [(C) /
(D)] is usually used in a proportion of 0.01 to 100, preferably 0.2 to 100.

Next, the method for producing the olefin polymer of the present invention, which is carried out using the above-mentioned catalyst system, will be described.

In the present invention, α is obtained by polymerizing at least one α-olefin in the presence of the above-mentioned catalyst system.
-Olefin homopolymer (eg, propylene homopolymer) or α-olefin copolymer (eg, propylene-α-olefin random copolymer, ethylene-propylene block copolymer) is produced.

In the present invention, the α-olefin used as a raw material is preferably one having 2 to 30 carbon atoms, for example, ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, peptene-. 1, octene-1, nonene-1, decene-1 and the like, and these may be used alone or in combination of two or more kinds.

As a polymerization method, a solventless polymerization method such as gas phase polymerization or bulk polymerization is used, and gas phase polymerization is preferably used.

Here, the gas phase polymerization includes a case where the polymerization is carried out in one step (a gas phase one-step polymerization method) and a case where the polymerization is carried out by a gas phase multi-step polymerization method. Here, the gas-phase one-step polymerization method is used when producing an α-olefin homopolymer (for example, a propylene homopolymer) or a propylene-α-olefin random copolymer. Further, the gas phase multi-stage polymerization method is used when producing an ethylene-propylene block copolymer, an ethylene-propylene-polyene ternary block copolymer, or the like.

Regarding the reaction conditions when carrying out the polymerization by the gas phase one-stage polymerization method, the polymerization pressure is usually 10 to 45 Kg / cm ² , preferably 20 to
30Kg / cm ² , polymerization temperature is usually 40 ~ 90 ℃, preferably 60 ~
It is appropriately selected within the range of 75 ° C. The molecular weight of the polymer can be adjusted by known means, for example, adjusting the hydrogen concentration in the polymerization vessel. The polymerization time depends on the type of olefin as a raw material and the reaction temperature and cannot be determined in a general manner, but about 5 minutes to 10 hours is sufficient.

Particularly preferable α-olefin used as a raw material when carrying out the polymerization by a gas-phase one-stage polymerization method is propylene in the case of homopolymerization, and propylene and α-C 4-30 in the case of copolymerization. Examples include olefins. In the case of this copolymerization, α-
The molar ratio of olefin is preferably in the range of 0.2-20.

When a polymer is produced by a gas phase multi-stage polymerization method, the first polymerization (first stage polymerization) is homopolymerization or copolymerization of α-olefin, and homopolymerization of propylene or α-olefin having 4 to 30 carbon atoms. -Copolymerization with olefins is preferred. The molecular weight can be adjusted by known means (for example, adjustment of hydrogen concentration). Polymerization temperature is usually 40 ~ 90 ℃,
The temperature is preferably 60 to 75 ° C., the polymerization pressure is 10 to 45 Kg / cm ² ,
Preferably, 20 to 30 kg / cm ² , and the polymerization time is 5 minutes to 10
It's time.

The second to final polymerization (nth stage polymerization) is ethylene-propylene copolymer or ethylene-propylene-polyene copolymer.

Here, the polyene is preferably a non-conjugated polyene, and examples thereof include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and 5 -Isopropylidene-2-norbornene,
5-isopropenyl-2-norbornene, 5- (1-butenin) -2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatriene,
6-methyl-4,7,8,9-tetrahydroindene, 2-
2'-dicyclopentenyl, trans-1,2-divinylcyclobutane, 1,4-hexadiene, 4-methyl-1,4-
Hexadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, Examples include 1,4,7-octatriene, 5-methyl-1,8-nonadiene, norbornadiene, vinylnorbornene and the like. Of these non-conjugated polyenes,
Particularly, dicyclopentadiene, 5-ethylidene-2-norbornene and 1,7-octadiene are preferable.

In each polymerization step, the molecular weight can be adjusted by a known means (for example, adjustment of hydrogen concentration). In the case of an ethylene-propylene copolymer, the ethylene unit content can be adjusted by adjusting the composition of the charged gas. Also in the case of an ethylene-propylene-polyene copolymer, the polyene unit content can be adjusted by adjusting the charged amount of the polyene compound. The polymerization temperature is
20 to 90 ° C, preferably 40 to 50 ° C, the polymerization pressure is 5 to
30 kg / cm ² , preferably 10 to ²⁰ kg / cm ² , and the polymerization time is 5 minutes to 10 hours.

In addition, an ethylene-propylene block copolymer, an ethylene-propylene-polyene ternary block copolymer and the like are produced by the gas phase multi-stage polymerization method.

Further, in the above-mentioned polymerization, the respective components constituting the catalyst system, that is, the components (A) to (D) are mixed at a predetermined ratio and brought into contact with each other, and then olefin is immediately introduced to initiate the polymerization. Alternatively, the olefin may be introduced after aging for about 0.2 to 3 hours after the contact. Furthermore, this catalyst component can be supplied by suspending it in an inert solvent or olefin.

In the present invention, post-treatment after polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after the polymerization, a nitrogen stream or the like may be passed through the polymer powder discharged from the polymerization vessel in order to remove the olefin and the like contained therein. If desired, pelletizing may be carried out by an extruder, and in this case, a small amount of water, alcohol or the like may be added in order to completely deactivate the catalyst. Further, in the bulk polymerization method, after the polymerization, the monomer may be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The invention is in no way limited by these examples.

Example 1 (1) pressure-resistant glass three-neck flask was sufficiently purged with nitrogen content volume 0.5 liters of the solid catalyst component (B), purified heptane 20 ml, Mg (OEt) ₂ 4g and phthalate -n- butyl 1.2 After adding g, keeping the system temperature at 90 ° C and adding ₄ ml of TiCl ₄ while stirring, add TiCl ₄ 1
An additional 11 ml was added and the temperature in the system was raised to 110 ° C. 1
After reacting at 10 ° C for 2 hours, the mixture was washed with purified heptane at 80 ° C. 115 ml of TiCl ₄ was added to the obtained solid phase portion, and the mixture was reacted at 110 ° C. for 2 hours. After the reaction was completed, the product was washed several times with 100 ml of purified heptane to obtain a solid catalyst component (b).

(2) Preparation sufficiently purged with nitrogen content volume 2.5 l glass pressure three-neck flask in purified heptane 1.7 liters of solid component (A), A1Et ₃ 0.07
Mol, diphenyldimethoxysilane (DPDMS) 0.05 mmol, and the solid catalyst component (b) 12 prepared in (1) above.
0g was added. The inside of the system was maintained at 30 ° C., propylene was continuously supplied while stirring, and the internal pressure was maintained at 0.5 Kg / cm ² . The reaction was continued for 1 hour and then washed with 1 liter of purified heptane 5 times to obtain a solid component (A).

(3) Gas phase first stage polymerization A1Et ₃ 3 mmol, 1-into a stainless steel pressure autoclave of 5 liter containing 20 g of polypropylene powder, 1-
20 ml of a heptane solution containing 0.15 mmol of allyl-3,4-dimethoxybenzene (ADMB), 0.23 mmol of diphenyldimethoxysilane (DPDMS) and 100 mg of the solid component (A) of (2) (0.06 mmol in terms of Ti atom). added. After evacuating the system for 5 minutes, gas phase polymerization was carried out at 70 ° C. for 1.7 hours while supplying propylene gas until the total pressure reached 29 kg / cm ² .

The above implementation conditions are shown in Table 1.

As a result of the above polymerization, the melt index (MI) was 0.07 (g /
370 g of polypropylene homopolymer of 10 minutes) was obtained. Among them, boiling heptane soluble content (HSP content) was 35.1 wt%, intrinsic viscosity ([η]) was 1.95 (dl / g), and bulk density was 0.33 (g / dl).
The powder properties were also good.

The results are shown in Table 1.

Examples 2 to 4 In Example 1, the amounts of 1-allyl-3,4-dimethoxybenzene (ADMB) which is the component (C) of the catalyst system and dimethoxydiphenylsilane (DMDPS) which is the component (D) of the catalyst system were changed. The procedure was the same as in Example 1 except for the above.

Examples 5 to 7 The procedure of Example 1 was repeated, except that the types of components (C) and (D) of the catalyst system were changed.

Examples 8 and 9 The procedure of Example 1 was repeated, except that hydrogen was added during the polymerization.

Examples 10 and 11 Example 1 was repeated except that the polymerization temperature was changed.

Examples 12 to 14 The procedure of Example 1 was repeated, except that the amount and / or type of the component (A) in the catalyst system was changed.

Example 15 The procedure of Example 1 was repeated, except that the preparation of the solid component (A) was changed as follows.

Pour 0.4 liters of purified heptane, 90 g of polypropylene powder, 0.01 mol of A1Et ₃ , 0.005 mol of diphenyldimethoxysilane (DPDMS) and 30 g of solid catalyst component (b) into a pressure-resistant _three- necked glass flask with an internal volume of 0.5 liter that has been sufficiently replaced with nitrogen while stirring. did. After stirring for 15 minutes, the supernatant was removed and vacuum dried to obtain a solid component (A).

Comparative Example 1 Example 1 was repeated except that the component (D) (DMDPS) of the catalyst system was not added.

Comparative Example 2 The procedure of Example 1 was repeated except that the component (C) of the catalyst system (ADMB) was not added.

Table 1 shows the working conditions and results of Examples 2 to 15 and Comparative Examples 1 and 2 described above.

Example 16 (1) Preparation of solid catalyst component (b) A solid catalyst component (b) was prepared in the same manner as (1) in Example 1 above.

(2) Preparation of solid component (A) A solid component (A) was prepared in the same manner as (2) in Example 1 above.

(3) Gas-Phase First Stage Polymerization Gas-phase polymerization was carried out in the same manner as (3) in Example 1 above.

(4) Gas-Phase Second Stage Polymerization After the gas-phase polymerization reaction of (3) above is completed, the system is depressurized,
After exhausting, ethylene-propylene mixed gas (molar ratio 1 /
4) was supplied up to 11 kg / cm ² and vapor phase polymerization was carried out at 50 ° C. for 1.4 hours.

Table 2 shows the above implementation conditions.

As a result of the above polymerization, 65% by weight of a polypropylene homopolymer having an intrinsic viscosity ([η]) of 3.86 dl / g and 35% by weight of an ethylene-propylene block copolymer having an intrinsic viscosity ([η]) of 4.81 dl / g. %, And 810 g of an ethylene-propylene block copolymer having a melt index (MI) of 0.1 (g / 10 min) was obtained. The results are shown in Table 3.

Examples 17 to 19 The procedure of Example 16 was repeated except that the second-stage polymerization time was changed.

Examples 20 and 21 Example 16 was repeated except that the gas composition in the second stage was changed.

Examples 22 to 24 Examples 16 to 16 except that hydrogen was added during the polymerization.
The same procedure as 16 was performed.

Comparative Example 3 The procedure of Example 16 was repeated except that the component (C) (ADMB) of the catalyst system was not added.

The working conditions of Examples 17 to 24 and Comparative Example 3 are shown in Table 2 and the results are shown in Table 3.

Next, for each of the polymer compositions obtained in Examples 16 to 24 and Comparative Example 3 above, melt index (MI) Shore hardness, yield stress, breaking stress, breaking elongation, tensile elastic modulus, Izod impact test value, etc. The physical property value of was measured. The measurement results are shown in Table 3.

In addition, each measurement was performed by the following method.

Melt index (MI) measurement As test conditions, test temperature 230 ℃ and test load 2.16Kgf
Was measured according to JIS-K7210.

Shore hardness D (durometer D hardness) As a test piece, a 3 mm-thick plate (press molded product) was used and measured at a test temperature of 23 ° C. according to JIS-K7215.

Tensile test Using JIS No. 2 type dumbbell (thickness 1mm, press molded product) as a test piece, yield stress, breaking stress, breaking elongation in accordance with JIS-K7113 under the conditions of test speed of 50mm / min and test temperature of 23 ℃. And the tensile modulus was measured.

Izod impact test As a test piece, JIS No. A notch (thickness 3 mm, press-molded product) is used and JIS-K7110 is used at a test temperature of -20 ° C.
It was measured according to.

EFFECTS OF THE INVENTION According to the present invention, an olefin polymer having practical tensile strength even in an unvulcanized state, sufficient flexibility and low temperature characteristics, low surface tackiness, and low production cost can be obtained. A manufacturing method is provided.

The vulcanized rubbery olefin polymer produced by the present invention is suitably used as a material for automobile parts, industrial machine parts, electronic / electric parts, building materials, and the like.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps of the method for producing an olefin polymer of the present invention.

Claims (1)

[Claims] 1. A method for producing an olefin polymer by a solventless polymerization method, which comprises (A) (a) a crystalline polyolefin and (b) magnesium, titanium (tetravalent), a halogen atom and an electron donor. A solid component composed of a catalyst component, (B) an organoaluminum compound, and (C) a general formula [In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms; R ² is 1 carbon atom
To 10 hydrocarbon groups; m is an integer of 1 to 6; n is an integer of (6-m). ] The manufacturing method of the olefin polymer characterized by using the catalyst system which consists of the alkoxy group containing aromatic compound represented by these, and (D) electron donating compound.