JPH1045834A - Polymerization of propylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for polymerizing propylene by which the propylene is stably polymerized in high activity and excellent productivity to form a polymer having a high stereoregularity by polymerizing the propylene under a specific condition. SOLUTION: Propylene is carried out a solventless polymerization at a polymerization temperature higher than the critical temperature of the reaction system in a polymerization system and lower than the melting point of the polymer to be polymerized under a polymerization pressure higher than the critical pressure of the reaction system in the polymerization system, preferably, at 90-160 deg.C polymerization temperature under 45-500kg/cm<2> polymerization pressure. Moreover, a Ziegler catalyst or magnesium-supporting type catalyst, especially a catalyst by which a compound containing a vinyl group is previously polymerized is preferably used as the catalyst, and components comprising the propylene, hydrogen, ethylene and an α-olefin are preferably used as the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for polymerizing propylene. More specifically, it relates to a method for polymerizing propylene having extremely high activity and high stereoregularity.

[0002]

2. Description of the Related Art Conventionally, methods for polymerizing propylene include a slurry method using hexane, heptane or the like as a solvent, a bulk method using propylene itself as a solvent, and a gas phase method using an inert gas as a medium. I have. In these methods, a polymer having high activity and high stereoregularity has been obtained by improving the performance of the catalyst used and the polymerization technique. However, in the slurry method, the concentration of the monomer in the reaction system in the solvent is low, and the polymerization temperature is low, so that the polymerization activity is low. Further, there is a problem that the solvent remains in the polymer to deteriorate the odor level of the polymer.

[0003] On the other hand, a bulk polymerization method in which polymerization is performed in a liquid monomer is also performed. However, the bulk polymerization has a low polymerization temperature and thus does not have sufficient polymerization activity. There is a problem that a large amount of energy is required for reuse and the cost is high. Further, the gas phase method does not have the above-mentioned problem of the solvent, but has an operational problem such as easy formation of a bulk polymer. A polymerization method which solves these problems and realizes higher activity and higher productivity has been desired.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to produce a polymer having a very high polymerization activity, a high productivity and a high stereoregularity without problems such as odor caused by a solvent and formation of a bulk polymer in a gas phase method. It is to provide a way to do it.

[0005]

The present inventors have studied various polymerization methods in order to solve the above-mentioned problems.
By polymerizing propylene under specific conditions, the inventors have found a method capable of providing a polymer having high polymerization stability and high activity and high stereoregularity, which has not been known so far, and reached the present invention. That is, the present invention, under a condition that the polymerization temperature is higher than the critical temperature of the reaction system in the polymerization system and lower than the melting point of the polymer to be polymerized, and the polymerization pressure is higher than the critical pressure of the monomer in the polymerization system. An object of the present invention is to provide a method for polymerizing propylene, which comprises subjecting propylene to solventless polymerization.

[0006]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, polymerization is carried out at a temperature above the critical temperature of the reaction system in the polymerization system and below the melting point of the polymer to be polymerized. That is, the polymerization temperature is propylene used for polymerization, a reaction system composed of hydrogen used as needed, or propylene used for producing a copolymer, ethylene, and / or α- having 4 or more carbon atoms. The range is higher than the critical temperature of the reaction system composed of the olefin and, if necessary, hydrogen, and lower than the melting point of the produced polymer.

The polymerization pressure is higher than the critical pressure of the above reaction system.
Pressure. The polymerization temperature is higher than the critical temperature of the reaction system.
If it is too low, the polymerization monomer will liquefy and the density of the monomer will increase.
Therefore, it is impossible to enjoy the advantages of the present invention.
In addition, the cost of separating and reusing the monomer increases. In addition, polymerization
If the melting point of the polymer is higher than
No. When the polymerization pressure is lower than the critical pressure of the reaction system,
A supercritical phenomenon does not occur and high activity cannot be obtained. Heavy
The polymerization temperature and polymerization pressure are homopolymerization or copolymerization, or
Varies depending on conditions such as the presence or absence of molecular weight regulators such as hydrogen.
For example, when producing a propylene homopolymer,
90 ° C to 160 ° C, preferably 95 ° C to 150 ° C
You. The polymerization pressure is 45 kg / cm^Two~ 500kg / c
m^TwoAnd preferably 50 kg / cm ^Two~ 150kg
/ Cm^TwoIt is.

[0008] In the present invention, solventless polymerization is carried out at the above-mentioned temperature and pressure. In the present invention, the solventless polymerization refers to a method for slurry polymerization using a solvent, a method for solution polymerization, and is different from a method in which polymerization is carried out in a state where a catalyst and a polymer are dissolved or dispersed by adding a solvent to a polymerization system. The polymerization is carried out in a composition containing a monomer as a main component. Typically, polymerization proceeds in the supercritical monomer composition. Therefore, the present invention does not exclude the coexistence of a small amount of a solvent, but rather is preferably used as a diluent or carrier when supplying catalyst components, additives, monomers and the like.

The polymerization apparatus that can be used in the present invention is not particularly limited as long as it can withstand the conditions such as temperature and pressure employed in the method of the present invention, and known polymerization apparatuses can be used. A stirring tank having an attached power unit, a loop-type reaction tank that circulates the reaction system by a blower, and the like can be used. In the present invention, propylene may contain a comonomer, and ethylene or an α-olefin having 4 or more carbon atoms is used as a comonomer usable in the present invention. Specifically, ethylene, butene-1, 4-methyl -Pentene-1, hexene-1, octene-1, decene-1, 3-methyl-butene-1, and the like. The amount of comonomer is not particularly limited, but may be 0.0
It is about 1 to 30% by weight, preferably about 0.1 to 15% by weight.

The catalyst used in the present invention may be any catalyst as long as the effects of the present invention are recognized. A catalyst having excellent activity at a high temperature is desirable, and specifically, the following component (A):
And component (B) or a combination of component (A), component (B) and component (C). here,
"Consisting of" means that the components used are only those listed (ie, components (A) and (B), components (A), (B) and (C)). It does not preclude the co-existence of other components that are purposeful.

<Component A> The component (A) is a solid component for a Ziegler-type catalyst containing titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that in addition to the three components shown, other suitable elements may be contained, and each of these elements is present as any suitable compound. Good thing,
And that these elements may be present as bonded to each other. The solid components themselves containing titanium, magnesium and halogen are known. For example, Japanese Patent Application Laid-Open Nos. 53-45688 and 54
No.-3894, No.54-31092, No.54-394
No. 83, No. 54-94591, No. 54-118484
No. 54-131589, No. 55-75411,
Nos. 55-90510, 55-90511, 55
-127405, 55-147507, 55-
155003, 56-18609, 56-70
Nos. 005, 56-72001, 56-86905
No., 56-90807, 56-155206,
No. 57-3803, No. 57-34103, No. 57-
Nos. 92007, 57-121003, 58-53
No. 09, No. 58-5310, No. 58-5311, No. 58-8706, No. 58-27732, No. 58-3
No. 2604, No. 58-32605, No. 58-6770
No. 3, No. 58-117206, No. 58-127708
Nos. 58-183708 and 58-183709
And JP-A-59-149905 and JP-A-59-149906.

The magnesium compound used as a magnesium source in the present invention includes magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like. can give. Of these, preferred are magnesium halide, dialkoxymagnesium, and alkoxymagnesium halide.

[0013] The titanium compound serving as a titanium source is
General formula Ti (OR ')_4-qX_q(Where R 'is the hydrocarbon residue
Group, preferably having about 1 to 10 carbon atoms.
X represents a halogen, and q represents a number satisfying 0 ≦ q ≦ 4.
You. )). As a specific example
Is TiCl_Four, TiBr_Four, Ti (OC_TwoH_Five) Cl
_Three, Ti (OC_TwoH_Five)_TwoCl_Two, Ti (OC_TwoH_Five)
_ThreeCl, Ti (O-iC_ThreeH ₇) Cl_Three, Ti (On-
C_FourH₉) Cl_Three, Ti (O-nC_FourH₉)_TwoCl_Two,
Ti (OC_TwoH_Five) Br_Three, Ti (OC_TwoH_Five) (OC
_FourH₉)_TwoCl, Ti (O-nC_FourH₉)_ThreeCl, Ti
(OC₆H_Five) Cl_Three, Ti (O-iC_FourH ₉)_TwoC
l_Two, Ti (OC_FiveH₁₁) Cl_Three, Ti (OC₆H₁₃)
Cl_Three, Ti (OC_TwoH_Five)_Four, Ti (O-nC
_ThreeH₇)_Four, Ti (O-nC_FourH₉)_Four, Ti (O-i
C_FourH₉)_Four, Ti (O-nC₆H₁₃)_Four, Ti (O-
nC₈H₁₇)_Four, Ti [OCH_TwoCH (C_TwoH_Five) C_Four
H₉]_FourAnd the like.

Further, a molecular compound obtained by reacting an electron donor described later with TiX ' ₄ (here, X' represents a halogen) can be used. As a specific example, TiCl ₄
・ CH ₃ COC ₂ H ₅ , TiCl ₄・ CH ₃ CO ₂ C ₂
H ₅ , TiCl ₄ .C ₆ H ₅ NO ₂ , TiCl ₄ .CH
₃ COCl, TiCl ₄ · C ₆ H ₅ COCl, TiCl
₄・ C ₆ H ₅ CO ₂ C ₂ H ₅ 、 TiCl ₄・ ClCOC
_{2 H 5, TiCl 4 · C} 4 H 4 O and the like.

Preferred among these titanium compounds are
Is TiCl_Four, Ti (OC_TwoH _Five)_Four, Ti (OC
_FourH₉)_Four, Ti (OC_FourH₉) Cl_ThreeAnd so on.

The halogen source is usually supplied from the above-mentioned halogen compounds of magnesium and / or titanium, but known halogenating agents such as aluminum halides, silicon halides and phosphorus halides. Can also be supplied from

The halogen contained in the catalyst component is fluorine,
It may be chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

The solid component used in the present invention is the above-mentioned essential component.
Other than SiCl_Four, CH_ThreeSiCl _ThreeSilicon compound such as
Substances, polymers such as methyl hydrogen polysiloxane
Silicon compound, Al (OiC_ThreeH₇)_Three, AlCl_Three,
AlBr_Three, Al (OC_TwoH_Five)_Three, Al (OCH_Three)
_TwoAluminum compound such as Cl and B (OCH_Three)_Three,
B (OC_TwoH_Five)_Three, B (OC₆H_Five)_ThreeBoration of etc.
Compound, WCl₆, MoCl_FiveIt is also possible to use other components such as
These are components such as silicon, aluminum and boron.
It may be left in the solid component as a part. Change
When producing this solid component, an electron donor is
It can also be manufactured using as a donor.

Electron donors (internal donors) which can be used for producing the solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, diethers. And oxygen-containing electron donors such as acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol and isopropylbenzyl alcohol, (ii) phenol, cresol, xylenol, ethyl phenol,
C6 to C25 phenols which may have an alkyl group, such as propylphenol, cumylphenol, nonylphenol, and naphthol; and (C) C3 to C15 phenols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone. Ketones, (d) acetaldehyde, propionaldehyde,
C2 to C15 aldehydes such as octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl (fo) formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, propionic acid ethyl,
Methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate,
C2-C2 such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
Organic acid esters 0, (f) inorganic acid esters such as silicates such as ethyl silicate, butyl silicate and phenyltriethoxysilane, (g) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid C2 to C15 acid halides such as chloride, phthaloyl chloride and phthaloyl chloride; and C2 to C2 such as (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether.
0, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-
diethers such as sec-butyl-1,3-dimethoxypropane, acid amides such as (li) acetic acid amide, benzoic acid amide and toluic acid amide; (nu) methylamine;
Ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine,
Examples thereof include amines such as picoline and tetramethylethylenediamine, and nitriles such as (ル) acetonitrile, benzonitrile and tolunitrile. Two or more of these electron donors can be used. Of these, preferred are organic acid esters and organic acid halides, and diethers. Particularly preferred are phthalic esters, cellosolve acetate, phthalic halides and diethers.

The amount of each of the above components can be arbitrary as long as the effects of the present invention can be recognized.
The following range is preferred.

The amount of the titanium compound to be used is 1 × 10 ^-4 to 1 in molar ratio with respect to the amount of the magnesium compound to be used.
000, preferably 0.01 to 10. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio with respect to the amount of magnesium used irrespective of whether the titanium compound and / or the magnesium compound contains halogen or not. ^{-2 to} 1000, preferably 0.1 to 10
0.

The amount of the silicon, aluminum and boron compounds to be used is 1 × 10 ^{−3 to} 100, preferably 0.01 to 0.01 in terms of a molar ratio with respect to the above-mentioned magnesium compound.
1, within the range. The amount of the electron donating compound used is 1 × in molar ratio with respect to the amount of the magnesium compound.
It is in the range of 10 ^-3 to 10, preferably 0.01 to 5.

The solid component for producing the component (A) includes:
Using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, other components such as an electron donor, it is produced, for example, by the following production method. (A) A method in which a magnesium halide is brought into contact with an electron donor, if necessary, and a titanium-containing compound. (B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and is contacted with a magnesium halide, an electron donor, and a titanium halide-containing compound. (C) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound. As the polymer silicon compound, a compound represented by the following formula is suitable.

[0025]

Embedded image

(Where R ² is a hydrocarbon residue having about 1 to 10 carbon atoms, and r is a polymer silicon compound having a viscosity of 1
And a polymerization degree of about 100 centistokes). Of these, methyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentane Methylcyclopentasiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane and the like are preferable.

(D) A method in which a magnesium compound is dissolved with a titanium tetraalkoxide and an electron donor, and the solid component precipitated with a halogenating agent or a titanium halide compound is brought into contact with the titanium compound. (E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, and the like, and then contacted with an electron donor and a titanium compound as necessary. (F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor.

The production conditions of the component (A) of the present invention include:
The following range is preferred. The contact temperature is -50 to 200
° C, preferably about 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Inert diluents used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes and the like.

The component (A) used in the present invention can be used as a component which has undergone a prepolymerization step comprising contacting and polymerizing a vinyl group-containing compound such as an olefin, a diene compound, or styrene. . Specific examples of the olefins used when performing the pre-polymerization,
For example, those having about 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene, 3-methylbutene-1,
1-pentene, 1-hexene, 4-methylpentene
1,1-octene, 1-decene, 1-undecene, 1-
There are eicosene and the like, as specific examples of the diene compound,
1,3-butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, 1,3-pentadiene,
1,4-pentadiene, 2,4-pentadiene, 2,6
-Octadiene, cis-2, trans-4-hexadiene, trans-2, trans-4-hexadiene, 1,3-heptadiene, 1,4-heptadiene,
1,5-heptadiene, 1,6-heptadiene, 2,4
-Heptadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4- Hexadiene, 1,9-decadiene, 1,13-tetradecadiene, p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, dicyclopentadiene and the like. Further, specific examples of styrenes include styrene,
α-methylstyrene, allylbenzene, chlorostyrene and the like.

The reaction conditions of the titanium component and the above-mentioned vinyl group-containing compound may be any conditions as long as the effects of the present invention are recognized, but generally the following ranges are preferable. The prepolymerization amount of the vinyl group-containing compound is 0.001 to 1000 g, preferably 1 to 1 g per 1 g of the titanium solid component.
-100 grams, more preferably in the range of 5-50 grams. The reaction temperature during the prepolymerization is -150 to 85
° C, preferably from 0 to 50 ° C. Further, a polymerization temperature lower than the polymerization temperature at the time of “main polymerization”, that is, the polymerization of α-olefin is preferable. In general, the reaction is preferably carried out with stirring, in which case n-hexane and n-hexane are used.
An inert solvent such as heptane or the like can be present, the above-mentioned vinyl compound itself can be used as a medium, and depending on the type of the vinyl compound, it can be carried out in a gas phase. Further, two or more kinds of the vinyl group-containing compounds can be used in combination.

<Component (B)> Component (B) of the present invention is an organoaluminum compound represented by the following general formula (I):
Or organic aluminum compound represented by the following general formula [II] and a mixture of an organic aluminum compound represented by the following general formula _{^{[III], AIR 3 3-n X 1}} n (I) (wherein, R ³ is A hydrocarbon residue having 1 to 20 carbon atoms, X ¹ is halogen or hydrogen, and n is 0 ≦ n ≦ 1
AIR ⁴ _3-m X ² _m [II] (where R ⁴ is a hydrocarbon residue having 1 to 20 carbon atoms, X ² is halogen or hydrogen, and m is 0 ≦ m ≦ 3
AIR ⁵ _3-p (OR ⁶ ) _p [III] (where R ⁵ is a hydrocarbon residue having 1 to 20 carbon atoms, and R ⁶ is 1 carbon atom which is the same as or different from R ³⁾ -20 hydrocarbon residues, p is a number 0 <p <3)

Specific examples of the organoaluminum compound represented by the general formula [I] include (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum. , (B) alkyl aluminum halides such as diethylaluminum monochloride and diisobutylaluminum monochloride, and (c) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

Organic aluminum represented by the general formula [II]
Examples of the compound include Al (CH_Three)_Three, Al
(C_TwoH_Five)_Three, Al (iC_FourH₉)_Three, Al (C_FourH
₉)_Three, Al (n-C₆H₁₃)_Three, Al (n-C
₈H₁₇)_Three, Al (C_TenH_{twenty one})_Three, (CH_Three)_TwoAlC
l, (C_TwoH_Five)_TwoAlCl, (C_TwoH_Five)_ThreeAl_TwoC
l_Three, (C_TwoH_Five) AlCl_Two, (N-C_ThreeH₇)_TwoA
ICl, (i-C_ThreeH₇)_TwoAlCl, (n-C
_FourH₉)_TwoAlCl, (i-C_FourH₉) AlCl_Two,
(N-C ₆H₁₃)_TwoAlCl, (n-C₈H₁₇)_TwoAl
Cl, (n-C_TenH_{twenty one})_TwoAlCl and (C_TwoH_Five)
_TwoAlBr and the like.

Organic aluminum represented by the general formula [III]
Specific examples of the aluminum compound include (CH_Three)_TwoAl (OC
_TwoH_Five), (C_TwoH_Five)_TwoAl (OCH_Three), (C_TwoH
_Five) _TwoAl (OC_TwoH_Five), (I-C_ThreeH₇)_TwoAl
(OC_TwoH_Five), (N-C_ThreeH ₇)_TwoAl (OC
H_Three), (N-C_FourH₉)_TwoAl (OC_TwoH_Five), (N
-C₆H₁₃)_TwoAl (OC_FourH₉), (N-C₈H₁₇)
_TwoAl (OCH_Three), (N-C _TenH_{twenty one})_TwoAl (OC_Two
H_Five), (CH_Three) Al (OCH_Three)_Two, (C_TwoH_Five)
Al (OC_TwoH_Five)_Two, (I-C_ThreeH₇) Al (OC_Four
H₉)_Two, (N-C_FourH ₉) Al (OC₆H_Five)_Two,
(N-C₆H₁₃) Al (OC₆H₁₃)_TwoAnd (n-C
_TenH_{twenty one}) Al (OCH_Three)_TwoEtc.

When a mixture of an organoaluminum compound of the general formula [II] and an organoaluminum compound of the general formula [III] is used as the component (B), the mixture ratio thereof is as follows:
The molar ratio of the latter to the former is in the range of 0.1 to 100, preferably 0.1 to 10. Component (B) is used in a molar ratio of (A) to the titanium component in component (A).
1 / Ti) is in the range of 0.1 to 1000, preferably 1 to 200.

<Component (C)> In the present invention, an electron donor can be used as the component (C), and specific examples thereof include esters of organic or inorganic acids, diethers, ethers and amines. One selected from the class can be used.

The organic acid esters include those having 1 to 2 carbon atoms.
0 to 1 to 2 basic carboxylic acid or carbonic acid (in the present invention,
An ester (including an intramolecular ester) of a carbon dioxide having 1 to 20 carbon atoms (including an ether alcohol) having 1 to 20 carbon atoms is typical. Specifically, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, 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, cellosolve benzoate, Methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone α- valerolactone, coumarin, phthalide, such as ethylene carbonate and the like.

Examples of the inorganic acid esters include esters of oxygen acids such as silicon, boron, phosphorus and aluminum with alcohols as described above for organic acid esters. Some of the valences of these elements may be filled with hydrocarbon residues (about 1 to 8 carbon atoms) or halogen atoms. Among such inorganic acid esters, esters of silicon oxyacids are preferred. As a specific example,

(CH_Three) Si (OCH_Three)_Three, (C
H_Three) Si (OC_TwoH_Five)_Three, (C_TwoH_Five)_TwoSi (O
CH_Three)_Two, (N-C₆H₁₃) Si (OCH_Three)_Three,
(C_TwoH_Five) Si (OC_TwoH_Five)_Three, (N-C_TenH_{twenty one})
Si (OC_TwoH_Five)_Three, (CH_Two= CH) Si (OCH
_Three)_Three, Cl (CH_Two)_ThreeSi (OCH_Three)_Three, Si
(OCH _Three)_Four, Si (OC_TwoH_Five)_ThreeCl, (C_TwoH
_Five)_TwoSi (OC_TwoH_Five)_Two, (C₁₇H₃₅) Si (OC
H_Three)_Three, Si (OC_TwoH_Five)_Four, (C₆H_Five) Si
(OCH_Three)_Three, Si (OCH_Three)_TwoCl_Two, (C₆H
_Five)_TwoSi (OCH_Three)_Two, (C₆H_Five) (CH_Three) S
i (OCH_Three)_Two, (C₆H_Five) Si (OC
_TwoH_Five) _Three, (I-C_ThreeH₇)_TwoSi (OCH_Three)_Two,
(I-C_ThreeH₇) Si (OC_TwoH _Five)_Three, (I-C_FourH
₉)_TwoSi (OCH_Three)_Two, (C₆H₁₁)_TwoSi (OC
H _Three)_Two, (C₆H₁₁) (CH_Three) Si (OC
H_Three)_Two, (C_FiveH_Five) Si (OCH_Three)_Two, (C₆H
_Five)_TwoSi (OC_TwoH_Five)_Two, (C₆H_Five) (CH_Three)
Si (OC_TwoH_Five)_Two, (N-C_ThreeH₇) Si (OC_Two
H_Five)_Three, (CH_Three) Si (OC_ThreeH₇)_Three, (C₆H
_Five) (CH_Two) Si (OC_TwoH_Five)_Three,

[0040]

Embedded image

(CH_Three)_ThreeCSi (CH_Three) (OC
H_Three)_Two, (CH_Three)_ThreeCSi (HC (CH_Three)_Two)
(OCH_Three)_Two, (CH_Three)_ThreeCSi (CH_Three) (OC
_TwoH_Five)_Two, (CH_Three)_ThreeCSi (C_TwoH_Five) (OCH
_Three)_Two, (C_TwoH_Five)_ThreeCSi (CH_Three) (OCH_Three)
_Two, (CH_Three)_ThreeCSi (n-C_ThreeH₈) (OCH_Three)
_Two, (CH_Three) (C_TwoH_Five) CH-Si (CH_Three) (O
CH_Three)_Two, (CH_Three), CSi (sec-C_ThreeH₈)
(OCH_Three)_Three, ((CH_Three)_TwoCHCH_Two) Si (O
CH_Three)_Two, (CH_Three)_ThreeCSi (i-C_ThreeH₈) (O
CH_Three)_Two, C_TwoH_FiveC (CH_Three)_TwoSi (CH_Three)
(OCH_Three)_Two, (CH_Three)_ThreeCSi (n-C_FourH₉)
(OCH_Three)_Two, C_TwoH_FiveC (CH_Three)_TwoSi (C
H_Three) (OC_TwoH_Five) _Two, (CH_Three)_ThreeCSi (OCH
_Three)_Three, (CH_Three)_ThreeCSi (OC_TwoH_Five)_Three, (C_Two
H_Five)_ThreeCSi (OC_TwoH_Five)_Three, (CH_Three)_ThreeCSi
(I-C_FourH₉) (OCH_Three)_Two, (CH_Three) (C_TwoH
_Five) CHSi (OCH_Three)_Three, (CH_Three)_ThreeCSi (s
ec-C_FourH₉) (OCH_Three)_Two, (I-C_ThreeH₇)_Two
Si (OCH_Three)_Two, (C₆H₁₁) (CH_Three) Si (O
CH_Three)_Two, (CH_Three)_ThreeCSi (n-C₆H₁₃) (O
CH_Three)_Two, (C₆H₁₁)_TwoSi (OCH_Three)_Two, (C
H _Three)_ThreeCSi (C₆H₁₁) (OCH_Three)_Two, (I-C
_ThreeH₇)_TwoSi (OC_TwoH _Five)_Two, ((CH_Three)_ThreeC)
_TwoSi (OCH_Three)_Two, (CH_Three)_ThreeCSi (C
_FiveH_Five) (OCH_Three)_Two, (I-C_FourH₉)_TwoSi (O
CH_Three)_Two, HC (CH_Three)_TwoC (CH_Three)_TwoSi (C
H_Three) (OCH_Three)_Two, (C₆H₁₁) (CH_Three) Si
(OC_TwoH_Five)_Two, HC (CH_Three)_TwoC (CH_Three)_TwoS
i (OCH_Three)_Three, (C_FiveH_Five)_TwoSi (OC
H_Three)_Two, (I-C_ThreeH₇) Si (OCH_Three)_ThreeEtc.
I can do it. Of these, the carbon at the α-position is preferably 2
Grade or Tertiary C3-20 Branched Hydrocarbon Residue
Is a silicon compound having

As the amines, so-called "hindered amines" are suitable. Particularly N-substituted (substituent is lower alkyl group or lower alkylaluminum group) or unsubstituted pyrrolidine or piperidine 2,2,5,5- (in the case of pyrrolidine) or 2,2,6,6-tetra-lower alkyl Substitutes are typical. Examples of such amines include the following.

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As ethers, those which can be called hindered ethers are suitable. In particular, those having at least two lower alkoxy groups on one carbon atom and the carbon atom further having at least one 6-membered ring substituent are typical. The following can be illustrated as such ethers.

[0046]

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[0047]

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[0048]

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[0049]

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In the present invention, a diether compound can be used as the component (C). There is no limitation as long as it is a diether compound. Among them, a diether having a branched aliphatic hydrocarbon and / or a cycloaliphatic hydrocarbon group is preferable. Among them, 1,3-diethers are preferably used, and in particular, 2,2-diisobutyl-1,3
-Dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, , 2-Diisopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-
1,3-dimethoxypropane, 2-cyclopentyl-2
-S-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3
-Dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2
-Isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl- 1,3-
Dimethoxypropane, 2-benzyl-2-s-butyl-
1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-1,
3-Dimethoxypropane is preferably used. Component (C) is used in a molar ratio of 0.0 to component (B).
It is in the range of 1-100, preferably in the range of 0.1-10.

<Formation of Catalyst> The catalyst according to the present invention comprises the components (A) and (B) or the components (A), (B) and (C). According to the above, the fourth component is passed several times at a time, stepwise or divided, in the polymerization tank or in the presence of the olefin to be polymerized, or outside the polymerization tank or in the presence of the olefin to be polymerized. Can be formed by contact.

The method of supplying the components (A), (B) and (C) to the contact site is not particularly limited, but each is dispersed in an aliphatic hydrocarbon solvent such as hexane or heptane, and separately polymerized. It is usually added to the tank. Component (A) can be added to the polymerization tank separately from component (B) or component (C) in a solid state.

[0053]

【Example】

Example 1 [Production of component (A)] In a flask sufficiently purged with nitrogen,
100 ml of dehydrated and deoxygenated toluene was introduced, and then 10 g of Mg (OEt) ₂ was introduced to form a suspension. Then, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., and 1.9 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was introduced, and the temperature was raised to 110 ° C. and reacted for 3 hours. Was.
After the completion of the reaction, the resultant was washed with toluene. Then TiCl ₄ 2
0 ml and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, n-
It was sufficiently washed with heptane to obtain a solid component (A-1) for producing the component (A). This had a titanium content of 2.5% by weight.

Next, 200 ml of n-heptane purified in the same manner as above was introduced into an autoclave sufficiently purged with nitrogen, 5 g of the solid component synthesized above was introduced, and 1.5 g of triethylaluminum was introduced. Propylene was prepolymerized at 20 ° C. After the completion of the pre-polymerization, the component (A) is sufficiently washed with n-heptane.
And A portion was taken out and the amount of prepolymerization was examined. As a result, 8.7 g polypropylene / g solid component (A-
1).

[Polymerization of propylene] 100 ml of propylene sufficiently dehydrated and deoxygenated in a stainless steel autoclave having an internal volume of 1.0 liter and equipped with a stirring and temperature control device at 25 ° C, and triethylaluminum 17 as a component (B). .8 milligrams were introduced. While introducing propylene into the autoclave, the temperature was raised and the pressure was raised to 95 ° C. and 100 kg / cm ² to bring the reaction system into a supercritical state. Then, the component (A) produced above was replaced with the component (A-
1) 2 milligrams were introduced on a standard basis, polymerization was started and polymerization was carried out for 1 hour. After completion of the polymerization, 15 ml of ethanol was added to stop the reaction. 183 grams of polymer were obtained, MFR = 3.6 g / 10 min, polymer bulk density = 0.45 g / cc, I.V. by boiling n-heptane extraction. I = 97.2 wt%.

Example 2 [Production of Component (A)] In a flask sufficiently purged with nitrogen,
200 ml of dehydrated and deoxygenated n-heptane are introduced, then 0.4 mol of MgCl ₂ , Ti (O
-NC ₄ H _{9) 4} was 0.8 mol introduced and reacted for 2 hours at 95 ° C.. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours.
The resulting solid component was washed with n-heptane.

Next, into a flask sufficiently purged with nitrogen,
50 ml of n-heptane purified in the same manner as above was introduced, and the solid component synthesized as above was added in an amount of 0.1 g in terms of Mg atom.
24 moles were introduced. Next, 0.4 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Next, 0.024 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, and the mixture was introduced into the flask at 70 ° C. for 30 minutes.
The reaction was performed at 0 ° C. for 1 hour. After the completion of the reaction, the resultant was washed with n-heptane. After the completion of the reaction, the resultant was washed with n-heptane. Next, 25 ml of TiCl ₄ was introduced and reacted at 100 ° C. for 3 hours. After completion of the reaction, the solid component (A-A) for sufficiently washing with n-heptane to produce the component (A) is obtained.
1). Its titanium content was 2.6% by weight.

Next, 200 ml of n-heptane purified in the same manner as above was introduced into the autoclave sufficiently purged with nitrogen, 5 g of the solid component synthesized above was introduced, and 1.5 g of triethylaluminum was introduced. Propylene was prepolymerized at 15 ° C. After the completion of the pre-polymerization, the component (A) is sufficiently washed with n-heptane.
And A portion was taken out and the amount of prepolymerization was examined. As a result, 12.7 g of polypropylene / g solid component (A-
1).

[Polymerization of propylene] Propylene was introduced into the autoclave in the same manner as in Example-1. Then, 9.3 mg of triethylaluminum was used as the component (B), and (CH ₃ ) ₃ CSi (n-C ₃ H) was used as the component (C).
₇ ) (OCH ₃ ) ₂ 1.5 milligrams, then hydrogen 3
0 ml was introduced. The temperature is increased and pressure is increased while introducing propylene into the autoclave, and the temperature is increased to 110 ° C and 75 kg / c.
The reaction system was brought to a supercritical state with m ² . Then, 1.5 mg of the component (A) produced above was introduced based on the component (A-1), polymerization was started, and polymerization was carried out for 1 hour to terminate the reaction in the same manner as in Example-1. 184 grams of polymer were obtained, MFR = 9.8 g / 10 min, polymer bulk density = 0.46 g / cc, I.V. by boiling n-heptane extraction. I = 98.3 wt%.

[Polymerization of propylene] Using the component (A) produced in Example 2 and the components (B) and (C) shown in Table 1, the reaction system is shown in Table 1. Polymerization was carried out under exactly the same conditions as in Example 2 except that the supercritical state was established.
Table 1 shows the results.

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[Table 1]

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hideo Aihara 1 Tohocho, Yokkaichi-shi, Mie Prefecture Inside Yokkaichi Office of Mitsubishi Chemical Corporation

Claims (7)

[Claims] 1. Propylene under the condition that the polymerization temperature is higher than the critical temperature of the reaction system in the polymerization system and lower than the melting point of the polymer to be polymerized, and the polymerization pressure is higher than the critical pressure of the reaction system in the polymerization system. A polymerization method of propylene, which is subjected to solventless polymerization. ^2. The method for polymerizing propylene according to claim 1, wherein the polymerization temperature is 90 ° C. to 160 ° C. and the polymerization pressure is 45 to 500 kg / cm ² . 3. The method for polymerizing propylene according to claim 1, wherein a Ziegler catalyst is used. 4. The method for polymerizing propylene according to claim 1, wherein a magnesium-supported catalyst is used. 5. The method for polymerizing propylene according to claim 1, wherein a catalyst prepolymerized with a vinyl group-containing compound is used. 6. The method according to claim 1, wherein a component composed of propylene and hydrogen is used as a reaction system. 7. The polymerization method according to claim 1, wherein a component composed of propylene, hydrogen, ethylene and / or an α-olefin having 4 or more carbon atoms is used as a reaction system.