JPH02229807A - Method for producing propylene copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having excellent heat-sealing properties or transparency, etc., by copolymerizing propylene and alpha-olefin in the presence of a catalyst comprising specific solid Ti catalyst component, organic Al compound catalyst component and specific organic silicon catalyst component. CONSTITUTION:The aimed copolymer is obtained by copolymerization of propylene and 2C or 4-20C alpha-olefin so as to be 7-50mol% of the alpha-olefin contained in resultant copolymer in the presence of a catalyst composed of (A) solid titanium catalyst component containing magnesium, titanium and halogen as essential ingredients [preferably halogen/Ti (atomic ratio) is 5-100, electron donor/Ti (molar ratio) is 0.2-6 and Mg/Ti (atomic ratio) is 2-50], (B) organic aluminum compound catalyst component (e.g. triethylaluminum) and (C) organic silicon compound catalyst component containing cyclopentyl group, cyclopentenyl group or cyclopentadienyl group).

Description

[Detailed description of the invention]

Technical Field of the Invention The present invention relates to a propylene-based random copolymer with excellent heat-sealability, heat-sealing properties, transparency, and anti-blocking properties, and a propylene-based random copolymer with excellent rigidity, impact resistance, fluidity, and low-temperature heat-sealability. The present invention relates to a method for producing propylene-based copolymers such as block copolymers with high catalytic efficiency and good operability. Technical background of the invention and its problems Polypropylene has excellent physical properties and is therefore used in a wide range of applications. For example, it is widely used in the packaging film field, but in order to improve heat sealability at low temperatures in this type of application, ethylene is usually copolymerized in an amount of about 1 to 5% by weight.
It is generally provided as a propylene/ethylene copolymer. Polypropylene film modified in this way has the advantage of good transparency and scratch resistance compared to low-density polyethylene film, which is also used as a packaging film, but it still has good transparency and scratch resistance. Heat sealing is poor. In order to further improve heat-sealability, it is known to further increase the amount of ethylene copolymerized, but in this case, the proportion of soluble copolymer that has no utility value increases, and the desired copolymer There is a problem that the yield of On top of that,
In slurry polymerization, the properties of the slurry during polymerization may deteriorate, and the polymerization may even become difficult. In order to avoid such problems, a method of copolymerizing propylene with ethylene and an α-olefin having 4 or more carbon atoms using a conventional titanium trichloride catalyst was proposed in Japanese Patent Application Laid-Open No. 49-1989.
No. 35487, JP-A-51-79195, JP-A-52
It has been proposed in various publications such as No.-18588. According to these proposals, it can be said that the production rate of solvent-soluble polymer is reduced compared to the case of binary copolymerization of propylene and ethylene, but compared to the case of homopolymerization of propylene, Note that the proportion of solvent-soluble polymers produced is large, and this tendency becomes even greater as the amount of copolymerized ethylene or α-olefin having 4 or more carbon atoms increases. The present inventors have developed a supported catalyst formed from a specific solid titanium catalyst component, an organometallic compound catalyst component, and an electron donor catalyst component, using a copolymer of propylene, ethylene, and an α-olefin having 4 or more carbon atoms. When used in polymerization, it is possible to further reduce the amount of soluble polymer compared to the case of using the titanium trichloride catalyst in the above proposal, and the yield of the desired copolymer and catalyst efficiency are also significantly superior. Knowing that it is possible to obtain
This was proposed in Publication No. 91. Although significant improvement was observed by using the catalyst specifically disclosed in this publication,
However, when attempting to produce a copolymer with a fairly high ethylene content, a porridge-like polymer may be formed and the slurry properties may deteriorate, making it difficult to continue polymerization, or the solid polymer may not be produced at a sufficiently high yield. The problem of not being able to obtain it remained. If it is not possible to increase the ethylene content to obtain a copolymer with a low melting point, the only way to obtain a copolymer with a low melting point is to increase the content of α-olefins having 4 or more carbon atoms. is smaller and the rate of copolymerization is also slow, so it was not a good idea to increase the content of the α-olefin having 4 or more carbon atoms more than necessary. Furthermore, the present inventors have disclosed in JP-A-59-47210 that a copolymer of propylene, ethylene, and α-olefin having 4 or more carbon atoms, which has a narrow composition distribution and is suitable for use as a film with excellent heat-sealing properties, has disadvantages. We have proposed a method that can obtain high yields of soluble copolymers while reducing the amount of by-products. However, the copolymers obtained by this method do not necessarily have sufficient heat sealability, heat sealability, transparency, and blocking resistance, and the hydrocarbon soluble content is not sufficiently low. On the other hand, propylene copolymers obtained by block copolymerization rather than random copolymers are also known. Such block copolymers are often used, for example, in containers, automobile parts, low-temperature heat-sealable films, high impact-resistant films, and the like. Generally, in order to further improve the impact strength of the block copolymer described above, it is effective to increase the content of the rubbery copolymer, but this also increases the tendency of the polymer particles to stick, resulting in an increase in the content of the rubbery copolymer. In many cases, problems such as polymer particles attached to the inner walls of the equipment, which make stable long-term continuous operation difficult. Particularly in gas phase polymerization, deterioration in the fluidity of polymer particles due to an increase in the tendency of polymer particles to stick becomes a fatal defect in operation. Furthermore, in slurry polymerization, the amount of solvent-soluble polymer increases, which not only causes problems such as an unreasonable increase in the viscosity of the slurry and makes the polymerization operation difficult, but also increases the amount of rubbery polymer incorporated into the solid polymer more than desired. There is also the problem that it does not increase. The polymer particles obtained by such unsatisfactory polymerization have low bulk density and poor fluidity, and are accompanied by many defects during post-processing operations such as transportation and melt processing. Purpose of the Invention The present invention aims to solve the above-mentioned problems in the prior art, and it is possible to produce a propylene-based copolymer with high polymerization activity and a narrow composition distribution. The purpose of this study is to provide a method for producing propylene-based copolymers that can The present invention also provides a method for producing a propylene-based copolymer, such as a propylene-based random copolymer, which has excellent heat-sealability, heat-sealability, transparency, and blocking resistance, and has a small amount of hydrocarbon soluble content. It is an object. Furthermore, the present invention is directed to the production of propylene-based copolymers such as propylene-based block copolymers with excellent rigidity, impact resistance, fluidity, and low-temperature heat-sealing properties with good operability. The purpose is to provide a method. Summary of the Invention The method for producing a propylene-based copolymer according to the present invention comprises: [A] a solid titanium catalyst component containing magnesium, titanium, and a halogen as essential components, [B] an organoaluminum compound catalyst component, and [C ]
In the presence of an olefin polymerization catalyst formed from an organosilicon compound catalyst component containing a cyclobentyl group, a cyclopentenyl group, a cyclopentadienyl group, or a derivative thereof, propylene and an α- olefin from 1'-7 to 1'-7 in the copolymer from which the α-olefin is obtained.
It is characterized in that it is copolymerized so that it is contained in an amount of 50 mol%. According to the present invention, when it is desired to impart heat-sealability to a propylene-based copolymer on the same level as conventional ones, it is possible to reduce the generation ratio of hydrocarbon-soluble components, thereby improving heat-sealability and A propylene copolymer with excellent transparency and blocking resistance can be obtained. Further, according to the present invention, even if the production ratio of the rubber-like copolymer is increased, the tendency of polymer particles to adhere does not increase much, and deterioration in the fluidity of the obtained propylene-based copolymer particles can be reduced. Therefore, when it is desired to provide a propylene copolymer with the same level of fluidity as before, a larger amount of the rubbery polymer component can be included in the propylene copolymer. DETAILED DESCRIPTION OF THE INVENTION The method for producing a propylene copolymer according to the present invention and the catalyst for olefin polymerization used therein will be specifically described below. In the method for producing a propylene copolymer according to the present invention, the following polymerization catalysts are used. The polymerization catalyst used in the present invention includes a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B],
It is formed from a specific organosilicon compound catalyst component [C]. FIG. 1 shows an example of a flowchart of the method for preparing the catalyst used in the present invention. The solid titanium catalyst component [A] used in the present invention is a highly active catalyst component containing magnesium, titanium, and halogen as essential components, and in particular, a solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components. A titanium catalyst component is suitable because it has excellent stereoregularity and high activity. Such a solid titanium catalyst component [A] is prepared by bringing the following magnesium compound, titanium compound, and, if necessary, an electron donor into contact with each other. In the present invention, the titanium compound used for preparing the solid titanium catalyst component (A) is, for example, TI(OR).
Examples include tetravalent titanium compounds represented by X (R is a hydrocarbon group, X is an 8g 4-g rogene atom, 0≦g≦4). More specifically, T.I.C.
Tetrahalogenated titanium such as DST IBr, TII4; TI(OCH3)(13, TI(QC2H5)C.I23, Ti(On-C4Hg)CD3, Tl(OCR)B r a, TI (Ol
trihalogenated alphoxytitanium such as so CH)Br3; TI(OCR)(12, T1(OC2H5)20g2, 1N(On-CH)Cl2, TI(QC
Dihalogenated dialkoxytitanium such as 2H5) 2Br 2; monohalogenated trialkoxytitanium such as rt(oca8) 3CD, TI(QC2H5) 3CD, 'rtcon-c4H9) 3Cg, TI(QC2H5) 3Br; 'ri(OCH3) ) 4, T l (O C 2 H 5) 4, TI (On-C
Examples include tetraalkoxytitanium such as 4H9) 4. Among these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound. In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [,l] include magnesium compounds having reducibility and magnesium compounds having no reducibility. Here, as a magnesium compound having reducing properties,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing properties include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, probylmagnesium chloride, and butylmagnesium. Examples include magnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, and butylmagnesium halide. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid. Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, improboxymagnesium chloride, and butoxymagnesium chloride. , alkoxymagnesium halides such as octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium,
isobroboxymagnesium, butoxymagnesium,
Alkoxymagnesiums such as n-octoxymagnesium and 2-ethylhexoxymagnesium; aryloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate; can be mentioned. These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds or compounds derived during the preparation of the catalyst component. A magnesium compound that does not have reducing properties,
To derive from a magnesium compound with reducing properties,
For example, a reducing magnesium compound may be brought into contact with a compound such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, or an alcohol. In addition, in the present invention, the magnesium compound includes, in addition to the above-mentioned magnesium compounds having reducing properties and magnesium compounds that do not have reducing properties, complex compounds, composite compounds, or other metal compounds of the above-mentioned magnesium compounds and other metals. It may be a mixture of. Furthermore, a mixture of two or more of the above compounds may be used. In the present invention, among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride, and alioxymagnesium chloride are preferably used. It will be done. In the present invention, when preparing the solid titanium catalyst component [A], it is preferable to use an electron donor, and specific examples of such electron donors include alcohols, phenols, ketones, aldehydes, Examples include oxygen-containing electron donors such as carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-
Alcohols with 1 to 18 carbon atoms such as ethyl hexa,nol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isoprobyl benzyl alcohol; phenol, cresol, xylenol, ethylphenol, probylphenol, Phenols with 6 to 25 carbon atoms that may have an alkyl group such as milphenol, nonylphenol, and naphthol; ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; acetaldehyde , propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, aldehydes having 2 to 15 carbon atoms such as naphthaldehyde; methyl formate, ethyl acetate, vinyl acetate, probyl acetate, octyl acetate, cyclohexyl acetate, ethyl probionate, methyl butyrate, Ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, dibutyl maleate, diethyl butylmalonate, diethyl dibutylmalonate, ethyl cyclohexanecarboxylate, diethyl 2-cyclohexanedicarboxylate , 1,2-cyclohexanedicarboxylic acid di2
-ethylhexyl, methyl benzoate, ethyl benzoate,
Probyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethoxy Ethyl benzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, and other esters preferably contained in the titanium catalyst component. Organic acid esters containing 2 to 30 carbon atoms; Inorganic acid esters such as ethyl silicate and butyl silicate; 2 to 1 carbon atoms such as acetyl chloride, penzoyl chloride, toluic acid chloride, anisyl chloride, and phthalic acid dichloride.
Acid halides of No. 5; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isobrobyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetate amide,
Acid amides such as benzoic acid amide and toluic acid amide;
Acid anhydrides such as benzoic anhydride and phthalic anhydride; amines such as methylamine, ethylamine, doethylamine, tributylamine, viverizine, tripendylamine, aniline, viridine, vicolin, and tetramethylethylenediamine; acetonitrile, penzonitrile, trinitrile, etc. Nitriles: etc. Furthermore, an organosilicon compound represented by the following general formula [1] can also be used as an electron donor. R Si (OR" 4-n -...U
l]n [wherein R and R' are hydrocarbon groups, and 0n<4
] Specifically, the organosilicon compound represented by the above general formula [1] includes trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diisobutyrdimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis 0-Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-}lyldimethoxysilane, bis-p
-Tolyldiethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chlorbutyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane, vinyltriethoxy silane,

[-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisobuboxysilane, vinyl 1-butoxysilane Silane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriarytoxysilane (at lyloxy) silane, vinyltris(β-methoxyethoxysilane), vinyl 1-lyacetoxysilane, dimethyltetraethoxydisiloxane,
Dicyclohexylmethyldimethoxysilane, cyclobentylmethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclobentyldiethoxysilane, di-n-propyldiethoxysilane, di-t-butyldiethoxysilane, cyclobentyltriethoxysilane, etc. are used. Among these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane silane,
Diphenyldiethoxysilane is preferred. Further, as the organosilicon compound containing a cyclopentyl group, a cyclobentenyl group, a cyclopentadienyl group, or a derivative thereof, the compounds described below are used. Two or more types of these electron donors can be used. The electron donor desirably contained in the titanium catalyst component is an ester, more preferably one having the general formula R'-C-OCOR5 (where R1 is a substituted or unsubstituted hydrocarbon group -, R
2 R5 R6 is hydrogen or a substituted or unsubstituted hydrocarbon group, R and -R4 are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. be. Further, R3 and R4 may be connected to each other. The substituted hydrocarbon groups for R1 to R5 above include those containing different atoms such as N, O, and S, such as C-0-CSCOOR, COOH.
It has groups such as OH, SoH, -C-N-C-NH2. ) can be exemplified by having 11 cases. Particularly preferred among these are diesters of dicarboxylic acids in which at least one of RR is an alkyl group having 2 or more carbon atoms. Specifically, the polyhydric carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, dioxyl ethyl malonate, and isobrovir. Diethyl malonate, butyl diethyl malonate, phenyl diethyl malonate, diethyl diethyl malonate, diethyl dibutyl malonate, di-n-butyl diethyl malonate, dimethyl maleate, monooctyl maleate, dioctyl maleate, dibutyl maleate, butyl maleate Aliphatic polycarboxylic acids such as dibutyl acid, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate, dioctyl citraconate, dimethyl citraconate, etc. ester, 1.2
-Alicyclic polycarboxylic acid esters such as diethyl cyclohexanecarboxylate, diisobutyl cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monophthalate Isobutyl, mono-normal butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl normal-butyl phthalate, di-n-propyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-isobutyl phthalate [1-Hebutyl, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineobentyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, Examples include aromatic polycarboxylic acid esters such as triethyl mellitate and dibutyl trimellitate, and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid. Further, specific examples of polyvalent hydroxy compound esters include 1,2-diacetoxybenzene, -methyl-2.
Examples include 3-diacetoxybenzene, 2,3-diacetoxynaphthalene, ethylene glycol diviparate, butanediol piperaate, and the like. Specific examples of the hydroxy-substituted carboxylic acid include benzoylethyl salicylate, acetyl isobutyl salicylate, and acetyl methyl salicylate. In addition to the above-mentioned compounds, examples of polyvalent carboxylic acid esters that can be supported in the titanium catalyst component include diethyl adipate, diisobutyl adipate, diisobutyl sebacate, and di-n-butyl sebacate. , di-n-octyl sebacate, di-2-ethylhexyl sebacate, and other long-chain dicarboxylic acid esters can be used. Among these polyfunctional esters, compounds having the skeleton of the above-mentioned general formula are preferred, and esters of phthalic acid, maleic acid, substituted malonic acid, etc. and alcohols having 2 or more carbon atoms are more preferred, with phthalic acid being particularly preferred. Diesters of acids and alcohols having 2 or more carbon atoms are preferred. Other electron donor components that can be supported on the titanium catalyst component include RCOOR'(RSR' is a hydrocarbyl group that may have a substituent, at least one of which is branched (including alicyclic) ) or a ring-containing chain group). Specifically, as R and R゛, (CH)CH-C2-H5CH, (CH
3) (CH) CHCH2- (CH3)
3 C-C H CH (CH3)CH2
stomach. If either R or R' is a group as described above, the other may be the group described above, or may be another group, such as a linear or cyclic group. Specifically, various monoesters such as dimethyl acetic acid, trimethyl acetic acid, α-methylbutyric acid, β-methylbutyric acid, methacrylic acid, and benzoyl acetic acid, various monocarboxylic acids of alcohols such as isoprobanol, isobutyl alcohol, and tert-butyl alcohol. An example is ester. Carbonic esters can also be selected as electron donors. Specific examples include diethyl carbonate, ethylene carbonate, diisopropyl carbonate, phenylethyl carbonate, diphenyl carbonate, and the like. When supporting these electron donors, it is not necessarily necessary to use them as starting materials, and it is also possible to use compounds that can be converted into these in the process of preparing the titanium catalyst component. Although other electron donors may coexist in the titanium catalyst component, their coexistence in too large a quantity will not have an adverse effect, so they should be kept to a small amount. In the present invention, the solid titanium catalyst component [A] can be produced by contacting the above-described magnesium compound (or magnesium metal), a titanium compound, and preferably a turtle donor. In order to produce the solid titanium catalyst component [A], a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. Note that the above components may be brought into contact with each other in the presence of other reaction agents such as silicon, phosphorus, and aluminum. Several examples of methods for producing these solid titanium catalyst components (A) will be briefly described below. (1) A method of reacting a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be carried out in the presence of a grinding aid or the like. Moreover, when reacting as described above, a solid compound may be pulverized. (2) a liquid magnesium compound that does not have reducing properties;
A method of precipitating a solid titanium complex by reacting a liquid titanium compound in the presence of an fli donor. (3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound. (4) A method in which the reaction product obtained in (1) or (2) is further reacted with an electron donor and a titanium compound. (5) A solid material obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with either a halogen, a halogen compound, or an aromatic hydrocarbon. how to. In this method, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound consisting of a magnesium compound and an electron co-ensemble may be ground in the presence of a titanium compound, then pretreated with a reaction aid, and then treated with a halogen or the like. Examples of reaction aids include organoaluminum compounds and halogen-containing silicon compounds. (6) A method of treating the compounds obtained in the above (1) to (4) with a halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of contacting a contact reaction product with a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol with an electron donor and a titanium compound. (8) Magnesium salts of organic acids, alkoxymagnesiums, aryloxymagnesiums, etc. A method of reacting a nesium compound with an electron donor, a titanium compound and/or a halogen-containing hydrocarbon. Solid titanium catalyst component [A] listed in (1) to (8) above.
Among the preparation methods, a method using liquid titanium halide during catalyst preparation, a method using a titanium compound after use, or a method using a halogenated hydrocarbon when using a titanium compound are preferred. The amount of each of the above-mentioned components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be unconditionally defined, but for example, the amount of electron donor per 1 mole of magnesium compound is about 0. In an amount of 0.01 to 5 mol, preferably 0.05 to 2 mol, the titanium compound is about 0.0
It is used in an amount of 1 to 500 mol, preferably 0.05 to 300 mol. The solid titanium catalyst component [A] thus obtained is:
It contains magnesium, titanium, and halogen as essential components, and preferably contains an electron donor in addition to these. In this solid titanium catalyst component [A], the halogen/titanium (atomic ratio) is about 4 to 200, preferably about 5 to 10.
0, and the electron group Ii/titanium (molar ratio) is about 0.
．． 1 to 10, preferably about 0.2 to about 6, and the magnesium/titanium (atomic ratio) is preferably about 1 to 100, preferably about 2 to 50. This solid titanium catalyst component [A] contains magnesium halide with a smaller crystal size than commercially available magnesium halides, and usually has a specific surface area of about 50 r.
rr/g or more, preferably about 60-1000
i/g, more preferably about 100 to 800 rn'/g. Since the solid titanium catalyst component [A] is composed of the above-mentioned components to form a catalyst component, the composition of the solid titanium catalyst component [A] is not substantially changed by washing with hexane. Such a solid titanium catalyst component [A] can be used alone, or can be diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound, or a polyolefin. In addition,
When a diluent is used, high catalytic activity is exhibited even if the specific surface area is smaller than the above-mentioned specific surface area. Regarding the preparation method of such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-108385.
-126590 publication, 51-20297 publication, 51-28189 publication, 51-64588 publication,
No. 51-92885, No. 51-136825, No. 52-87489, No. 52-100596
No. 52-147H8, No. 52-1045
Publication No. 93, Publication No. 53-2580, Publication No. 53-400
Publication No. 93, Publication No. 53-40094, Publication No. 53-43
No. 094, No. 55-135102, No. 55-
Publication No. 135103, 55-! ．． Publication No. 52710,
No. 58-811, No. 5B-11908, No. 5B-18806, No. 58-83008,
5g-138705, 58-138708, 58-138707, 58-1387
Publication No. 08, Publication No. 58-138709, Publication No. 58-1
Publication No. 38710, Publication No. 58-138715, Publication No. 6
It is disclosed in JP 0-23404, JP 61-21109, JP 61-37802, JP 81-37803, and the like. A compound having at least one aluminum-carbon bond in the molecule can be used as the aluminum compound catalyst component (13). Examples of such compounds include (1) general formula R1ffli (OR2) H
n p q (wherein R and R2 usually have 1 to 15 carbon atoms,
Preferably it is a hydrocarbon group containing 1 to 4, and these may be the same or different from each other. X represents a halogen atom, 0<m≦3, n haO≦n<3, p is 0≦p<3,
q is a number of 0≦q<3, and m + n +
p + q - 3); (i) Group 1 compound represented by the general formula M AffR'4 (wherein 11 is LI Na, K and R1 is the same as above); Examples include complex alkylated products of metal and aluminum. Examples of the organic aluminum compounds belonging to (i) above include the following compounds. ■ General formula RAΩ (OR2) ri 3 shoes (in the formula, R
and R2 are the same as above. m is preferably a number of 1.5≦m≦3), l general formula R A D X 3-1 m (wherein R1 is the same as above, X is halogen, m is preferably Q < m < 3), l general formula RAΩH3-, R1 and R2 are the same as above. X is halogen, Q<m
3, 0≦n<3, 0≦q<3, and m+n+q-3. More specifically, the aluminum compounds belonging to (i) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide. ; Alkylaluminium sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; Rl 2 2 .; Partially alkoxylated alkyl aluminum having an average composition of 0.5 expressed as r A 9 (OR); Dialkyl aluminum halides such as diethyl aluminum chloride and dibutyl alto; Ethyl aluminum sesquichloride and butyl aluminum sesquichloride ,
Alkylaluminum sesquihalides such as ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, probylaluminum dichloride, butylaluminum dibromide; diethylaluminum hydride, dibutylaluminum hydride, etc. dialkylaluminum hydrides; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, probylaluminum dihydride; etc. Partially alkoxylated and halogenated alkyl aluminums may be mentioned. Compounds similar to (i) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C H ) AJ2
0AR (C2H5) 2, (C H )
AN OAK! (C4H9) 2, C 2 H 5 methylaluminoxane, and the like. Compounds belonging to (i) above include LI Aff (C2H5) 4, LiAil (
Examples include C7Hl5)4. Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminum compounds are combined. As the organosilicon compound catalyst component CCE, an organosilicon compound containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, or a derivative thereof in its structure is used. As such an organosilicon compound, a compound represented by the following general formula [■] is preferably used. l2 SIR R (OR”) m 3-s ... [II] (0≦m<3, preferably O≦m≦2,
Particularly preferred is m-2). In the above formula [■], Rl is a cyclobentyl group, a cyclopentenyl group, a cyclopentadienyl group, or a derivative thereof, and specifically, Rl is a cyclopentyl group, a 2-methylcyclobentyl group, a 3-methyl Cyclobentyl group, 2-ethylcyclobentyl group, 3-propylcyclobentyl group, 3-isobrobylcyclobentyl group, 3-butylcyclopentyl group, 3-tert-butylcyclopentyl group, 2.2 -dimethylpentyl group, 2.3-dimethylpentyl group, 2.5
-dimethylcyclopentyl group, 2.2.5-trinotylcyclopentyl group, 2.3,4.5-tetramethylcyclobentyl group, 2,2,5.5-tetramethylcyclopentyl group, ■-cyclopentylprobyl group, ■-methyl-1-cyclobentylethyl group, cyclopentenyl group, 2-cyclobentenyl group, 3-cyclobentenyl group, 2-methyl-L-cyclobentenyl group, 2-methyl-3-cyclopentenyl group group, 3-methyl-3-cyclobentenyl group, 2-ethyl-3-cyclopentenyl group, 2,2-dimethyl-3-cyclopentenyl group, 2,5-dimethyl-3-cyclopentenyl group, 2,
3,4.5-tetramethyl-3-cyclobentenyl group,
2,2,5.5-tetramethyl-3-cyclobentenyl group, ■,3-cyclopentadienyl group, 2,4-cyclopentadienyl group, 1,4-cyclopentadienyl group,
2-methyl-1,3-cyclopentadienyl group, 2-methyl=2,4-cyclobentadienyl group, 3-methyl-
2,4-cyclopentadienyl group, 2-ethyl-2.4
-cyclopentadienyl group, 2.2-dimethyl-2.4
-cyclopentadienyl group, 2.3-dimethyl-2.4
-cyclopentadienyl group, 2,5-dimethyl-2,4
-cyclopentadienyl group, 2.3,4.5-tetramethyl-2.4-cyclopentadienyl group, indenyl group, 2-methylindenyl group, 2-ethylindenyl group, 2-indenyl group, l-methyl-2-indenyl group, 1,3-dimethyl-2-indenyl group, indanyl group, 2-methylindanyl group, 2-indanyl group, ■,3-dimethyl-2-indanyl group, 4.5, 11
．． 7-tetrahydro-indenyl group, 4,5.8.7-tetrahydro-2-indenyl group, 4.5.6.7-tetrahydro-1-methyl-2-indenyl group, 4.5.6
．． Examples include a 7-tetrahydride-1,3-dimethyl-2-indenyl group and a fluorenyl group. Further, in formula [I1], RR is a hydrocarbon group, and examples of R R include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. l2 Furthermore, in formula [■], RR may be crosslinked with an alkylene group or the like. Among these, Rl is a cyclopentyl group, and R2
It is preferred to use organosilicon compounds in which R is an alkyl group or a cyclopentyl group and R3 is an alkyl group, especially a methyl group or an ethyl group. Specific examples of such organosilicon compounds include cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2.3-dimethylcyclopentyltrimethoxysilane, 2.5-dimethylcyclopentyltrimethoxysilane, and cyclobentyltrimethoxysilane. Trialkoxysilanes such as triethoxysilane, cyclopentenyltrimethoxysilane, 3-cyclobentenyl-1-rimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane, and fluorenyltrimethoxysilane. Classes: dicyclopentyldimethoxysilane, bis(2-methylcyclobentyl)dimethoxysilane, bis(3-tert-butylcyclobentyl)dimeth-i=silane,
Bis(2,3-dimethylpentyl)dimethoxysilane, bis(2,5-dimethylpentyl)dimethoxysilane, dicyclobentyldiethoxylin, dicyclopentenyldimethoxysilane, di(3-cyclobentenyl) Dimethoxysilane, bis(2,5-dimethyl-
3-cyclobentenyl)dimethoxysilane, di2.4
- Cyclopencdienyldimethoxysilane, bis(2.
5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane, bis(1-methyl-l-cyclobentylethyl)dimethoxysilane, cyclopentylcyclobentenyldimethoxysilane, cyclobentylcyclobentadienyldimethoxysilane, Diindenyldimethoxysilane, bis(l,3-dimethyl-2-indenyl)dimethoxysilane, cyclopentadienylindenyldimethoxysilane/, diphnoleolenyldimethoxysilane, cyclobentylfluorenyldimethoxysilane, indenyl Dialkoxysilanes such as fluorenyldimethoxysilane: tricyclobentylmethoxysilane, tricyclobentenylmethoxysilane, tricyclopentadienylmethoxysilane, tricyclobentylethoxysilane, dicyclobentylmethylmethoxysilane, Cyclobentyl ethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclobentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclobentyldimethylethoxysilane, bis(2,5-dimethylbentyl)cyclobentylmethoxysilane, dicyclopentyl Monoalkoxysilanes such as cyclopentenylmethoxysilane, dicyclopentylcyclopentadienylmethoxysilane, and diindenylpentylmethoxysilane; other examples include ethylenebiscyclopentyldimethoxysilane. In the method for producing a propylene copolymer according to the present invention, propylene and an α-olefin having 2 or 4 to 20 carbon atoms are copolymerized in the presence of the catalyst as described above. It is preferable to carry out preliminary R polymerization as described below before carrying out the polymerization (main polymerization). By performing such prepolymerization, the activity of the catalyst in the main polymerization can be adjusted, and by doing so, it tends to be possible to obtain a powder polymer with a high bulk density. Further, when prepolymerization is carried out, the powder shape of the produced polymer becomes spherical, and in the case of slurry polymerization, the properties of the slurry become excellent. Therefore, according to the method for producing a propylene-based copolymer according to the present invention, the obtained copolymer/copolymer powder or copolymer slurry can be easily handled. In prepolymerization, the solid titanium catalyst component [
A] is used in combination with at least a portion of the organoaluminum compound catalyst component [B]. At this time, an organosilicon compound can also be allowed to coexist. Examples of such an organosilicon compound include, in addition to the organosilicon compound catalyst component [C], the organosilicon compound represented by the formula [1] used as the electron donor. Such organosilicon compounds can be used alone or in combination of two or more. In the pre-1if polymerization, a catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization. The a degree of the solid titanium catalyst component [A] in P-preparation polymerization is:
It is desirable that the amount is generally about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atoms, per 1iI of the inert hydrocarbon medium described below. The amount of organoaluminum catalyst component [B] is 0.1 to 500 g, preferably 0.1 to 500 g, per Ig of solid titanium catalyst component [A].
The amount may be such that 3 to 300 g of polymer is produced, and is usually about 0.1 to 100 mol, preferably about 0.5 to 5 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A].
Preferably, the amount is 0 mole. The polymerization is preferably carried out under mild conditions by adding the olefin and the above-mentioned catalyst components to an inert hydrocarbon medium.Specifically, the inert hydrocarbon medium used at this time includes propane, Aliphatic hydrocarbons such as butane, pentane, hexane, hebutane, octane, decane, dodecane, kerosene; Alicyclic hydrocarbons such as cyclopenkune, cyclohexane, methylcyclobentane; Aromatic hydrocarbons such as benzene, toluene, xylene; ethylene Examples include halogenated hydrocarbons such as chloride and chlorobenzene, or mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. The olefin to be used may be the same as or different from the olefin used in the main polymerization described below. In addition, in the present invention, a liquid olefin may be used in place of part or all of the above-mentioned inert hydrocarbon medium. When such an olefin is used in pre-61 polymerization, a highly crystalline polymer can be obtained from an α-olefin having 2 to 10 carbon atoms, preferably 3 to 1 o. Pre-(Rffi reaction) The temperature may be such that the prepolymer to be formed does not substantially dissolve in the inert hydrocarbon medium, and is usually about -20 to +100°C, preferably about -20 to +80°C, more preferably 0°C. It is desirable that the temperature is in the range of ~+40°C.In the prepolymerization, a molecular Q modifier such as hydrogen can also be used.Such a molecular Ml modifier can be
The intrinsic viscosity [η] of the polymer obtained by pre-1itit polymerization determined by JPI in decalin at 135°C is approximately 0.2 d.
It is desirable to use it in an amount of N/g or more, preferably about 0.5 to 10 dil/g. The prepolymerization is carried out using the titanium catalyst component [A] 1. as described above.
About 0.1-1000g per g, preferably about 0.3-5
It is desirable to conduct the process so that 00 g of polymer is produced. If the amount of prepolymerization is too large, the production efficiency of the olefin polymer in the main polymerization may decrease, and furthermore, when a film or the like is formed from the obtained olefin polymer, fish eyes may easily occur. . Prepolymerization can be carried out batchwise or continuously. After pre-polymerization as described above or after pre-polymerization,
7 Without polymerization, in the presence of the olefin polymerization catalyst formed from the solid titanium catalyst component [A], the organoaluminum catalyst component [B], and the organosilicon compound catalyst component [C], propylene and the carbon number 2 or 4~
Main polymerization with α-olefin No. 20 is carried out. In the main polymerization, propylene and an α-olefin having 2 or 4 to 20 carbon atoms are copolymerized. The α-olefin having 2 carbon atoms is ethylene, and the α-olefin having 4 to 20 carbon atoms include 1-butene, l-pentene, 4-methyl-l-pentene, l-octene, ■-hexene, 3-methyl -■-bentene, 3-methyl-1-butene, ■-decene, ■-tetradecene, etc. are used. Further, in the main polymerization, propylene and two or more types of α-olefins as described above can be copolymerized, for example, propylene, ethylene, and i-butene can be copolymerized. In particular, in the present invention, it is preferable to copolymerize propylene and ethylene, or propylene and 1-butene, or copolymerize propylene, ethylene, and 1-butene. When block copolymerization of propylene and other α-olefins is carried out, the copolymerization can be carried out separately into an earlier stage polymerization and a later stage polymerization. The pre-stage polymerization may be a homopolymerization of propylene or a copolymerization of propylene with other α-olefins, but especially a copolymerization of propylene with ethylene or a copolymerization of propylene with ethylene and butene. Copolymerization is preferred. The amount of polymerization in the previous step is about 50 to about 95% of the final product.
The desired amount is 1% by weight, preferably about 60% to about 90% by weight. In the present invention, such pre-stage polymerization itself can be further divided into two or more stages, and in that case, the polymerization conditions at each stage may be the same or different. In the later stage polymerization, the polymerization ratio (molar ratio) of propylene to other α-olefins is 10/90 to 90/10, preferably 20/80 to 80/20, particularly preferably 3
It is desirable to carry out the polymerization reaction so that the ratio is 0/70 to 70/30. In the latter stage polymerization step, a step for producing a crystalline polymer or copolymer made of another α-olefin may be further provided. The propylene copolymer thus obtained may be a random copolymer or a block copolymer as described above. In this propylene copolymer, the α-olefin having 2 or 4 to 20 carbon atoms has 7
Preferably present - in an amount of ~50 mol%. In particular, in the propylene random copolymer, the α-olefin having 2 or 4 to 2 carbon atoms is 7 to 20 mol%, preferably 7 to 18 mol%, more preferably 8 to 15 mol%.
It is desirable that it be present in an amount of In addition, in propylene block copolymers, α-
The olefin is 10 to 50 mol%, preferably 20 to 5
Desirably, it is present in an amount of 0 mol%, more preferably 25-45 mol%. Further, the FM (tensile strength) of the obtained propylene copolymer is usually 8000 kg/cd or less, preferably 6000 kg/cd or less.
000 kg/cd or less is desirable. The melting point of the above-mentioned propylene-based random copolymer measured by a differential scanning calorimeter [hereinafter sometimes abbreviated as DSG melting point] is 90 to 130 °C, preferably 9
It is in the range of 5 to 125°C, particularly preferably 100 to 120°C. Here, using a Perkin Elmer DSC-7 model, a press sheet with a thickness of 0.1 mm that had been red-filtered for 20 hours after molding was heated once to 200°C, and then heated to 25°C at a rate of 10°C/min.
After cooling to 25-200℃ at a heating rate of 10℃/min
℃, and the temperature Ts showing the maximum endothermic peak is measured by DSC.
It was taken as the melting point. In addition, 23 of the propylene block copolymer as mentioned above
The amount of soluble components in n-decane solution at °C is 20 to 7
0% by weight, preferably 30-60% by weight, particularly preferably 40-60% by weight. In addition, the amount of components soluble in n-decane at 23° C. of the copolymer was measured by the following method. That is, 3 g of copolymer sample, -20 mg of 2,6-di-tert-butyl-4-methylphenol, and 500 ml of n-decane were placed in a 1 g flask equipped with a stirring blade, and dissolved on an oil bath at 145°C. let After the copolymer is dissolved in this manner, it is allowed to cool naturally at room temperature for about 8 hours, and then left on an oil bath at 23° C. for 20 hours. The n-decane solution containing the precipitated copolymer and dissolved polymer was filtered and fractionated using a G-4 glass filter, and the resulting solution was dried at 150°C under 10 fins of Hg until it reached a constant weight, and its weight was measured. The soluble amount of the copolymer in the mixed solution was calculated and determined as a percentage of the weight of the sample copolymer. In addition, when copolymerizing propylene and an α-olefin having 2 or 4 to 20 carbon atoms, a compound having polyunsaturated bonds such as a conjugated diene or a non-conjugated diene can also be used as a raw material. In the method for producing a propylene copolymer according to the present invention, the main polymerization of propylene and α-olefin having 2 or 4 to 20 carbon atoms can usually be carried out in a gas phase or a liquid phase. It is preferable to carry out the main polymerization by a method that includes a phase polymerization step. When the main polymerization takes the reaction form of slurry polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, or an olefin that is liquid at the reaction temperature can also be used. In the method for producing a propylene copolymer according to the present invention, the titanium catalyst component [A] is T per 11 polymerization volumes.
It is usually used in an amount of about 0.001 to 0.5 mmol, preferably about 0.005 to 0.5 mmol, in terms of i atom. In addition, the organoaluminum compound catalyst component [B] is usually about 1 to 2000 moles of metal atoms in the organoaluminum compound catalyst component [Bl] per 1 mole of titanium atom in the titanium catalyst component [A] in the polymerization system. , preferably about 5 to 50
It is used in an amount such that 0 mole. Further, the organosilicon compound catalyst component [Cl] is calculated in terms of 81 atoms in the organosilicon compound catalyst component [C] per 1 mole of metal atoms in the organoaluminum compound catalyst component [B], and is usually about Q. 0
0.01 to 10 mol, preferably about 0.01 to 2 mol, particularly preferably about 0.05 to 1 mol. In the method for producing a propylene copolymer according to the present invention, the titanium catalyst component [A], the organoaluminum compound catalyst component CB], and the organosilicon compound catalyst component [C] may be brought into contact during main polymerization, or the The contact may be made before polymerization, for example, during prepolymerization. In this contacting before main polymerization, only two arbitrary components may be freely selected and brought into contact, or a portion of each component may be brought into contact with each other or in combination. In the method for producing a propylene copolymer according to the present invention, each catalyst component may be contacted in an inert gas atmosphere or in an olefin atmosphere before polymerization. In addition, when a part of the organoaluminum compound catalyst component [B] and the organosilicon compound catalyst component [C1 is used in the pre-6ml polymerization, the catalyst used in the pre-(a) polymerization is used together with the remaining catalyst. , the catalyst used in the prepolymerization may contain a prepolymerization product.If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted, resulting in a copolymer with a high melt flow rate. Even in this case, the catalytic activity does not decrease in the method for producing a propylene copolymer according to the present invention.
The copolymerization temperature with α-olefin is usually about 20 to 2
00°C, preferably about 50-180°C, the pressure is usually
Normal pressure to 100kg/c, preferably about 2 to 50kg/c
c-. In the present invention, copolymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, the copolymerization can be carried out in two or more stages by changing the reaction conditions. According to the present invention, polypropylene-based copolymers such as low-melting-point polypropylene-based random copolymers can be obtained in high yields, and the by-product of hydrocarbon-soluble copolymers is reduced. be able to. Furthermore, polymerization can be carried out without any problem in the suspension polymerization step. Furthermore, since the copolymer yield per unit amount of titanium is large, a catalyst removal operation after polymerization can be omitted. The polypropylene random copolymer obtained by the present invention has excellent heat-sealability, heat-sealability, transparency, and blocking resistance, and has a small amount of hydrocarbon soluble content, so it can be used for packaging such as films, especially shrink films. It is suitable for applications such as films such as food packaging films. Further, according to the present invention, a polypropylene block copolymer having excellent melt flowability, moldability, rigidity, impact resistance, and powder flowability can be produced with high catalytic efficiency and good operability. Effects of the Invention The olefin polymerization method of the present invention uses a specific polymerization catalyst formed from a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and a specific organosilicon compound catalyst component [C]. Propylene and 2 or 4 carbon atoms
Since copolymerization is carried out with ~20 α-olefins, a propylene copolymer with high polymerization activity and a narrow composition distribution can be produced. The propylene random copolymer obtained by the polymerization method of the present invention has excellent heat-sealing properties, heat-sealing properties, transparency, and anti-blocking properties, and has a small amount of hydrocarbon soluble content, so it can be used particularly in films. It is suitable for use in packaging films such as shrink films, such as food packaging films. Furthermore, the propylene block copolymer obtained by the polymerization method of the present invention has excellent rigidity, impact resistance, fluidity, and low-temperature heat sealability, and can be produced with high catalyst efficiency and good operability. Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples. Example 1 [Preparation of solid titanium catalyst component [A]] A high-speed stirring device (manufactured by Tokushu Kika Kogyo ■) with an internal volume of 2 g was sufficiently replaced with N2, and 700 ml of refined kerosene and commercially available Mg
C1 2 10 g - 24.2 g of ethanol and 3 g of sorbitan distearate (trade name: Mazol 320, manufactured by Kao Atlas Building) were added, and the system was heated with stirring, and 1
The mixture was stirred at 800 rpm for 30 minutes at 20°C. Separately, 1fI of refined kerosene was placed in a 112 il glass flask equipped with a stirrer and cooled to -10°C. The above refined kerosene containing MgC12 was transferred to the above purified kerosene 11 cooled to -10°C using a 5 mm Teflon tube. The solid matter produced was collected by filtration, thoroughly washed with hexane, and
A carrier was produced. 7.5 g of the carrier obtained in this way was heated to 15
After suspending in 0 ml of titanium tetrachloride, 1.3 ml of diisobutyl phthalate was added and the temperature was raised to 120°C. After stirring and mixing at 120°C for 2 hours, the solid part was collected by filtration.
Suspend again in 150 ml of titanium tetrachloride and resuspend at 130 ml.
Stirring and mixing were performed at ℃ for 2 hours. Then, the reaction solid was collected by filtration, and the reaction solid was washed with a sufficient amount of purified hexane to obtain a solid titanium catalyst component [A]. This solid titanium catalyst component [A] has a titanium content of 2.2% by weight, a chlorine content of 63% by weight, a magnesium content of 20% by weight, and a diisobutyl phthalate content of 5.0% by weight in terms of atoms.
It was 0% by weight. [Prepolymerization] 200 ml of purified hexane was placed in a 400 ml glass reactor purged with nitrogen, and 20 mmol of triethylaluminum, 4 mmol of dicyclopentyldimethoxysilane, and the solid titanium catalyst component [A
] after adding 2 mmol in terms of titanium atoms, 5.9N
Propylene was supplied at a rate of I/hour for 1 hour, and 2.8 g of propylene was polymerized per Ig of solid titanium catalyst component [A]. After prepolymerizing in this manner, the liquid portion was removed by filtration, and the solid portion collected by filtration was again dispersed in decane. [Main Polymerization] 150 g of sodium chloride (Wako Pure Chemical Industries, Ltd.) was placed in a stainless steel autoclave with an internal capacity of 2 g that had been sufficiently purged with nitrogen, and the mixture was dried under reduced pressure at 90° C. for 1 hour. Thereafter, the inside of the system was cooled to 65°C, and 1 mmol of triethylaluminum and 0.0 mmol of dicyclopentyldimethoxysilane were added.
A mixture of 1 mmol and 0.01 mmol of the solid titanium catalyst component [A] used in the preliminary IWffl synthesis in terms of titanium atoms was charged. After that, 150Nml of hydrogen was charged, and propylene/ethylene/butene mixed gas (74.8/8.8/
7.6 mol/mol/mol) was started. Total pressure 5
The polymerization was carried out at 70°C for 1 hour while maintaining the weight at kg/cd gauge. After the polymerization was completed, the sodium chloride was removed by washing with water, the remaining polymer was washed with methanol, and then heated to 80°C.
It was dried under reduced pressure overnight. The polymerization activity of the catalyst used was 7400 g-PP/millimol-T1, and the MFR of the obtained polymer 7 polymer was 3.3 g/1
At 0 minutes, the apparent density is 0.34 g/ml, the ethylene content is 5.3 mol%, the butene content is 6.2 mol%, the FM is 2300 kg/cd, and the melting point by DSC is 103 ℃, and the amount of n-decane soluble component is 4
It was 2% by weight. Example 2 In Example 1, the mixed gas composition to be supplied was changed to propylene/'ethylene/butene (88.5/5.3/8.
Copolymerization was carried out in the same manner as in Example 1, except that the ratio was 2 mol/mol, /mol). The polymerization activity of the catalyst used was 6400sr-PP/mmol-T1, and the MFR of the obtained polymer was 2.5g/1.
0 minutes, the apparent bulk density is 0.38 f/mi,
The ethylene content is 2.8 mol% and the butene content is 6.
4 mol%, FM is 4600 kg/c-, D
The melting point determined by SC was 121.1°C, and the amount of n-decane soluble component was 8.2% by weight. Example 3 After adding 2.5 kg of propylene and 9N liter of hydrogen at room temperature to a polymerization vessel of 171, the temperature was raised, and at 50°C, 15 mmol of triethylaluminum, 1.5 mmol of dicyclopentyldimethoxysilane, and the same preparation as in Example 1 were added. Add 0.05 mmol of catalyst component [A] in terms of titanium atoms,
The temperature inside the polymerization vessel was maintained at 70°C. 10 after reaching 70℃
The vent valve was opened and propylene was purged until the inside of the polymerization vessel reached normal pressure. After purging, copolymerization was carried out subsequently. That is, 480 NN/hour of ethylene and 720 Nj of propylene! /h, hydrogen was supplied to the polymerization reactor at a rate of 12 Nl/h. Pressure force inside the polymerization vessel 1 0
The opening degree of the vent of the polymerization reactor was adjusted so that the amount of polymerization was kg/cd・G. The temperature during copolymerization was kept at 70°C. After 85 minutes of copolymerization time, the pressure was removed and the resulting polymer weighed 2.8 kg.
The MFR at 230℃ and 2 kg load is 1.8.
g/10 min, the ethylene content is 29 mol%, the apparent bulk density is 0.431/1, and the FM is 360
It was 0 kg/cd. Further, at 23°C, the amount of n-decane soluble component was 41% by weight, and the ethylene content in the soluble component was 43 mol%.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing an example of a catalyst preparation method in the olefin polymerization method according to the present invention.

Claims (1)

[Scope of Claims] 1) [A] a solid titanium catalyst component containing magnesium, titanium and halogen as essential components, [B] an organoaluminum compound catalyst component, and [C] a cyclopentyl group, a cyclopentenyl group, a cyclopentadiene group; In the presence of an olefin polymerization catalyst formed from an organosilicon compound catalyst component containing an enyl group or a derivative thereof, propylene and an α-olefin having 2 or 4 to 20 carbon atoms are combined to obtain the α-olefin. 7 to 50 in the copolymer
1. A method for producing a propylene copolymer, which comprises copolymerizing the propylene copolymer so that the content thereof is mol %. 2) The method for producing a propylene copolymer according to claim 1, wherein the solid titanium catalyst component [A] is a solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components.