Production of olefin polymer

[Detailed Description of the Invention]

Use field 1 on [industry The present invention relates to how to have been improved for manufacturing an alpha olefin polymer.

Art 1 of [former Although manufacture of the olefin polymer was conventionally performed using the Ziegler catalyst, the molecular weight of the atactic polyolefin which carries out subraw, especially atactic polypropylene (^PP) was very low deficient in a number average molecular weight (about 10,000 Mn) and practical use value. It is a cyclo pen as a manufacturing process of amount of recent-years and polymers^PP. The method (JP,60-245604,A) of using the catalyst which makes the main ingredients a Tajianil machine content titanium compound and aluminoxane is proposed. By this method, there was a fault whose number average molecular weight Mn is about 1~30,000 that this molecular weight still was not enough, and also the molecular weight of generation APP fell in the range (50~90degreeC) of the usual practical propylene polymerization temperature although ^PP of the amount of polymers can be manufactured comparatively, in a room temperature field. although the method of on the other hand using the catalyst which made alumina support a zirconium compound as a manufacturing process of the with a number average molecular weight [ Hn ] of about 30~1 million amount of polymers elastic polypropylene is known (the I JP,61-179247,A public and a molecular weight are too high, and are not suitable for the use of a film etc.)

An object of the problem 1 present invention which [invention tends to solve is to manufacture 7 Tactical polypropylene of number average molecule 11Mn5~200,000 useful as a bright film or a resin property modification agent which has elasticity.

Means 1 for solving [problem It Tactical crumbio(ed) seven times, and these artificers achieved the above-mentioned object about 5~200,000 large number average molecular weight Mn [ of a practical use ] by combining a solid catalyst ingredient and a specific external electron donor wholeheartedly as a result of research that a fin polymer should be manufactured by quantity yield, found out scales, and completed the present invention. Namely, the solid catalyst ingredient for which the present invention contains (A) magnesium, titanium, halogen, and an electron donor as an essential ingredient, (B) An organic aluminium compound and the (C) type (1111 is a Alkyl machine of R prime number 1~20) As for R2, the hydrocarbon group of carbon number 1~10, a hydroxyl group or a nitro group, and m are the integers of 1~6, n -- the integer of 0~ (6 m) -- it is -- the bottom of existence of the catalyst acquired from the alkoxy group content aromatic compounds expressed -- alpha - the manufacturing method of the olefin polymer carrying out talent and polymerizing a fin is provided. The solid catalyst ingredient (A) used for the present invention is prepared by contacting a magnesium compound, a halogenation titanium compound, and an electron donor. Halogenation magnesium like for example, chlorination magnesium as a magnesium compound used here, Magnesium oxide, magnesium hydroxide, hydro-Tulsa Ito, carboxylate salt of magnesium, Alkoxy magnesium, such as diethoxy magnesium, allyloxy magnesium, Alkoxy magnesium halide, allyloxy magnesium halide, A reaction thing with Alkyl magnesium, such as 2 Chilbutyl magnesium, Alkyl magnesium halide, an organic magnesium compound and an electron donor, Halosilane, alkoxysilane, Syros Knoll, an aluminium compound, etc. can be used. Also in these magnesium compounds, magnesium halide, alkoxy magnesium, full kill magnesium, and full kill magnesium halide can use it conveniently. As the example of the titanium compound used as one of the (A) ingredients of a catalyst used for the manufacturing method of the present invention, Tetramethoxy titanium, tetra-ethoxy titanium, tetra n-propoxytitanium, Tetraisopropoxy titanium, tetra-n-butoxytitanium, tetra-iso butoxytitanium, Tetra-ethoxy titanium shown by formula Ti(OR') 4, such as tetracyclo hexyl titanium and tetraphenoxy titanium, Tetra halogenation titanium, such as TiCl4, TiBr, and Ti1. (CH=O) TiC1, (CzllsO) TICli (CJ70) TiC1-1(n C-tl-0)TiCL, (C2HsO) Tori halogenation alkoxy titanium, such as TiBr-, 2(CHJ)TiCL, (CJsO) 2TiC4'2, 2(C-R70)TiC&2 (n-c), II, o2Ticz2, dihalogen I reflex 11.-14 of (C211sO) zTiBr2 grade Knee 4- a nu tru-n>-T;rtheta-1'r-1 t-n-Tirsigma-(C211sO) zTicrho, (n-C 411-0) Mono-halogenation alkoxy titanium of 3TiC1 grade, etc. are mentioned. Also in these, it is preferred to use a high containing halogen thing, and it is preferred to use especially titanium tetrachloride. The titanium compound of these various kinds may be used alone, and these two or more sorts may be mixed and used for it. As an electron donor which is one of the materials of a solid catalyst (A) ingredient used for the present invention, the organic compound containing oxygen, nitrogen, Lynn, or sulfur can be used. As such an electron donor, ester, Thioester, amine, amide, ketone, nitril, phosphines, ether, thioether, an acid anhydride, acid halide, acid amide, aldehyde, and organic acid can be used, for example. Specifically, they are dimethyl phthalate, Diethyl 7 Talate, and Dipro pill phthalate, Shiso butyl 7 Talate, methylethyl 7 Talate, methylpropyl 7 Talate, Methyliso butyl 7 Talate, ethyl propyl 7 Talate, ethyl isobutyl phthalate, Propyl isobutyl phthalate, dimethyl terephthalate, Diethyl terephthalate, Dipro pill tele 7 Talate, diisobutyl tele 7 Talate, methylethyl terephthalate, Methylpropyl terephthalate, methyliso butyl terephthalate, Ethyl propyl tele 7 Talate, ethyl isobutyl tele 7 Talate, Propyl isobutyl tele 7 Talate, Dimethyl isophthalate, Diethyl iso 7 Talate, Dipro pill iso 7 Talate, diisobutyl iso 7 Talate, methylethyl isophthalate, A methyl pro, Ruiso 7 Talate, methyliso butyl iso 7 Talate, Aromatic-dicarboxylic-acid diester, such as ethyl propyl iso 7 Talate, ethyl isobutyl iso 7 Talate, and propyl isobutyl iso 7 Great, Methyl formate, ethyl acetate, acetic acid vinyl, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl acetate, Valeric acid ethyl, Krol acetic acid methyl, dichloroacetic acid ethyl, methyl methacrylate, Ethyl crotonate, pivalate ethyl, dimethyl maleate, cyclohexane-carboxylic-acid ethyl, Benzoic acid ethyl, benzoic acid propyl, benzoic acid butyl, benzoic acid octyl, Benzoic acid cyclohexyl, rest i acid phenyl, benzyl benzoate, toluic acid ethyl, Toluic acid Amir, anisic acid ethyl, ethoxy benzoic acid ethyl, p-butoxy benzoic acid ethyl, 0-Krol benzoic acid ethyl, and A / S Tenope of To 7 Toe acid Ethylnato gamma-Valero lactone, Ester of carbon numbers 2~18, such as Kumarin, 7 Talid, and carbonic acid ethylene Organic acid like aromatic carboxylic acid like benzoic acid and p-oxybenzoic acid The acid anhydrides like a succinic anhydride, anhydrous benzoic acid, and anhydrous p-toluic acid Acetone, methyl ethyl ketone, methyl isobutyl ketone, aceto Phenone, The aldehyde of carbon numbers 2~15, such as the ketone of carbon numbers 3~15, such as benzophenone and benzoquinone, acetaldehyde, octyl aldehyde, benzaldehyde, Tolaldehyde, and Naphthyl aldehyde, Acetyl chloride, Benzyl chloride, toluic acid chloride, Acid A Reid of carbon numbers 2~15, such as anisic acid chloride, methyl ether, Ethyl ether, isopropyl-ether, n-butyl ether, amyl ether, Ether of carbon number 2~20 of tetrahydro 7 run, Anisole, diphenyl ether, ethylene glyph Rubble ether, etc., Acid 7 Mid, such as acetic acid friend r, benzoic acid amide, and toluic acid amide Nitril, such as amine, such as tributylamine, N, and N'-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylene diamine, acetonitrile, benzonitrile, and a Torni trill, can be mentioned. Ester, ether, ketone, and an acid anhydride can use it conveniently especially in these. Alkyl ester of Aromatic carboxylic acid which also especially spreads aromatic-dicarboxylic-acid diester, such as 7 Tal acid di-n-butyl and 7 Tal acid Noiso butyl, The Alkyl ester of carbon number 1~4 of aromatic carboxylic acid like benzoic acid, p-methoxybenzoic acid, p-ethoxy benzoic acid, and toluic acid, etc. are preferred. Especially since aromatic-dicarboxylic-acid diester increases the tacticity of the polymer obtained, it is desirable while raising catalyst activity and active durability. The solid catalyst ingredient of the present invention (A> can be prepared based on the method described in JP,53-43094,A, JP,55-135102,A, JP,55-135103,A, JP,56-18606,A, etc., for example.) namely, -- as the concrete method as a method of obtaining the solid catalyst ingredient (A) of the present invention -- the following several examples -- it can mention . (1) Grind a magnesium compound or a magnesium compound, and the complex compound of an electron donor under existence of the electron donor added by request or grinding aid, make them react to a titanium compound, and prepare them. (2) Make the liquefied thing and liquefied titanium compound of a magnesium compound which do not have reduction ability react under existence of an electron donor, deposit a solid-like titanium complex, and prepare. A titanium compound is made to react to what was obtained by (3) above (1) or (2). (4) Make an electron donor and a titanium compound react to what was obtained by above (1) or (2) further. (5) Grind the complex compound of a magnesium compound or a magnesium compound, and an electron donor under existence of the electron donor, the grinding aid, or the titanium compound added by request, and process and prepare it with halogen or a halogenated compound. (6) The above (1) The compound obtained by ~ (4) is processed and prepared with halogen or a halogenated compound. The preparing method of a statement can also be used also for these ponds as a preparing method of the solid catalyst of the present invention at JP,56-166205,A, JP,57-63309,A, JP,57-190004,A, JP,57-300407,A, JP,58-47003,A, etc. (The oxide of the element belonging to periodic table ■~■ fellows, for example, silicon oxide) The oxide or compound oxide of an element belonging to oxides, such as magnesium oxide and an aluminum oxide, or periodic table ■~■ fellows, For example, a solid catalyst ingredient can be prepared by the temperature of 0~200 degrees contacting in a solvent the solid, electron donor, and titanium halogenation thing which made silica alumina etc. support the above-mentioned magnesium compound by C1, preferably 10~150 degreeC for 2 minute~24 hours. In manufacture of a solid catalyst ingredient (A), it is a magnesium compound as;8 intermediation, It is an un-active organic solvent, for example, hexane, to an electron donor and a titanium compound, Halogenated hydrocarbon, such as a halogenated compound of the saturation of aromatic series carbide hydrogen, such as fatty series carbide hydrogen, such as heptane, benzene, and toluene, or carbon number 1~12 or unsaturated fat fellows, alicycle fellows, and aromatic hydrocarbon, can be used. Thus, magnesium / titanium atom ratio of a composition rate of a solid catalyst ingredient (A) of the present invention obtained is 2~100. Halogen / titanium atom ratio is 5~200, and an electron donor/titanium (molar ratio) is 0.1~10. The organic aluminium compound of the (B) ingredient used for the catalyst of the present invention is In general formulas % type %. (R3 is a Alkyl machine of carbon number 1~10 among a formula, V is the number of 1~3, and X is halogen atoms, such as chlorine and bromine) It comes out and can use what is expressed. For example, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum triisobutylaluminum, Truffe Lukil aluminum and Diethyl aluminum mono-chloride, such as trioctyl aluminum, Diisopropyl aluminum mono-chloride, diisobutyl aluminum mono-chloride, Alkylaluminium sesquihalide, such as Dialkylal kill mono-halide, such as Noooctyl aluminum mono-chloride, and ethylaluminium sesquichloride, can use it conveniently, and it can also use these mixtures. The alkoxy content aromatic compounds used as a (C) ingredient of the catalyst of the present invention are alkoxy content aromatic compounds denoted by the above-mentioned formula (1), m-methoxy toluene, 0-methoxy phenol, m-methoxy phenol, 2-methoxy 4-methyl phenol, a Vinyl ani sole, p-(1-propenyl) Aniso- / Mutt p-7 Liliani sole, 1, 3-bis(p-methoxypheny)2-1-pentene, 5-ant roux 2-methoxy 7 D 7-Le, 4-7 Lilu 2-methoxy phenol, 4-hydroxy 3-methoxy Benoru alcohol, 77 Alfoxy content compounds, such as methoxybenzyl alcohol, a Nitroani sole, and nitroglycerine phenetol, 0-dimethoxy Tonsen, m-dimethoxybenzene, rho-N-methoxy benzene, A Noflex content compound and], such as 3, 4-dimethoxy toluene, 2.6-Simoxy phenol, 1-ant roux 3, and 4-dimethoxybenzene, ]3.5-trimethoxy Benset * A 5-ant roux 1,2,3-trimethoxy benzene, 5-ant roux 1,2,3~trimethoxy benzene, 1,2.3-trimethoxy 5-(1-propenyl) Benset * A, 1, 2.4-dimethoxy 5 - (1-) doria, such as Robenyl benzene, 1, 2.3-dimethoxybenzene, 1, and 2.4-dimethoxybenzene, -- a Lucox content compound can be used -- especially -- a dialkoxy content compound and doria -- a Lucox content compound is preferred. The amount of each ingredient used of the catalyst of the present invention is the (A) ingredient, It converts into Ti atom and is 0.0005~1 vbzo (using the quantity used as l, a part for (B) rM is used by (B) / Ti(molar ratio)1~3000, preferably 40~SOO, and catalyst activity becomes insufficient in case of outside this range.) per reaction capacity 11. (C)/Ti (molar ratio) can use the (C) ingredient, setting it to 0.01~500, preferably 1~300. If the molecular weight and selectivity of a generation polymer fall by less than 0.01 and this exceeds 500, catalyst activity will fall. With the manufacturing method of the present invention, in performing the polymerization reaction of Olefin, an above-mentioned catalyst ingredient is added to the system of reaction, and Olefin which is materials subsequently to this system is introduced. After mixing and contacting the specified quantity, respectively, Olefin can be introduced immediately, and a polymerization can also be made to start, but three ingredients, such (A), (B), and (C), may be used after making it ripe after contact for 0.2~3 hours. In the present invention, restriction in particular does not have polymerization form, conditions, etc., and they are possible also for any, such as solution polymerization, suspension polymerization, and a gaseous phase polymerization, and both a continuation polymerization and a discontinuous polymerization are possible for them. In particular, a solution continuation polymerization and a suspension continuation polymerization are preferred from efficiency and quality. The Olefin pressure of the polymerization system of reaction of the present invention can be chosen by 1-50 kg/cx 2G, and reaction temperature can be suitably chosen in the range of 20-200"C, preferably 60~100 degreeC. A publicly known means, for example, hydrogen etc., can perform molecular weight regulation for a polymerization. J which is selected [ in the case of ethylene ] in ~ 10 hours during 10 minutes for ~ 2 hours during 1 minute, for example in the case of propylene although reaction time changes with kinds etc. of Olefin which is materials -- [Example] An example explains the present invention still in detail. Example 1 (1) Manufacture of a solid catalyst ingredient Butane and 4 g of Mg(oEt) z and 7 Tal acid di-n-butyl of 1.22 were added to 20-d refining at content volume 500R1 Russ 3 Thu mouth 7 Rasp which fully carried out replacement by nitrogen gas. The additional injection of TiC1 after [ 110z1 ] TiC1 of 5xl is dropped is carried out, 90 degreeC Maintaining and stirring the inside of a system, 110 degreeC -- After raising the temperature -- it washed several times with butane to refining of 100zl after the end of 6 reactions which added 1 which washed the output which was made to react for 2 hours, and which was produced by ranking next six by butane 100ij+ to refining of 80 degreeC, next TiC1 of 11511, and was made to react by 110 degreeC for 2 hours, and obtained the solid catalyst ingredient. (2) The polymerization of propylene They are butane and ^IEt of IIIIIIol to refining of 400z1 in the autoclave made from Sulanres of 11, Solid catalyst ingredient Sag shown in the 1st table with 1-ant roux 3 of the amount of statements, 4-dimethoxybenzene (it omits following ADMB), and the above (1) was supplied, and propylene was polymerized by all the Pressure 8 kg/cz2.70"C for 2 hours. A result is shown in a table. Example 2~7 Comparative example 1.2 In Example 1, it carried out similarly except having changed the conditions shown in a table. In comparative example 1, the polymer yield was low, and the rate of the butane fusible part was small to heat, and the ultimate viscosity (molecule fi) was also small. Example 8 (1) Manufacture of a solid catalyst ingredient Butane and 10-g flg(oEL) z were added to the same device as Example 1 to refining of 150i1, and it stirred. Next, it is the reaction product which added carbon tetrachloride 2.08g and 1.32 g of tetraisopropoxy titanium at room temperature, and performed the reaction by 80 degreeC for 2 hours and which was acquired by ranking next zero at room temperature! 1 It washed with butane to refining of 5011. Next, TiCl4 of benzoic acid n-butyl 3.69g and 5011 was added, and it Temperature rising(ed) to 98 degreeC, and performed the reaction for 1 hour. Then, room temperature washed with butane to refining of 150z1, and also TiC1 of 5011 was added, and it Temperature rising(ed) to 98 degreeC, and performed the reaction for 0.5 hour. It washed several times with butane to refining of 10011j! after the end of a reaction, and obtained the solid catalyst ingredient. (2) The polymerization of propylene It carried out like Example 1. Example 9 (1) Manufacture of a solid catalyst ingredient After adding butane, the titanium tetra-butoxide of 75I11, and anhydrous-salts-ized magnesium of Log to refining of 7511, the flask was heated to 90 degreeC and chlorination magnesium was completely dissolved in glass 3 Lofrasco of 300z7 content volume which carried out replacement by nitrogen gas over 2 hours. Next, a chlorination magnesium titanium butoxide complex is deposited by cooling a flask to 40degreeC and adding methil hydrogen polysiloxane and 1511. After washing this with butane to refining, silicon tetrachloride 8.7x1 and 7 Tal acid diheptyl 1.Sx1 were added, and it held by 50 degreeC for 2 hours. Subsequently, it washes with butane to refining, and also titanium tetrachloride 25 shoulder ! is added, and it holds by 70 degreeC for 2 hours. This was washed with butane to refining and the solid catalyst ingredient (A) was obtained. The titanium content in this ingredient (A) was 3.0 % of the weight, and the diheptyl phthalate content was 25-fold% [ 1 ]. (2) The polymerization of propylene It carried out like Example 1. Comparative example 3 In Example 1, it carried out like this except having used TiC1, 0, and 25mzo1 instead of the solid catalyst ingredient. /' /' /' Effect 1 of [invention According to the method of the present invention, moderate amount of polymers deltaPP of molecular weight 5~200,000 can be manufactured by quantity yield, and it can be widely used as a transparent elastic film and a polymer property modification agent, and is useful.

[Brief Description of the Drawings]

A drawing is 70-chart figure of the manufacturing method of the present invention.