SU654175A3 - Method of obtaining catalyst of polymerization and copolymerization of c3-c8-alpha-olefins - Google Patents

Description

However, this method does not use a combination of two electron donors. In particular, the combined use of an organic compound containing an active hydrogen atom, such as an alcohol, and an ester based on an organic acid is not indicated. A known method for producing a katapizator consisting of a component based on a transition metal compound, obtained by the interaction of an active magnesium halide and a titanium compound in the presence of a donor selected from the group of esters of oxygen-containing organic acids and inorganic acid potassium, trialkylaminum, and the above ester 3 This method does not mention the combined use of two electron donors or the use of a carrier obtained by treatment with an organometallic compound alla groups 1-III of the periodic system. But even in this case, when the proposed catalyst is used for the polymerization of opefins containing at least three ugly atoms, for example, propylene, it is difficult to obtain high yields of paggaolefins with high stereoregularity. A known method for the preparation of the polymerization catapizator of the copolymerization of C — oC-olefins by the interaction of an organometallic compound of the metal of the 1P group of the Periodic System with a solid titanium component is a hydrocarbon-insoluble product of the reaction of the titanium compound with a fibrous carrier and organometallic compound. . the use of meta-1-I groups of the Periodic System 4 .. However, the catalyst obtained by this method has insufficient activity. The chain of the invention is an increase in catalyst activity. This is achieved by using the reaction product of magnesium hapogenide (1), C.-Cd aliphatic or C:. Aromatic alcohol (2), a primary alkyl ester and aromatic monocarboxylic acid (3), and an organoaluminum compound (4 ) followed by separation of the precipitate formed and washing it with an inert solvent. The molar ratio of compounds (1) :( 2): (3) :( 4) and titanium compound (5) is preferably l: (2O-0, l) :( , 005) :( 2O-O, 1) :( at least 0, Ol, preferably 1: (GO, 1): {3-0,1.): (6-0,2) :( 100- OD). A solid catalytic composition based on a titanium compound is obtained by sweeping a solid component based on magnesium compound obtained by separating solid precipitate from the suspension of the reaction product obtained by reacting the above components (1) to (4), for example, using an inert solvent to remove the free organometallic compound (4), the interaction of the magnesium compound in the absence of the free organomethagone compound (4) and the separation of the solid residue from the resulting product that reaction. Upon receipt of the reaction product from. the above four components (1) (4) the sequence of administration of these compounds or the method of their administration can be modified accordingly. For example, four components may be administered simultaneously, or two or more of these components will interact first, and then the remaining components will be entered. Or one component can be introduced in parts. Preferably, the magnesium hapogenide initially interacts with alcohol and ester either all or first with one of them, and then with the other, after which the product of their reaction interacts with the organoaluminium compound. In another embodiment, the magnesium halide reacts with the alcohol, and then the product of their reaction interacts with the organotinium compound, after which the reaction product interacts with the ester. For example, in accordance with these preferred embodiments, a solid catalytic component based on a titanium compound can be prepared by speduccium in the following way: 1). Magnesium papogen is pretreated with alcohol and ester, and then mixed with an organoaluminum compound. The solid reaction product recovered from the suspension of the reaction product is washed with an inert solvent and suspended in titanium compound or solution in an inert solvent in the absence of an organometallic compound of the Group III metal of the Periodic System, and the solid component is separated and reduced. h 2 | The first type of magnesium is pretreated with alcohol, and the pretreatment is a treated product, it is reactive with the compound. The resulting reaction product interacts with the feminine efrom. The solid reaction product isolated from the resulting suspension of the reaction product is flushed with an inert solvent and, in the absence of free metal, the organic compound metapp 111 of the Periodic System suspends TM in a titanium compound or its solution in an inert solvent and the solid component is separated and reduced . 3) Magnesium halide is pretreated with ester ether and then the pretreated product is reacted with alcohol. Then with an organo-aluminum compound. The solid reaction product expelled from the suspension is washed with an inert solution and, in the presence of c-bob-soro compound of the metal of the PG group of the Periodic System, is suspended in the compound of titanium or its solution in an inert solvent, and the solid component is reduced and restored. carrying out a pretreatment operation and obtaining a reaction product of the four components as pretreatment agents for magnesium halide with one of the compounds chosen from alcohols, esters, and aluminum organoaluminum compounds. In addition, various contacting methods can be used. Preferably, the magnesium halide is suspended in an inert solvent such as hexane and added from the alcohol. The mixture is stirred and then reacted with the ester ester and the organoaluminum compound in the form of its solution in an inert solvent, if necessary, in the sequence indicated above in 1) and 2. The reaction to produce the reaction product of the four components can be carried out at room temperature, but usually In a preferred embodiment, it is carried out at a twisted temperature. The upper limit of the treatment temperature range is preferably lower than the temperature of the decomposition or decomposition at atmospheric pressure of compounds containing an active hydrogen atom, esters of organic acids and organoparasic compounds used to obtain the above suspension. Of course, the upper limit may be 75b upward through the use of overpressure. A suspension of tetrak: the homogenous reaction product may contain unreacted compounds. Accordingly, the solid constituent is separated and washed with an inert solvent such as hexane, heptane or kerosene upon receipt of the solid magnesium catalyst component. The resulting solid compound based on the magnesium compound interacts with the titanium compound in the absence of a free organometallic compound of a metal of Group III of the Periodic System. This reaction (carrier reaction) can be carried out by contacting the solid magnesium compound with the titanium compound, preferably in the presence of an inert solvent, such as hexane, heptane, kerosene, ben-ZIN or toluop. The method allows to obtain polymers or copolymers based on olefins containing 3 to 8 carbon atoms, characterized by high stereoregularity and high reaction yields, as well as good reproducibility of quality and yield. Examples of suitable C-olefins containing from 3 to 8 carbon atoms are such as propylene, 1-butane, 4-methi-1-pentene, 3-methi-1-6j-TeH. The polymerization reaction can be carried out in the presence or absence of liquid solvents. It can be carried out in a liquid medium in the presence of a solid olefin monomer, as well as in the gas phase, for example, in a layer of a pseudo-reacted catalyst. The polymerization temperature may be that used to polymerize sc. α-olefins on a Ziegler catalyst, for example, 20 ° -20 ° C, preferably 50 ° -18 ° C. The polymerization pressure ranges from atmospheric pressure to 50 kg / cm, preferably from 2 to 30 kg / cm. The polymerization reaction of olefins can be carried out in the same way as the polymerization reaction of olefins with conventional catalysts. Zieger, i.e., the reaction is carried out in a significant absence of oxygen and moisture. When an inert solvent is used, such as hexane, heptane or kerosene, the catalyst and olefin, and if necessary, the diolefin comonomer is placed in the solvent, where the polymerization is carried out. A suitable concentration of the catalyst is such that the solid catalytic component based on the titanium compound (a) is taken in an amount, based on the number of titanium atoms, preferably from 0.0001 to 1.0 mi ppi MO l / liter gas phase, more than respectfully - from 0, OO1 to 0.5 miplimol / liter of the liquid phase. A suitable amount of the organometallic compound (b) is preferably from 0.1 to 50 mlpliol / liter of liquid phase, based on the number of metal atoms. When the reaction is carried out in the gas phase, the solid catalytic component fa) is used in an amount of preferably from 0.001 to 1 mmol / liter of the gas phase, based on the number of titanium atoms. Component Hb) is preferably used in an amount of from 0.1 to 50 cillimoles / liter of gas phase, based on the number of metal atoms. The ratio of components (a) and (b) is that the ratio of metal to titanium atoms is 1 / 1-1OOO / 1, preferably from 1/1 to 10O / 1. In the polymerization of opefins, the weight of the product can be controlled to some extent by changing the conditions of polymerization, such as the polymerization temperature or the polar ratio of the catalyst. But the most effective is the introduction of hydrogen into the polymerization system. When polymerization. In the presence of hydrogen introduced for the purpose of adjusting the molecular weight, there is a tendency to increase the amount of the resulting non-crystalline polymer. Example. A, Preparation of the composition of the catalyst (a). 0.1 mol of anhydrous chloride map is suspended in 0.3 liters of kerosene. At a combined temperature of .Natal, 0.4 mol of ethanol and 0.1 iol of ethylbenzonate are added, and the mixture is stirred for one hour. Then, at a room temperature, 0.3 mop diethylalumium chloride was added dropwise, the mixture was stirred for an hour. The solid precipitate of the obtained suspension of the reaction product is separated, thoroughly washed with kerosene, in the absence of a free organometallic compound of metal P1 of the Periodic System group suspended in 0.3 liters of kerosene containing 30 ml of titanium tetrachloride. The reaction is carried out at 80 ° C for 2 hours. After completion of the reaction, the upper liquid layer is decanted. The precipitate formed is thoroughly flushed with a fresh portion of kerosene, B. Polymerization, 0.75 Lkerosin, 0.375 mmol of aluminum triethyl and 0.0375 mmol per catalyst (a) f, the mixture is heated to 7 ° C in a 2 l autoclave. The polymerization of propylene proceeds at the moment it enters the sieve, so that the total pressure is 7 kg / cm. The solid component is filtered off, washed with hex., San, dried, get gprolipipena in the form of a white powder. The polymer content after extraction of polypropylene with boiling N. heptane is 96.2%, and its apparent density is 0.32 g / ml. The liquid phase is evaporated, 4.0 g of polymer soluble in solvent are obtained. Tab, 1 shows the yield and properties of the pyropyropene obtained by polymerization of propylene on the catalytic system prepared as described above. Table 1

0.4 0.1

the use of activated JVigCt, obtained by grinding on a shorovon and smaller than the separation of the solid component, after the formation of the titanium component of the catalyst does not produce the reaction of titanium tetrachloride in the presence of free chloride

diethylaluminum;

 after reaction with diethyl aluminum chloride, the solid component is not separated, but the obtained product is reacted with tetrachloride titanium, and after the completion of the reactions the solid component is not separated. Example .2. - Catalytic components (a) are prepared in the same manner as in Example 1, except that the ratio and type of alcohol, ester and meta-organic compound are changed, then the wire is polymerized with propylene using each component of the catalyst ) in the amount of 0.05 mppimop / l, based on the number of titanium atoms, and meta-organic compounds. Example 3. A. Preparation of the catalyst component (a). 0.1 mol of anhydrous magnesium chloride is suspended in 0.3 p of kerosene and, at room temperature, 0, 3-liter of ethanol is added. The mixture is moved for an hour. Then, 0.2 mop of diethylapuminium is added dropwise at room temperature and the mixture is stirred for an hour. Then 0.2 mol of ethyl benzoate was added, the temperature was raised to 7 ° C. After stirring for an hour, the precipitate is washed off, washed with a fresh portion of kerosene, and 30 ml of titanium tetrachloride are added.

Continued table. I on I In the absence of a free meta-organic compound of a metal of the 1P group of the Periodic System, the mixture is heated to 10 ° C and stirred for 2 hours. At the end of the reaction, the precipitate is separated by decantation, thoroughly washed with a fresh portion of kerosene. B. Polymerization. Propylene polymerisation proceeds under the same conditions as in Example 1, except that 0.0375 millimole of the catalytic component (a) is used in conjunction with 0.375 mipimony triisobutypapyumin instead of triethyl palyuminium. 419.5 g of a white, powdered polymer and 4.8 g of a solvent soluble polymer are obtained. The content of the polymer after extraction boiling n. heptane is 96.4%, and its apparent density is 0.32 g / MP, Table. Figure 2 shows the yield and properties of polypropylene obtained using catalytic systems, containing the catalyst component (a) of different composition.

oj "n ia e Yu

03 H

1LG5-1

Thus, the supposed cgc) allows us to stimulate the highly active cationizer for the polymerization and copolymerization of C-opefins.

Claims (4)

DETAILED DESCRIPTION OF THE INVENTION A method for producing a catalyst for polymerization and copolymerization of C „-o (- α-olefins by reacting an organometallic compound of a metal of Group 1 of the Periodic Table of Tablets with a solid titanium-containing component, which is an insoluble hydrocarbon of the titanium compound reacting with a carrier, characterized in that increase catalyst activity as a carrier used product L7514 reaction galpg: n1schp magnesium, C - Cg SH1CH | {| / s cally PPI S.-C - alcohol flpoNfaTH4ccKoro, primary alkipp ester and aromatic monocarboxylic acids and alyuminiyorganichoskogo soslino1P1Ya followed by separation of the resulting precipitate and washing it with an inert rastvoritepem. Sources of information taken into account in the examination D. Patent of Great Britain, №1271411, CP. SIR, 1974. 2. Published in the Federal Republic of Germany KSCh143346, 121 33/20, 1974. cl 3. The patent of Germany No. 2260672, class, 58a 1/32, 1974. 4.Patent of the USSR No. 463263, class, from 07 D 233/91, 197O.