Component of the catalyst for polymerization of olefins
(57) Abstract:The components of the catalyst for polymerization of olefins, obtained by the reaction of halide compounds of tetravalent titanium or halogen alcoholate and an electron-donor compound with a solid substance containing a porous metal oxide that includes a hydroxyl group on a surface on which is supported diploid magnesium or a magnesium compound that does not contain Mg-C bonds and can turn into diploid, characterized in that the amount of magnesium that is supported on the oxide to reaction with a compound of titanium and titanium present in the catalyst after the reaction with the compound of titanium is 5-12 wt.% in relation to the weight component of the catalyst. 1 C.p. f-crystals, 6 PL. The invention concerns a component of catalysts for the (co) polymerization CH2= CHR olefins, where R is hydrogen or the radical of a linear or branched alkyl with 1 to 6 carbon atoms or arrowy radical, and catalysts derived from them.Known to produce catalyst components containing halide compound of titanium and magnesium halides, by maintaining the halides of titanium and magnesium oxides of metals, for example, dioxide SS="ptx2">In particular in the United Kingdom patent N 2028347 disclosed the preparation of catalyst components supported on inert substrates, for example, of silicon dioxide and aluminum oxide by impregnation of substrates with solutions of MgCl2, solvent evaporation and the resulting solid reaction product compound of the transition metal, especially titanium. The maximum content of MgCl2deposited on the substrate before reaction with the compound of the transition metal is 75 wt. corresponding to 19 wt. magnesium. In this case, the activity of the catalysts obtained from these catalyst components, depending on the magnesium content is such that it increases when the content of magnesium is increasing and begins to decrease when the magnesium content below 2 wt. Maximum activity is achieved when the content of magnesium is 2-3 wt. and in accordance with the examples get about 5000 g of polypropylene/g of catalyst component per hour and in an atmosphere of ethylene. Due to the lack of electron-donor compounds in the supported component catalysts are not suitable for obtaining highly stereoregular alpha-olefin polymers.Supported on the substrate components of the catalyst, Poluchenie, selected in particular from manilkara and Grignard compounds, and then by reaction of the substrate with a halide compound of titanium, is known from the patent UK N 1306044. Compounds of magnesium in the resulting supported component is about 4 wt. as shown in the examples. The catalysts used in the polymerization of ethylene, where, however, does not reach a high enough output (500-1400 g polymer/g catalyst component per hour and where they work under the pressure of ethylene of 10 ATM.).In U.S. patent N 4263168 describes the components of the catalyst for polymerization of propylene and other alpha-olefins, obtained by reaction of metal oxide, for example, of silicon dioxide and aluminum oxide containing hydroxyl groups on the surface, with organometallics a magnesium compound of the formula Mg R2-xXx(where R is a hydrocarbon radical, X is halogen; x is a number from 0.5 to 1.5) and subsequent reactions with electron-donating compound and titanium tetrachloride.Organometallics the magnesium compound is reacted with a molar excess content in relation to the hydroxyl groups, while electrothermo connection applies up to 1 gram-molecules/gram-molecule entered into niem excess TiCl4.Alternatively, the reaction of the metal oxide before or after the reaction with organometallics compound of magnesium, can be performed with halogenation agent who will submit at least one halogen atom on the hydroxyl group.Halogenide agent can also be added during the reaction with electron-donating compound. The content of magnesium in supported the compounds described in the examples, does not exceed 7%, However, the activity of the catalysts obtained from these catalyst components, very low, i.e. of the order of several tens of grams of polymer per gram catalyst component at atmospheric pressure.Catalysts based on halide compounds of magnesium, supported on porous substrates, which have high activity and stereoregularity, in addition to reducing the amount of undesirable halogenated compounds, which remain in the polymer, allow you to control the morphology of the polymer relatively simple way. Indeed in modern industrial processes for the production of polyolefins, there is a need for catalysts capable of forming a polymer with controlled morphological characteristics of opaski application N344755 describes the components of the catalyst, obtained by keeping minicipality or compounds of magnesium, which can turn into diploid, on a porous polymeric substrate, and then by reaction of the solid product with a halide compound of titanium halide or an alcoholate is possible in the presence of electron-donating compounds. The content of magnesium in the catalyst components described in the Examples is at most 5,16 wt.The activity of the resulting catalyst does not exceed 4000 g polymer/g catalyst component in the polymerization of propylene, when the content of titanium in the catalyst component is 2-3 wt.The polymerization is carried under a propylene pressure of about 7 ATM.The examples also show that in the catalyst component ratio Ti/Mdweight varies from about 0.4 to 0.8.Additionally, in European application N0434082 describes the components of a catalyst containing a porous metal oxide (e.g. silicon dioxide or magnesium oxide), which are supported minidialog, halide compound of titanium halide or an alcoholate and an electron-donating compound selected from specific classes of ethers.The examples show the maximum is eat propylene approximately 7 bar, and the output of 14000 g of polypropylene/g of catalyst component employed in liquid propylene.In this case, the high activity is the result of the presence of the aforementioned ethers.In the catalyst components specified in the Examples, the magnesium content is at most 5.5 wt. the titanium content varies from about 0.3 to 0.7.In U.S. patent N5064799 describes the components of the catalyst obtained by the reaction of a halide compound of tetravalent titanium and Elektrodinamika connection with the solid product obtained through the reaction of metal oxides containing hydroxyl groups on the surface (for example, silicon dioxide or aluminum oxide), with organometallics a magnesium compound of the formula MdR2-xXxwhere R is a hydrocarbon radical, X is halogen or a radical or or COX (where X is Galaga) and x is a number from 0.5 to 1.5, applied in such quantity to cause a decrease in titanium content during subsequent reaction of the solid product with a halide compound of titanium.In the catalyst components mentioned in the Examples, the maximum content of magnesium is 10,65 wt. the titanium content of 2.5 wt. up to 5 wt. moreover, the ratio of Ti/Mdchanges from the catalyst in liquid propylene.Now unexpectedly discovered that it is possible to obtain catalysts supported on metal oxides, which are particularly active in the polymerization of CH2=CHR olefins, where R is hydrogen or an alkyl radical with 1-6 carbon atoms or arrowy radical, in particular phenyl, having a high stereoregularity and capable of forming a polymer having a controlled morphology. These catalysts are prepared from catalyst components obtained by reaction of the halide compounds of tetravalent titanium or halogen alcoholate and an electron-donor compound with the solid product containing porous metal oxide that includes a hydroxyl group on a surface on which is supported mineraloid or magnesium compound not containing Md-C bond, which can turn into diploid, and these components of the catalysts are characterized in that the content of magnesium supported on metal oxides, to reaction with a compound of titanium and titanium present in the final component of the catalyst after the reaction with the compound of titanium is 5% -12 wt. preferably 6%-12 wt. better to 7.5%-12 wt. Performance of catalysts prepared from these components are unexpected is key in values of activity and morphological properties of the polymer can be obtained when the magnesium content of from 5 to 12 wt.Particularly amazing is this result, because the components of the catalyst in accordance with the present invention is able to provide output stereoregular polypropylene is significantly higher than the catalyst obtained from the components described in U.S. patent N5064799, although the titanium content and the ratio of Ti/Mdare fully comparable.In accordance with the present invention, the amount of magnesium supported on a porous magnesium oxide, to reaction with a compound of titanium, preferably chosen so that the content of compounds of magnesium deposited on the porous substrate, consistent with the volume on the porous substrate, respectively, by volume porosity of the substrate. When the content of compounds of magnesium is higher than the porosity of the substrate receive the catalysts that form polymers with poor morphological properties. In the catalyst components and the relation of Md/T is from 0.5:1 to 30:1, preferably from 3:1 to 20:1; the molar ratio of compounds of titanium to electrothermo from 0.3:1 to 8:1.The metal oxide preferably has a porosity (BET) is higher than 0.3 ml/g, typically from 0.5 to 3.5 ml/g, for example, between 1 and 3 ml/g, the surface Area of the safe group on the surface. Preferred are silicon dioxide, aluminum oxide, magnesium oxide, silicates of magnesium, titanium oxide, thorium oxide and mixed oxides, silicon dioxide aluminum oxide. The preferred oxides are silicon dioxide, aluminum oxide and mixed oxides of silicon dioxide and aluminum oxide. The number of hydroxyl groups present in the oxides, may be reduced to 3 mmol per gram of oxide or more.Preferably in the case of the use of silicon dioxide and other oxides other than aluminum oxide, in addition to hydroxyl groups is also present unbound water in an amount up to 0.015 mol per gram of oxide.The amount of chemically unbound water can be adjusted by exposure of the oxide to heating at a temperature of from 150oC to 250oC, the number of hydroxyl groups regulate by exposure of the oxide to heating at a temperature of 150oC-800oC. higher processing temperatures, the lower the content of hydroxyl groups present.Chemically unbound water is added in various ways; one of the preferred ways is in the direction of the stream of moist nitrogen over the oxide as such or pre-mo is t on the morphological properties of the polymer. It was found that the addition of alcohols, such as ethanol or butanol in an amount up to 1 mol/mol of compound of magnesium during the stage at which the magnesium compound is supported on metal oxides, has a beneficial effect on the morphology of the polymer. In particular, it allows to restore, in the case of catalysts prepared from oxides, calcined at high temperature, the morphology typical for catalysts prepared from oxides, which contain chemically unbound water or which were subjected to calcination at a temperature lower than 600 700oC.The content of hydroxyl groups is preferably 1-3 mmol/g oxide/, and water when it is present, preferably 1 to 10 mmol per gram of oxide. The content of hydroxyl groups present in the oxide of the metal, determined by titration in accordance with the method described in the journal J. Phys chem, volume 66, 800 (1962), and the number of water through the reactor Fisher.Preparation of catalyst components in accordance with the present invention can be made by suspension of metal oxide in solution dualitneho compounds of magnesium or compounds of magnesium, which can turn odnogo compounds or compounds of magnesium in the solid product as long until a solid product will not become fluid; and the procedure can be repeated many times. Usually operating temperature 0oC-150oC.The impregnated oxide can be performed in a fluidized layer, thus maintaining the impregnated solid product in a fluid state.The example of magnesium compounds that can be applied and which is different from duraleigh compounds include alkyl-Md-halides, Md-dialkyl, alkyl-Md-alcoholate, Md-dialcohol, Md-halogen-alcoholate, Md-dicarboxylate, Md-halogenocarboxylic and Md-alkalicarbonate.These compounds are usually soluble in aliphatic or aromatic hydrocarbons or ethers. Some of these compounds can be obtained on the spot.Mineralogy dissolved in solvents, for example alcohols, ethers, ketones and esters. In this case, mineraloid present in the oxide in the form of complex compounds with the solvent.Preferred compounds of magnesium are: MgCl2, RMgCl, RMgBr, MgRR, Mg(OR')2, ClMgORi, Mg(OCOR)2, RMgOR and mMg(OR)2-p TiOR)4where the radical C1-20of alkyl, C3-Ala from 1 to 4.When the substrate containing compounds of magnesium, which already halogenation and do not contain Md-C bonds, the component of the catalyst was prepared by reaction of the substrate with a halide compound of titanium or hydrogen alcoholate in an excessive amount, preferably TiCl4and electron-donor compound at a temperature of 0oC-135oC. the Solid product is separated in a hot state from unnecessary amount of compounds of titanium and washed with anhydrous hexane or heptane as long as the filtrate will not disappear all chlorine ions. Processing connection titanium can be repeated.When a substrate of metal oxide impregnated with compounds of magnesium, containing Md-C bonds, in order to obtain high catalytic activity, it is necessary to transform these compounds of magnesium, to reaction with a compound of titanium, dogalogue compounds of magnesium or compounds that are not able to restore the tetravalent titanium (i.e., they do not contain Md-Communication) and can become dogalogue compounds of magnesium by reaction with a halide compound of titanium or halogen alcoholate. To achieve this, the substrate of the oxide of the metal containing compound of magnesium with Md-C aluminiumgie, water, alcohols, carboxylic acids, areafile, esters, aldehydes, ketones and carbon dioxide.These compounds react in stoichiometric amount or in an excess amount relative to the Md-C relations usually at a temperature of from 0oC to 150oC.Electron-donor compound can also react before or after treatment with compound of titanium. When it reacts after treatment with compound of titanium, usually the reaction is performed in the environment of aromatic hydrocarbon, e.g. benzene or toluene, or in halogenosilanes hydrocarbon such as dichloroethane.However, best results are obtained by reaction of electron-donor compound before or at the same time as the connection of titanium. The preferred compounds are the halides, especially TiCl4. To obtain a catalyst component in accordance with this invention can be applied to any electrothermo compound, capable of forming complex compounds with mineralogie and/or halide compounds of tetravalent titanium or halogen alcoholate. Examples of compounds which can be used are complex and esters are esters of carboxylic acids of the aromatic series, for example, phthalic and malonic, trimethyloxonium, succinic acid and carbonic acid.Especially preferred are ethers described in published European application N 364494 (corresponding to U.S. patent N 4971937) having the formula:
< / BR>where
R, R11and R2the same or different and represent groups of linear or branched C1-18of alkyl, C3-C18cycloalkyl, C6-C18aryl, C7-C18alkaryl or aralkyl, and R1or R2can also be hydrogen. In particular, R is methyl, and R1and R2the same or different and are ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, isopentyl, phenyl, benzyl or cyclohexyl. Typical examples of ethers are 2,2-Diisobutyl - 1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane, 2,2-bis (cyclohexyl) -1,3-dimethoxypropane.Specific examples of esters are Diisobutyl, dibutil, dioctyl and definiltely, benzylbutylphthalate, Diisobutyl and diethylmalonate, ethyl ester trimethylhexanoic acid, ethylvinylbenzene and diphenylcarbonate.Components catalyzatoroprovod catalysate, suitable for polymerization CH2CHR olefins, where R is hydrogen or alkilany radical with 1-6 carbon atoms or aryl and mixtures thereof, possibly the contents of a small amount of diene.Typical examples of Al trialkyltin compounds are Al triethyl, Al triisobutyl, Al-tri-n-butyl, and linear or cyclic compounds containing two or more aluminum atoms, connected by a bridge over the O or N atoms or groups SO4and SO3.You can also apply halide compounds aluminidecalcium in a mixture with Al-trialkyls. Connection Al-alkyl apply in respect of Al/Ti is usually from 1 to 1000.When the electron-donating compound component of the catalyst according to the present invention has a simple ester selected from those described in published European application N 361494, stereoregularity rises sufficiently, thus no need to apply the electron-donor compound with an Al-alkyl compound. In all other cases, to improve stereoregularity catalyst is usually used together with Al-alkyl compound is also electron-donating compound in a quantity of 0.01 to 0.25 mol per mol of compound Al-alkyl.Electronified, esters, silicon compounds containing at least one bond of Si-OR (R is a hydrocarbon radical) and 2,2,6,6-tetramethylpiperidine.When the solid catalyst component contains ester bicarbonate acid of the aromatic series, for example, phthalic acid or ester of malonic, maleic, trimethyloxonium, amber or carbonic acid, the electron-donating compound used together with Al-alkylbis compound, preferably selected from silicon compounds containing at least one bond of Si-OR.Examples of silicon compounds are phenyltriethoxysilane, diphenylmethylsilane, dicyclopentadienyliron, methyl-tert-butyldimethylsilyl, methylcyclohexylamine, di-tert-butyl-dimethoxysilane, ISO-propyl-tert-butyl-dimethoxysilane.The polymerization of olefins is carried out in accordance with known methods in the liquid phase, in the liquid monomer or monomer solution in an inert hydrocarbon solvent or in the gas phase or even by combining the stages of polymerization in the gas and liquid phases.The temperature during polymerization is usually from 0o150oC, preferably 60oC 100oC. what Britanie used in homopolymerization and copolymerization of olefins. They are particularly suitable for obtaining statistical crystalline copolymers of propylene with minor amounts of ethylene and butene and possibly for higher-olefin elastomeric copolymers of ethylene with propylene, possibly containing a small amount of diene (e.g. butadiene and hexadiene - 1,4).The catalysts in accordance with the present invention can also be applied in alternating polymerization of propylene and mixtures thereof, with ethylene and/or butene mi high-quality a-olefins to obtain impact-resistant polypropylene.Before polymerization, the catalyst can be contacted with a small amount of olefin monomer (pre-polymerization), working either in suspension in a hydrocarbon solvent (such as hexane and heptane) when the polymerization is carried out at a temperature from room temperature up to 60oC, the result is a certain amount of polymer in excess of 0.5-10 times the mass of the solid component of catalyst, or working in the liquid monomer, so get to 1000 g of the polymer, the solid component.The following examples are given to illustrate and not limit the invention.Example 1.3equipped with stirrer and cooler, introduced 40 g of anhydrous MgCl2and 1000 cm3tetrahydrofuran (THF). Using a temperature-controlled bath, the temperature was raised to the point of irrigation of tetrahydrofuran, and support within 72 hours the resulting solution was cooled to room temperature and then filtered. Analysis on the absorption of magnesium atoms showed a concentration of 3.9 g MgCl2100 cm3solution.B) Impregnation of silicon dioxide.In a flask with a capacity of 250 cm3connected with a rotary evaporator (the rotavapor), enter 7 g of spheroidal silica Grace Davison 952, which was not subjected to heat or chemical pre-treatment. The content is not related chemical water is approximately 2.4 mmol/gTemperature-controlled bath is brought to a temperature of 60oC and then injected 20.5 cm3the described solution MgCl2.After stirring for 1 h the solvent is evaporated. This operation is repeated five times. The number entered thus MgCl2equals 6 mmol in,Then the substrate is dried under vacuum at a temperature of 60oC for 3 hours composition of the obtained solid substrate is listed in table. 13 injected into the reactor with a capacity of 350 cm3equipped with a temperature controlled jacket and the filtration membrane in the bottom. The temperature quickly increased to 75oC in terms of mixing, then enter 2-isopropyl-2-isopentyl-1.3 dimethoxypropane (DFID) in such amount to have a molar ratio of 1:3 with respect to Mgcontained in the substrate, up to 1:3. Then the temperature was raised to 100oC and maintain it for 2 hours then the reaction mixture is filtered while hot and then spend the reaction filtered solid product with TiCl4(titanoboa) by inputting the filtered solid product and 200 cm3fresh TiCl4in the reactor, the temperature is again increased to 100oC and maintained for 2 hours Finally, TiCl4filtered, the solid product is washed twice with hexane at a temperature of 60oC and three times at ambient temperature, then dried in a stream of nitrogen for 2 hours at a temperature of 70oC.The composition of the obtained solid component of catalyst specified in table. 1A.D) Polymerization of propylene.In the autoclave volume 4 DM3, equipped with a stirrer and a thermostat was introduced at a temperature of 30oC and in conditions of sweat is mponent catalyst (in an amount specified in the table. 1B) previously mixed for 5 minutes, the Autoclave is closed and injected with 1.6 DM3hydrogen, then include a mixer and injected with 1.2 kg of propylene, the temperature is quickly brought to 70oC, and the autoclave support under these conditions for two hours. Then the stirring is stopped, do not enter into the reaction of propylene is removed, and the autoclave is cooled to room temperature. The obtained polymer is dried at a temperature of 70oC for 3 h in a flow of nitrogen, weighed and analyzed.The output is expressed in kg of polymer on the g component of the catalyst.Stereoregularity measured in a polymer insoluble in xylene at a temperature of 25oC.The rate of melting and the volumetric weight is determined in accordance with the methods of ASTM D-1238 (condition L) and D-1985, respectively.The results of polymerization are shown in table. 1B.Examples 2-3.Use the method and ingredients of example 1, except that at the stage of impregnation is used, the number of MgCl21 g AlO2specified in the table. 1B.The composition component of the catalyst indicated in the table. 1A, and the results of polymerization in the table. 1B.Example 4.Apply the method and the relation M
Use the method and ingredients of example 8 except that the magnesium compound used for impregnation of SiO2is C6H13MgOC2H5obtained by reaction, in a molar ratio of 1: 1 solution of heptane Mg(C6H13)2with C2H5OH.The amount used of the compound and the composition of the catalyst are shown in table. 2A, and the results of propylene polymerization in the table. 2B.Example 10.In the device used for example 1, enter 7 g (grace Davison, type 952) and 18.7 cm3solution SM CH3MgCl in tetrahydrofuran (h, after that, the entire evaporator is dissolved and injected 70 mmol C2H5OH, dissolved in n-hexane. Allow the mixture to react at a temperature of 60oC for 1.5 h, then the solvent is evaporated and the substrate is dried under vacuum.The manufacture of the catalyst and the polymerization carried out as in example 1. The results are shown in table. 2A and 2B.Example 11.In the device, which is used for example 1, enter 7 g SiO2after this drop serves 4.1 cm370 mmol C2H5OH, diluted in 5 cm3n-hexane, the result is a solid product, which is still fluid.After 1 hour of contact gradually add 23,4 cm3(70 mmol) of a solution SM CH3MgCl in tetrahydrofuran, the content is left for 30 minutes at ambient temperature, then the temperature was raised to 60oC and maintain at this level for 1.5 hours Then the evaporator is evaporated, and the solid product is dried at a temperature of 60oC under vacuum for 3 hSynthesis of catalyst and the polymerization is carried out in accordance with the method of example 1. The results are shown in table. 2A and 2B.Example 12.Use fashion and g(C6H13)2in heptane (10 mmol/g SiO2for impregnation, and the number of C2H5OH, used in the second stage, double in comparison with that used in example 10 (140 instead of 70 mmol).The preparation of the catalyst and the polymerization carried out as in example 1. The results are shown in table. 2A and 2B.Example 13.In a glass reactor with a capacity 0,350 DM3equipped with a temperature controlled jacket, stirrer and cooler, enter 7 g SiO2(Grace Davison 952) suspended in 40 cm3hexane. Maintaining the slurry under conditions of mixing, add one drop of 40 cm3(56 mmol) of hexane solution butylethylamine (BEM product company of Texas Alkyls).Suspension support under irrigation for 1 h and then evaporated the solvent and drying is carried out until then, until you get a flowable solid product. The latter is suspended in the same reactor 50 cm3hexane. Then within 2 h after suspension will verbatimout approximately 10 liters of dry gaseous HCl. After that, the solvent is evaporated and the solid product is dried. The solid substrate is treated with TiCl4and electron-donating compound in accordance with the method and ing polymerization are presented in table. 2B.Comparative example 1.Component of the catalyst was prepared as in example 1, but during phase impregnation the number of MgCl21 g of SiO2is indicated in the table. 2A.The composition component of the catalyst specified in table. 2A, and the results of polymerization in the table. 2B.Example 14 and comparative example 2.Synthesis catalyst component in example 14 and comparative example 2 is conducted the same as example 3 and comparative example 1, respectively, except that the electron-donating compound was diisobutylphthalate (DIBP) instead of 2-isopropyl-2-isopentyl-1,3 - dimethoxypropane.The composition of the substrate after treatment and a component of the catalyst indicated in the table. 3A.The polymerization is conducted as in example 1, but in the presence of diphenyldichlorosilane (DPMS) as stereoregulating agent (molar ratio DPMS/TEA=0,05). The results are presented in table. 3B.Example 15.In a stainless steel autoclave with a capacity of 2000 ml equipped with anchor stirrer, injected under vacuum at a temperature of 65oWith the suspension containing 1,000 ml of anhydrous n-heptane 5 mmol And (i-C4H9)3and 52 mg at a pressure up to 11 bar.Content will polimerizuet at a temperature of 70oC for 2 h, while continuing to serve the monomer to maintain a constant pressure. After filtration and drying 270 g of polymer are isolated, receiving the output 5/90 g PP/g catalyst component. The polymer has a characteristic viscosity of 1.9 DL/g and the ratio of the degrees of F/E is 30. 1. Component of the catalyst for polymerization of olefins, which is a product of the interaction of titanium tetrachloride and electrondonor General formula
< / BR>where R, R1and R2the same or different, linear or branched C1C18-cycloalkyl, C6- C18-aryl, C7C18-alkaryl and aralkyl;
R1, R2also hydrogen,
on a solid substrate of a porous oxide of silicon or aluminum oxide containing surface hydroxyl groups with the besieged her magnesium chloride, characterized in that it is a product of the interaction obtained with the use of silicon oxide or aluminum oxide with a porosity of 0.64 of 1.53 ml/g, the fixed content of magnesium in the solid substrate from 6 to 8 wt. on 100 wt. the solid substrate and the fixed content of magnesium in the end puts a product of the interaction, obtained using a solid substrate and silicon dioxide, optionally including not chemically bound water in the amount of 1.0 to 2.4 mmol/g of oxide.
a) processing an inert inorganic substrate to remove surface hydroxyl groups;
b) interactions treated in a similar manner to the substrate with a soluble hydrocarbon compound magnesium;
C) interaction of the product of stage b) with a modifying compound selected from the halides of silicon, boron, aluminum, alkylsilane and hexadecylamine, or mixtures thereof;
g) the interaction of the product of stage b) with a compound of vanadium structural formula V(O)S X'4-Swhere X1halogen and S is 0 or 1; the first compound of titanium with the structural formula Ti(OR2)nX2mwhere R2hydrocarbon radical, X2halogen, n is the target number from 1 to 4, and m is 1 or 0, or an integer from 1 to 3 provided that the sum of n and m is 4; a second compound of titanium with the structural formula TIX3p(OR3)qwhere R3hydrocarbon radical, X3halogen, R is an integer from 1 to 4 and q is 0 or an integer from 1 to 3 provided that the sum of p and q is 4, and these first and second titanium compounds are not identical
FIELD: polymer materials.
SUBSTANCE: invention relates to polyethylene molding mass with multimodule molecular weight distribution intended to manufacture hollow articles such as gas tanks, canisters, barrels, and bottles using extrusion. Molding mass has density at least 0.940 g/cm3, contains low-molecular polyethylene with viscosity index 40-150 cm3/g in amount 30 to 60%, high-molecular copolymer of ethylene with another C4-C10-olefin with viscosity index 150-800 cm3/g in amount 30 to 65%, and ultrahigh-molecular polyethylene with viscosity index in the region 900-3000 cm3/g in amount 1 to 30%. Molding mass is prepared by cascade-based suspension polymerization.
EFFECT: increased degree of blowing and improved balance between hardness and fissuring resistance.
3 cl, 2 tbl, 5 ex