A solid component of catalyst for the (co)polymerization of ethylene, a catalyst, a method of obtaining a (co)polymers of ethylene

 

(57) Abstract:

A solid component of catalyst for polymerization and copolymerization of ethylene consists of kremniikarbidnoi carrier and a catalytically active part containing titanium, magnesium, chlorine and CNS group and is obtained by: (i) activation kremniikarbidnoi media by contact with a solution dialkylamide or alkylacrylate in a solvent is a liquid aliphatic hydrocarbon; (ii) impregnation of activated silica solution in a liquid aliphatic or aromatic ether complex of titanium tetrachloride and tetrachlorogallate titanium in equimolar or nearly equimolar quantities of magnesium chloride; and (iii) processing the solids obtained in stage (ii) is proportional to the number of alkalinebattery-chloride. 3 S. p. f-crystals, 2 tab., 1 Il.

The present invention relates to a solid component of catalyst, the method of its production and its use in the polymerization of ethylene and copolymerization of ethylene with a-olefins.

It is well known that ethylene or α-olefins in General, you can polimerizuet using the process of low pressure catalysts of the Ziegler-Natta. These catalysts in enoungh with the ORGANOMETALLIC compound or hydride of elements of groups I to III of the Periodic system.

In the art already known catalysts, in which the compound of the transition metal is fixed on a solid carrier organic or inorganic nature, possibly treated physically and/or chemically. Examples of solid carriers are oxygen-containing compounds of divalent metals (e.g., oxides, oxygen-containing inorganic salts and carboxylates) or chlorhydroxide or chlorides of bivalent metals.

In accordance with U.S. patent N 3,642,746 the carrier of the catalyst is a halide of the divalent metal-treated electrondonor. In accordance with the description of U.S. patent N 4,421,674 catalyst carrier is a solid non-dusting product obtained by spray drying of a solution of magnesium chloride in ethanol.

In particular, in accordance with U.S. patent N 4,421,674 microspherical particles of a solid substance, such as silicon oxide, can be suspended in the ethanol solution of magnesium chloride to obtain a spherical catalyst carrier comprising microspherical solids and activated magnesium chloride. Patent application Italy 21.711 And/90, filed October 11, 1990 on behalf of the applicant, the op is Yes magnesium and tetrachlorogallate titanium aliphatic ester solvent and processing impregnated thus oxide silicon alkylamidoamines.

In accordance with the present invention it was discovered that it is possible to improve the activity deposited on the silicon oxide catalysts by impregnation of activated silica with a solution of magnesium chloride and an equimolar or nearly equimolar mixture of titanium tetrachloride and tetrachlorogallate titanium in the liquid ether complex and processing-impregnated silica critical quantities of alkylaminocarbonyl. In particular, it was found that these components of catalysts have unexpectedly high activity in the polymerization and copolymerization of ethylene and capable of giving polymers and copolymers having excellent rheology, in the form of non-dusting granules.

In accordance with this present invention relates to a solid component of catalyst for polymerization and copolymerization of ethylene, consisting of media, representing the silicon oxide small particles (50 to 90 wt.) and a catalytically active portion (50 to 10 wt.), containing titanium, magnesium, chlorine, aluminum, and CNS group, with the specified component get through:

(i) activating kremniikarbidnoi media by contact with a solution dialkylamide or alkylacrylate in solution idcm of magnesium chloride and tetrachloride and tetrachlorogallate titanium in liquid aliphatic or aromatic ether complex, when working with equimolar or nearly equimolar amounts tetrachloride and tetrachlorogallate titanium and at a molar ratio between the magnesium chloride and titanium compounds, equal to from 1 to 10;

(iii) processing the treated silicon oxide by contact with alkylaminocarbonyl, when working with a molar ratio between the titanium compounds and alkylaminocarbonyl equal from 0.91 to 9:1; and

(iv) separating the solid component of catalyst from the reaction product of stage (iii).

The silicon oxide suitable as a catalyst carrier, preferably, is a microspherical silica (particle size of 20 to 100 μm) having a surface area BET of 150 to 400 m2/g, a total porosity of 80% and the average radius of the pores of 50 to 200 A.

According to the method of the present invention the silicon oxide on the stage (i) is activated by contact with a solution dialkylamide or alkalinized in the solvent liquid aliphatic hydrocarbon. Dialkyl magnesium suitable for this circuit are compounds that can be determined by the formula MgR'R", where R' and R", identical or different, each independently, represent alkyl Gia are: determine, ethylbutylamine, directimage, butylaniline, and dioctylamine. You can also use the corresponding halides, for example chlorides alkaline. Hydrocarbon solvents suitable for soaking, you can choose from pentane, isopentane, hexane, heptane or octane. It is convenient to work with a number dialkylamide or alkylpolyglucoside varying from 10 to 25 weight parts per 100 weight parts of silicon oxide.

Stage (i) is carried out, resulting silicon oxide in contact with a solution dialkylamide or alkylpolyglucoside in the selected hydrocarbon solvent, operating at a temperature varying from 40 to 100oC for a period of time equal to 0.5 to 2 hours, and preferably at a temperature of about 60oC for 1 hour. At the end of processing the activated silica is separated, e.g. by filtration or by decantation.

At stage (ii) activated silicon oxide is brought into contact with a solution in a liquid aliphatic or aromatic ether complex of magnesium chloride and tetrachloride and tetrachlorogallate titanium, the latter are in equimolar or nearly equimolar amounts. Tetrachlorogallate titanium Ti/OR/4 you can choose Tetra-n-St for the purpose of the present invention, the magnesium chloride is an anhydrous or essentially anhydrous magnesium chloride (water content below than 1 wt.). Esters suitable as solvents are selected from methyl or ethyl esters of lower aliphatic carboxylic acids, chlorinated or non-chlorinated, or benzoic acid, for example, the ethyl ester of formic acid, methyl acetate, ethyl acetate, propyl, isopropylacetate, ethylchloride, methylbenzoate and ethylbenzoic. The preferred solvent is ethyl acetate.

At stage (ii) of the method of the magnesium chloride and the tetrachloride and tetralogy titanium in the above ratio is dissolved in the selected complex ether, working at temperatures higher than the value at room temperature, in order to facilitate dissolution. Activated silica is impregnated with the thus obtained solution, operating at a temperature, measured from 50 to 100oC for a period of time equal to 0.5 to 2 hours, and preferably at a temperature of 70oC for 1 hour. At the end of processing impregnated silica exhale, viparita the solvent under reduced pressure.

In accordance with the present invention impregnated silica is treated with a solution of alkylaminocarbonyl in a hydrocarbon solvent, for ical hydrocarbons, mentioned in the description of stage (i). More specifically, the impregnated silica phase (ii) is brought into contact with a solution alkylamine of polutoraglazyi preferably of ethylaminoethanol, working at a temperature varying from 10 to 100oC over a period of time varying from 10 minutes to 24 hours, depending on temperature. In a preferred embodiment, the operating temperature varies from 20 to 90oC over a period of time varying from 15 minutes to 2 hours. Even more preferably to operate at 60 70oC for 1 hour.

In the present invention, the number of polutoraglazyi used in stage (iii) is critical from the point of view of the activity of the solid catalyst component in the polymerization.

Drawing 1 shows the (y-axis) typical changes in the output polyethylene, expressed in kilograms of polyethylene per gram of Ti, depending on the molar ratio (x-axis) ethylaminoethanol Ti on stage (iii) when the work on the comparative method, using as the titanium component only of titanium tetrachloride; only tetrachlorogallate titanium; and equimolar mixture of thepoliceman equimolar mixture of titanium compounds, when the molar ratio of politolog Ti on stage (iii) is changed from 0.9:1 to 2.0:1 and preferably from 1.1:1 to 1.7:1, with best values from 1.2:1 to 1.3:1.

At the end of the processing stage (iv) a solid component of catalyst is isolated and conveniently washed with solvent liquid aliphatic hydrocarbon to until the chlorides are not removed from the wash liquid and possibly dried.

A solid component of catalyst of the present invention is a granular solid material consisting of a carrier of silicon oxide fine particles (50-90 weight.) and a catalytically active part (50-10 wt.), containing titanium, magnesium, chlorine, aluminum, and CNS group. In the preferred method, this component of the catalyst contains 3-5 weight. titanium, 3-5 weight. magnesium, 15-20 weight. chlorine, 1-5 weight. aluminum, and 10-50 weight. titanium is in the form of trivalent titanium, and the remaining amount is in the form of tetravalent titanium.

The present invention relates also to a catalyst for polymerization and copolymerization of ethylene, consisting of the solid catalyst component described above, and a co-catalyst, preferably selected from trialkyl aluminum hydrides alkylaryl the tee. Among them, preferred are trialkyl aluminum with 2 to 4 carbon atoms in the alkyl part, for example, triethylamine, tributylamine and triisobutylaluminum.

The catalysts of the present invention have an atomic ratio between the aluminum co-catalyst and the titanium in the solid component of catalyst, which usually varies from 1 to 500 and preferably from 50 to 200.

The present invention relates also to method of polymerization and copolymerization of ethylene using the above catalyst. a-Olefins that can be copolymerizable with ethylene, preferred are propylene and 1-butene, and the polymerization process can be carried out in suspension in an inert diluent, or in gas phase fluidized bed or mixed layer of the catalyst. The usual polymerization conditions are a temperature of from 50 to 110oC, the total pressure of from 5 to 40 bar with a ratio between the partial pressures of hydrogen and ethylene, 0 to 10. In all cases receive high performance polyolefin, the latter has excellent rheology and is, in particular, in the form of non-fragile granules (size mainly 2000-125 µm) and fine fractions.

as the carrier of the solid component of catalyst is used microspherical silica in particles with an average diameter equal to 40 μm and having the following properties:

apparent density of 0.21

surface area (BET) 320 m2/g

pore volume of 1.6 ml/g

the average pore diameter of 25 A.

Example 1

(i) 20 ml of 17.5 mmole) of 20 weight. Mg(C4H9)1,5(C8H17)0,5in n-heptane and 17 g of silicon oxide in nitrogen atmosphere loaded into the flask with a capacity of 500 ml, equipped with a reflux condenser, mechanical stirrer and thermometer. The mixture is heated to 60oC for 1 hour under stirring, and then separated by filtration activated silica.

(ii) 220 ml of ethyl acetate, 4,96 g (a 14.6 mmole) of Tetra-n-butyl titanium, 1.6 ml (14.5 mmole) of titanium tetrachloride and 2,79 (29,4 mmole) of magnesium chloride in the atmosphere of nitrogen loads into another flask with a capacity of 500 ml, equipped with a reflux condenser, mechanical stirrer and thermometer. The mixture for 1 hour, heated to a temperature at which the liquid begins to drain back (about 75oC) up until the magnesium chloride is dissolved completely. Then to the solution was added the activated silicon oxide thus obtained, as described in (i). Contact leave at 70oC for 1 hour and then the solution is dried, viparita solvent.

(iii81 g (35,6 mmole) of ethylaminoethanol at a temperature of 25oC. the Temperature is brought up to 66oC, and the suspension is left to interact for 1 hour.

(iv) At the end of this time the solid is separated from the suspension, washed with anhydrous n-hexane as long as the chlorides will not disappear from the wash liquid, and then dried.

Obtain 28 g of the solid catalyst component in the form of microspherical solids containing 4.3 weight. titanium (19% of which is in the form of trivalent titanium), 3.8 weight. magnesium, an 18.4 weight. chlorine and 2.2 weight. aluminum.

Example 2

Repeat Example 1 with the difference that in stage (iii) use of 1.40 g of ethylaminoethanol.

Thus obtain 28.4 g of catalyst component in the form of microspherical solids containing 4,25 weight. titanium (12% of which is in the form of trivalent titanium), 3.9 weight. magnesium, 17 weight. and 1.8 weight. aluminum.

Example 3

Repeat Example 1 with the difference that in stage (iii) use of 13.2 g of ethylaminoethanol.

So get 28,0 g component of the catalyst in the form of microspherical solids containing 4.3 weight. titanium (38% of which is in the form of trivalent titanium), 3.4 weight. magnesium, 19.3 in the stage (ii) use 9,92 g (of 29.1 mmole) of Tetra-n-butyl titanium, and the titanium tetrachloride is added.

Thus obtain 28.5 g component of the catalyst in the form of microspherical solids containing 3.7 weight. titanium (43% of which is in the form of trivalent titanium), 3.8 weight. magnesium, 12,4 weight. chlorine and 1.7 weight. aluminum.

Example 5 (comparative)

Repeat Example 1 with the difference that in stage (ii) use 9,92 g (of 29.1 mmole) of Tetra-n-butyl titanium, and titanium tetrachloride is not added, and in step (iii) is used to 17.6 g (71.2 mmole) of ethylaminoethanol.

So get to 26.6 g component of the catalyst in microspherical form, containing 4,4 weight. titanium (51% of which is in the form of trivalent titanium), 3.7 weight. magnesium, 19,7 weight. chlorine and 3.2 weight. aluminum.

Example 6 (comparative)

Repeat Example 1 with the difference that in stage (ii) use of 5.50 g (29,0 mmol) of titanium tetrachloride and Tetra-n-butyl titanium is not added, and in step (iii) use 3.03 g (12.3 mmole) of ethylaminoethanol.

So get of 28.2 g of catalyst component in the form of microspherical solids containing 4.2 weight. titanium (24% of which is in the form of trivalent titanium), 3.5 weight. magnesium, 17 weight. chlorine and 2.1 is result 5.50 g (29,0 mmol) of titanium tetrachloride, and Tetra-n-butyl titanium is not added, and in step (iii) does not hold processing alkylaminocarbonyl.

Thus obtain 23.3 g component of the catalyst in the form of microspherical solids containing 4,4 weight. titanium (100% in tetravalent form), 3.8 weight. magnesium and 13.7 weight. chlorine.

Example 8 (comparative)

Repeat Example 1 with the difference that in stage (ii) use of 5.50 g (29,0 mmol) of titanium tetrachloride and Tetra-n-butyl titanium is not added, and in step (iii) use 6,03 g ethylaminoethanol.

Thus obtain 24 g of the catalyst component in the form of microspherical solids containing 4.1 weight. titanium (35% of which is in the form of trivalent titanium) 3.6 weight. magnesium, up 19.4 weight. chlorine and 2.4 weight. aluminum.

Example 9

Solid component of catalyst obtained in Examples 1-8 (trials 1-8), used in the test polymerization of ethylene. More specifically, the polymerization is carried out in an autoclave having a volume of 5 liters, containing 2 liters of n-hexane. Working pressure is 15 bar in the presence of hydrogen, with a ratio between the pressure of the hydrogen and ethylene, equal to 0.47/1 or 0,64/1, temperature 90oC and time 1.5 hours, and titanium in the solid component, equal to 50/1. Tests 9-11 carried out with the solid component of catalyst of Example 1, but using the time of polymerization equal to 3 o'clock.

The following table 1 shows for each test correlation (RP) between the hydrogen pressure and the pressure of ethylene; output (Exit) of polyethylene, expressed as kg of polyethylene in g of the solid component of catalyst; output against the Titan (R/Ti), expressed as kg of polyethylene per gram of titanium in the solid component of catalyst; density (D) of polymer (S D 1505), expressed in g/ml; the melt flow index (MF1) polymer (ASTM D 1238; of 2.16 kg and 21.6 kg), expressed in g/10 minutes; and the apparent density (AD) of the polymer (ASTM D 1895), expressed in g/ml.

Table 2 shows the size distribution of particles, expressed in microns, in weight. the polyethylene obtained in polymerization experiments listed in table 1.

1. A solid component of catalyst for the (co)polymerization of ethylene, which is a product of the interaction of powdered media, compounds of magnesium, alyuminiiorganicheskikh connection and two transition metal compounds, characterized in that it is obtained when using as powdered media microspherical silica, in acetylaminofluorene and as the two compounds transition metal tetrachloride and tetrachlorogallate titanium interaction dissolved in ethyl acetate of titanium tetrachloride, tetrachlorogallate titanium and magnesium chloride at a molar ratio of 1: 1: 2 respectively, introducing into the resulting solution activated carrier obtained by processing microspherical silica by dialkylamines dissolved in the liquid hydrocarbon, the selection of a solid residue, and the interaction of its suspension hydrocarbon solvent with sesquiterpenoids when molar ratio of sesquiterpenoid to the titanium compounds 1,2 1,8, followed by separation of the solid resulting product, containing 4.2 to 4.3 wt. titanium, including 12 38 wt. trivalent titanium and 62 88 wt. tetravalent titanium, 3,4 3,9 wt. magnesium, 17,0 19,3 wt. chlorine and 2.2 to 3.5 wt. aluminum is 100 wt. the whole product.

2. The catalyst for the (co)polymerization of ethylene, comprising a solid component, which is a product of the interaction of powdered media, compounds of magnesium, alyuminiiorganicheskikh connection and two transition metal compounds, and socialization selected from the group comprising trialkylaluminium, alkylhalogenide and alkylaminocarbonyl, characterized in that use solid component under item 1.

3. The method of obtaining the (co)polymers of ethylene polymerization of atrendy component, representing the product of the interaction of powdered media, compounds of magnesium, alyuminiiorganicheskikh connection and two transition metal compounds, and socialization selected from the group comprising trialkylaluminium, alkylhalogenide and alkylaminocarbonyl, characterized in that the use of the catalyst according to p. 2.

 

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