The solid catalyst, process for its production and method for producing polypropylene

 

(57) Abstract:

The use of the invention: catalytic polymerization of propylene. The inventive polymerization of propylene is carried out in the presence of alyuminiiorganicheskikh activator and the solid catalyst. The latter is a product of the interaction subjected to subsequent heat treatment in the presence of titanium tetrachloride at a constant temperature of up to 90-110°C aging at this temperature, the separation and washing of the solid residue when used as the aluminum compounds of the reaction product trialkylamine or dialkylaminoalkyl branched aliphatic alcohol or misperton or alkoxyamines when they molar ratio of 0.6 to 4.0 and the atomic ratio of aluminum: titanium 0.2 to 1.0. The catalyst can be obtained by use of a complex of titanium tetrachloride with simple aliphatic ether formed in the presence of an inert carrier. 3 S. and 3 C. p. F.-ly, 5 PL.

The invention relates to catalysts suitable for the stereospecific polymerization of propylene, the way to obtain this solid substance and method of polymerization of propylene in the presence of this solid.

< / what trichloride titanium. These particles differ in their special structure. Indeed, they formed an agglomerate of particles, which themselves are extremely porous. This means that these particles have a very high specific surface area and porosity [1]

This unique structure results in the polymerization of exceptional results. Because of the porosity of the microparticles, manifested mainly in pores with radius smaller 200 , the catalytic activity is so high that it is possible to conduct the polymerization under such conditions, when the remains of the catalyst no longer need to be removed. Moreover, since these particles have the shape of a large regular spheres, the resulting polymer is also in the form of spherical particles. It follows that it has a high apparent specific gravity, and that he has a very good fluidity.

High density and porosity, mainly due to the very small pores of these particles comprehensive trichloride titanium, lead to the formation of homopolymer, low porosity which, in turn, allows to introduce a large amount of elastomer, which causes the most problems gluing the more acute, the more kolichestvennyh in accordance with the new methods, namely, in the polymerization of the monomer, held in the liquid state or in the gas phase.

Closest to the invention is known solid catalyst for propylene polymerization, which is a product of the interaction of a complex of titanium tetrachloride and simple aliphatic ether at a molar ratio of from 0.4 to 1.6, respectively, with suedeniam aluminum, and a method of its receipt by the interaction of a complex of titanium tetrachloride and simple aliphatic ether at a molar ratio of from 0.4 to 1.6, respectively, with a compound of aluminum and a method of producing polypropylene polymerization of propylene in the presence of alyuminiiorganicheskikh activator and the solid catalyst [2]

The porosity of the resulting solid catalyst is not less than 0.08 cm3/g in pore radii from 200 to 15,000 .

The technical problem of the invention is to obtain a solid catalyst having an adjustable porosity, simple way.

This technical result is achieved in that the solid catalyst for polymerization of propylene-based trichloride titanium is a product of the interaction subjected to subsequent heat treatment in pasture, separation and washing of the solid residue when used as the aluminum compounds of the reaction product trialkylamine or dialkylaminoalkyl branched aliphatic alcohol or misperton, or alkoxyamines when a molar ratio of from 0.6 to 4.0 respectively and the atomic ratio of aluminum titanium from 0.2 to 1.0.

The product of the interaction can be obtained from the use of a complex of titanium tetrachloride with simple aliphatic ether formed in the presence of an inert carrier.

This technical result is also achieved by the fact that in the method of obtaining the specified solid component interaction the above components provide additional heat treatment of the product of the interaction in the presence of titanium tetrachloride at a constant temperature of up to 90-110aboutWith, followed by exposure at this temperature, the separation and washing of the solid residue, and the aluminum compounds used above reaction product.

This technical result, moreover, is achieved by the fact that in the method of producing polypropylene polymerization of propylene in the presence of alyuminiiorganicheskikh activator Symbols symbols used in the examples, the units expressing the above variables, and methods of measurement of these quantities are as follows:

AFP volume of internal pores of the solid catalyst defined in radii been concluded between 1000 and 15000 , and expressed in cm3/g;

Dwiththe average particle diameter of the solid catalyst in microns;

OOP total pore volume of the obtained solid polymer, expressed in cm3/g;

ARF total pore volume of the carrier (N), expressed in cm3/g;

The code of criminal procedure, the specific surface of the solid catalyst, expressed in m2/g (British standard BS4359/1);

OTU specific surface area of the medium (N), expressed in m2/g (British standard BS4359/1);

catalytic activity, conditionally expressed in grams of polymer insoluble in the polymerization medium obtained per hour and per gram of TiCl3contained in the solid catalyst; this activity is estimated indirectly, based on the definition of the residual titanium content in the polymer by the method of X-fluorescence;

COUVE apparent specific weight of the insoluble polymer fraction, expressed in g/DM3;

fTrithe coefficient of isotacticity polymer, as measured by the molar fraction isolationary; this value is determined by the method of nuclear magnetic resonance 13Since, as described in the journal "Macromolecules", vol. 6, No. 6, page 925 (1973) and references 3-9 of this publication;

CT coefficient of fluidity in the molten state, as measured under a load of 2.16 kg at 230aboutWith and expressed in g/10 min (ASTM D 1238);

G module torsional stiffness to the polymer, measured at a temperature of 100aboutFor the angle of torsion value 60about(arc), and the mold temperature is set at 70aboutAnd conditioning duration is 5 min (standards: BS 2782 Part 1 method 150A; ISO458/1; method: IN 53447 and ASTM D 1043); this module is expressed in Dan/cm2;

Et ethyl radical WITH2H5;

Itamin isoamylenes radical (CH3/2CH-CH2-CH2-).

The average particle diameter of the solid catalyst is evaluated by observation with an optical microscope of this solid, translated in suspension in decaline (zoom factor of 200).

The porosity of the catalyst and the porosity of the polymers obtained in the following experiments on the polymerization, measured by the method of mercury penetration using Porosimeter (vehicles for the first cast out 75000 .

The ethylene content in the block copolymer is determined on the basis of the characteristic for these parts of the signals observed by the method of nuclear magnetic resonance13Since, as described in the journal Rubber Chemistryand Technology, volume 44 (1971), S. 781 and later.

P R I m e R s 1-3. And preparation of solid catalysts.

1 Obtaining compositions (C).

In a reactor with a volume of 200 ml equipped with a single blade stirrer rotating at a speed of 400 rpm./min, administered in a nitrogen atmosphere to 80 ml of anhydrous mixture containing aliphatic hydrocarbon which boils at a temperature of 175aboutWith (included in trade under the name of Isopar N firm N CHEMICALS), and 17 ml (136 mmol) of the chloride diethylamine (NDEA).

Maintaining the temperature of the solution below the 50aboutWith that added to it drop by drop selected number of isoamyl alcohol as described in table.1. The solution is kept under stirring for 20 h at room temperature before applying it.

Composition (C) can be represented by a gross formula:

AlEtp /Isoamyl/q Cl, for which the values of the numbers p and q, corresponding to the molar ratio between the various components shown in the table.1.

2 synthesis of the solid to the 250 rpm, pre-purged with nitrogen, injected 100 ml of Isopar N and 15 ml of TiCl4.

Maintaining the temperature of this solution at 30aboutC, add to it for 30 min 69 ml (340 mmol) of vitaminology ether (DIAE). After this addition impose 97 ml of the composition (C) as described in table.1, i.e., 136 mmol aluminium pre-treated TiCl4within half an hour. Finally add 45 ml of TiCl4within about 10 minutes, all the while raising the temperature to reach the 100aboutWith after 1 o'clock In the course of this heat treatment of the first solid particles.

The reaction medium consisting of a suspension of particles, maintained at that temperature for two hours (maturation), then brought to room temperature.

The liquid phase is then separated from the solid catalyst by desantirovaniya, and the solid product (about 45 g) is washed in hexane as a result of consistent decantate, then dried for two hours in a stream of nitrogen at 70aboutC.

The characteristics of these solid catalysts purple color also are given below in table.1.

Solid particles are in the form of spheroidal agglomerates, more IU the ore in the presence of solid catalysts (standard conditions).

In pre-dried autoclave of 5 l enter when blowing dry nitrogen:

400 mg DHEA in the form of a solution in hexane with a concentration of 200 g/l supply trade company SCHERING, whose atomic ratio Cl/Al is set when the value of 1.02 by adding dichloride ethylaluminum;

50 mg of the solid catalyst (molar ratio of DHEA and TiCl3present in the solid is thus about 10);

hydrogen with a partial pressure of about 1 bar;

3 l of liquid propylene.

Maintain the reactor at a temperature of 65aboutWith stirring for 3 hours Then Tegaserod excess propylene and remove the formed polypropylene (PP), which is in the form of grains with a regular morphology.

The results obtained in experiments on the polymerization with various solid catalysts are also provided in the table.1.

Thus, it was found that when other equivalent parameters modifiable content groups in the composition (C) allows you to adjust in a wide range of internal porosity of solid catalysts. See, in particular, the increase in the internal pores of radii been concluded between 1 CLASS="ptx2">

P R I m e R 4. In the dry autoclave with a volume of 1 l, maintained at a temperature of 30aboutC in an atmosphere of nitrogen, is injected sequentially with stirring (single blade stirrer rotating at a speed of 250 rpm./min) 100 ml of Isopar and 15 mA (136 mmol) of TiCl4. Then add 69 ml (340 mmol) of vitaminology ether for 30 minutes After this addition is introduced drop by drop within half an hour the solution composed of 80 ml of Isopar N and 17 ml DHEA. Finally, while gradually (over 1 h) increase the temperature of the solution to 100aboutWith added within 10 min 45 ml (408 mmol) of TiCl4. The reaction medium is maintained at this temperature for two hours, then brought to room temperature, washed in hexane and dried in a dry and hot nitrogen. This solid contains per kg: 635 g TiCl3, 12 g of aluminum and 10 g DEAE; its ORP is to 0.29 cm3/g; and the code of criminal procedure is 140 m2/,

Conducting experience by polymerization in the presence of the solid catalyst under conditions strictly identical to those described in example 1, part C. Upon completion of this experience extract 115 g of polymer ( 1280), in the form of grains with irregular morphology, which IMC is only 205 g/DM3.

Composition (C) obtained by mixing 80 ml of Isopar N, 8.5 ml (68 mmol) of DHEA and 22,75 ml (136 mmol) dibutylamino ether (the RHEED).

The solid catalyst contains 799 g/kg TiCl3, 1.3 g of aluminum and 86 g DEAE; AFP 0,26 cm3/,

The experience of polymerization (conditions: example 1, part b) allows to obtain the polymer only with activity 1190, whose coefficient isotacticity, measured by NMR, is only 86%

P R im e R s 6 and 7. Get a solid catalyst as in example 1, except with regard to added TiCl4.

Example 6 heat treatment of the liquid material resulting from contact between the pre-processed TiCl4and the solution (C) is carried out after the addition of all TiCl4.

In example 7 the whole TiCl4, i.e., 60 ml, is injected at one time at the beginning of the synthesis of the solid catalyst.

The characteristics of these solids, and the results of polymerization are collected in table.2.

P R I m e R 8. A solid catalyst was prepared in accordance with the methods described in examples 1-3, part a, paragraph 2, using the composition (C) obtained as OPI ml of Isopar N and 18.5 ml of triethylaluminum (tea). All the while maintaining this solution at a temperature of less than 50aboutTo add one drop of 22.5 ml of isoamyl alcohol. Brutto-formula composition is:

Et Al1,5Isoamyl1,5.

The solid catalyst contains 764 g/kg TiCl31 g of aluminum and 71 g DEAE; its ORP is 0.09 cm3/g, and its specific surface area is equal to 51 cm2/,

Carrying out the polymerization of propylene in a condensed medium leads to the formation of polypropylene with activity 2835, which has COUVE value 362, CT magnitude of 7.6, G value 535 and the coefficient of isotoxicity, measured by NMR, the value of 88% Is OOP for solid polymer is 0.09.

P R I m e R 9. This example illustrates a variant of the synthesis of the composition (C).

In pre-dried reactor is injected sequentially in a nitrogen atmosphere to 80 ml of Isopar N, 102 mmol DHEA (12,7 ml) and 34 mmol chloretocsitiodiasole to obtain compositions with the gross formula:

Et Al1,75OEtof 0.25Cl.

This solution is added pretreated TiCl4as described in examples 1-3, part a, paragraph 2, to obtain a solid catalyst purple color, containing 792 grams of TiCl3, 0.8 g aluminum/SUP>/,

The value of Dwithfor grains of catalyst were made between 15 and 20 microns.

The experience of polymerization (under standard conditions) allows to obtain 350 g of polymer (activity 3230) with the following features:

COUVE 340 g/DM3;

fth94.8% of

G 700 Dan/cm2;

CT 3 g/10 min;

OOP 0,12 cm3/,

P R I m e R 10. Composition (C) With gross formula:

Et Al1,65/OEt/0,35Cl. it turns out when exposed in accordance with the procedure described for example 1, 17 ml DHEA in 3 ml of ethanol.

Preparation of solid catalyst, identical to that described in example 1, leads to a solid purple substance that contains per kg: 879 g TiCl3, 0.9 g of aluminum and 127 g DEAE.

The ORP value is 0,067 cm3/,

This solid catalyst used in the experiment propylene polymerization under standard conditions, results in activity 4060 polymer, which IMC is 358, and the PLO is 0.1 cm3/g, the other characteristics of polypropylene are as follows: fTri92% CT of 3.8 G 546.

P R I m e R 11. And Obtaining a solid catalyst.

1 a composition (C).

In reactora sequentially 800 ml of Isopar N and 170 ml DHEA. Then enter 82 ml of isoamyl alcohol drop by drop (for 1 hour), all the while maintaining the temperature of the solution is less than 50aboutC.

The solution is stored at room temperature with stirring and blowing with nitrogen for 16 hours before using it.

This composition can be characterized by the empirical formula:

Et Al1,45(Isoamyl)0,55Cl

2 Synthesis of the solid catalyst.

In the dry reactor with a volume of 5 l equipped with a single blade stirrer rotating at a speed of 220 rpm./min, injected with 1 l of Isopar N and 150 ml of TiCl4. Maintaining this solution TiCl4at a temperature of 30aboutWith slowly injected (30 min) 690 ml DEAE, and then 970 ml of the above composition (S). The introduction song (s) performed within 60 minutes After reducing the stirring speed to about 85./minutes of entering, all the while raising temperature to achieve the 100aboutWith after 50 min, 450 ml of TiCl4for 20 minutes the Suspension is aged at a temperature of 100aboutWith in two hours, the formed solid substance stands out as the result of desantirovaniya, then washed 7 times with 2 liters of anhydrous hexane.

This solid catalyst purple contains per kg: 830 grams of TiCl3, 1 is A.

All the solid catalyst obtained in accordance with paragraph 2 (i.e., approximately 317 g of solid matter on the basis of the complex TiCl3), translated in suspension in 1.8 l of hexane at a temperature of 30aboutWith under stirring at 150 rpm./minutes

Injected slowly (over 30 min) 780 ml hexane solution prior activator (referred to below pre-activator D) prepared in advance by mixing with a liter of hexane, 80 g DHEA and 176 g 3(3'-, 5'-di-tert-butyl-4'-hydroxyphenyl)-propionate N-octadecyl supply trade under the name of IRGANOX 1076 firm Shiba-Geigy. This solution is used after 15 min after cessation of gas evolution observed in the course of its receipt.

After this addition is administered for thirty min 240 ml of propylene, the suspension is maintained under stirring for 30 additional minutes.

After desantirovaniya prior sopolimerizacii solid catalyst is washed 7 times with 2 liters of anhydrous hexane re-transfer in the slurry solids after each washing, and then dried by blowing nitrogen in a fluidized bed for 2 hours at a temperature of 70aboutC.

Pre is also a certain amount, estimated value of 142 g, pretrial activator D.

The redox potential of the catalyst is 0.09 cm3/g, and its specific surface area is 8 m2/,

In the Polymerization of propylene in the gaseous monomer.

Pre-activated solid catalyst is used in the experiment polymerization of propylene comprising the first stage, carried out in liquid monomer, and a second stage carried out in the gaseous phase under the experimental conditions, we specify below.

In an autoclave of 5 liters, used in accordance with example 1, part b, is introduced into a flow of nitrogen:

342 mg of the activator is formed by the mixture containing DHEA, such as those used above, and triethylaluminium, and ethylbenzoic (EB); molar ratio of DHEA/DL, tea/DL respectively 60/1 2.2/1;

35 mg pre depolimerization solid catalyst (molar ratio between DHEA and TiCl3, which is in a solid substance, is, thus, approximately 15).

Then create in the autoclave absolute hydrogen pressure value of 2 bar, then injected under stirring to 1 liter of liquid propylene and increase the temperature to 50aboutC. Conduct the polymerization under these conditions in aboutC. Create thereby an absolute hydrogen pressure value of 0.8 bar, then enter propylene in the gaseous state until the pressure at the considered temperature value 21 bar (absolute). After 4 hours of polymerization under these conditions, stop the reaction by injecting 25 ml of a solution of caustic soda with a concentration of 1 mol/l, and after washing the polymer with 2 l of water extract 214 g of dry polymer.

Therefore, the activity of the solid catalyst is equal to 1820, and productivity increases to 7280 g of polypropylene per gram of the pre-activated solid catalyst. This PP has a CT equal to 1408; fTriequal to 97, and the PLO, equal to 0.15 cm3/,

P R I m e R 12. Pre sopolimerizacii the solid catalyst described in example 11, is used in the experiment two-stage polymerization in order to obtain a block copolymer in accordance with the procedure described below.

In an autoclave of 5 liters, used in accordance with example 1, part b, is introduced into a stream of nitrogen:

342 mg of the activator is formed by the mixture containing DHEA, how were equal, triethylaluminium and ethylbenzoic (EB); molar ratio of DHEA/DL, tea/DL rawnie between DHEA and TiCl3, which is in a solid substance, is, thus, approximately 15).

Then create in the autoclave absolute hydrogen pressure value of 2 bar, then injected under stirring to 1 liter of liquid propylene and increase the temperature to 50aboutC. Conduct the polymerization under these conditions for 10 minutes Then the autoclave Tegaserod to a pressure of 7 bar (absolute), all the while heating to a temperature of 75aboutC. Then create the absolute hydrogen pressure value of 0.6 bar, then enter the propylene in the gaseous state until the pressure at the considered temperature value 21 bar (absolute). After 2 h of polymerization degenerous the autoclave until a pressure of 4.5 bar (absolute), all the while maintaining the temperature at 75aboutC. Introducing him first gaseous propylene to create the total pressure in the autoclave value of 15.4 bar at this temperature, then gaseous ethylene until a pressure value of 21 bar (absolute). Carry out the copolymerization of propylene with ethylene for 140 min, all the while continuously feeding into the autoclave gaseous mixture of propylene and ethylene with a composition corresponding to the formed by the copolymer, so as to maintain pasaulyje.stai soda with a concentration of 1 mol/l and extract (with activity 1433) 360 g of polymer, having a good fluidity, the characteristics of which are the following parameters:

CT 0,61;

G 185;

OOP 0,04.

The proportion of elastomer in the entire polymer increases to 59 wt. the ethylene content in the whole polymer is 265 g/kg

P R I m e p 13. This example illustrates a variant of the synthesis of the composition (C).

The solid catalyst is prepared as in example 1, but replacing 7.5 ml of isoamyl alcohol 8.5 ml of 3-methyl-1-butanethiol.

Characterization of the solid catalyst, and the characteristics of the polypropylene obtained in the standard experience, described in table.3.

P R I m e R s 14-17. These examples illustrate the preparation of solid catalysts in the presence of organic or inorganic carrier (N).

And preparation of solid catalysts.

I Receive songs (With).

In a flask with a volume of 100 ml, pre squared away by blowing nitrogen, injected 30 ml of Isopar H and 5.7 ml DHEA. Maintaining this solution at a temperature of 40aboutWith stirring, introducing him at the drop of 1.2 ml of isoamyl alcohol in about 30 minutes the resulting solution is kept under stirring for 12 h before it is used these syntheses, their characteristics and heat treatments, which they previously are given below in table.4.

In the autoclave of 1 l, equipped with a single blade stirrer rotating at a speed of 250 rpm./min, which was previously purged with nitrogen, is injected sequentially 160 ml of Isopar N, 23 ml of vitaminology ether and chosen number (as indicated in the table.4) media (N). Then add 20 ml of TiCl4to this suspension for 30 minutes

Maintaining the suspension at a temperature of 30aboutC, add to it within 1 h 35,7 ml of the above composition (S). Then increase the temperature to achieve the 100aboutWith after 1 h

The reaction medium is maintained at this temperature for 2 h, then brought to room temperature.

The liquid phase is then separated from the solid catalyst of desantirovaniya, and the solid product is washed in hexane by successive decantate, then dried for 1 h in a flow of nitrogen at 70aboutC.

The thus obtained solid catalyst has an identical appearance to the same object (it has a purple color). Below table.4 also shows the characteristics obtained twah (example 1, part b).

P R I m e R s 18-21 illustrate the preparation of solid catalysts according to the invention at different temperatures of heat treatment.

Solid catalysts receive under the conditions described for examples 1-3, the stage And, on the basis of the quantities specified for example 2 except that the temperature reached at the end of the treatment.

These solid catalysts are experiencing in standard conditions (examples 1-3, stage b).

The results of these tests, as well as achieved at the end of the heat treatment temperature shown in table.5.

1. A solid catalyst for propylene polymerization on the basis of trichloride titanium, which is a product of the interaction of a complex of titanium tetrachloride and simple aliphatic ether at a molar ratio of 0.4 to 1.6, respectively, with a compound of aluminum, characterized in that it is a product of the interaction subjected to subsequent heat treatment in the presence of titanium tetrachloride at a constant temperature of up to 90-110oWith, the exposure at this temperature, the separation and washing of the solid residue when used as the aluminum compounds of the reaction product trialkylamine or dialkyl is,6 to 4.0 respectively and the atomic ratio of aluminum:titanium 0,2 1,0

2. The catalyst p. 1, characterized in that it is a product of the interaction obtained with the use of a complex of titanium tetrachloride with simple aliphatic ether formed in the presence of an inert carrier.

3. A method of obtaining a solid catalyst for propylene polymerization on the basis of trichloride titanium interaction of a complex of titanium tetrachloride and simple aliphatic ether at a molar ratio of 0.4 to 1.6, respectively, with a compound of aluminum, characterized in that provide additional heat treatment of the product of the interaction in the presence of titanium tetrachloride at a constant temperature of up to 90-110oWith, followed by exposure at this temperature, the separation and washing of the solid residue, and the aluminum compounds used, the reaction product trialkylamine or dialkylaminoalkyl branched aliphatic or misperton when their molar ratio 0,6 4,0 process is carried out at an atomic ratio of aluminum: titanium 0,2 1,0.

4. The method according to p. 3, characterized in that the complex of titanium tetrachloride and simple aliphatic ether get in the presence of an inert carrier.

5. The method of obtaining poly is, representing a product of the interaction of a complex of titanium tetrachloride and simple aliphatic ether at a molar ratio of 0.4 to 1.6, respectively, with a compound of aluminum, characterized in that the use of a solid catalyst comprising a product of the interaction subjected to heat treatment in the presence of titanium tetrachloride with a gradual increase in temperature up to 90-110oWith, the exposure at this temperature, the separation and washing of the solid residue when used as a compound of aluminium product interaction trialkylamine or dialkylaminoalkyl branched aliphatic, or misperton, or alkoxyamines when the molar ratio of aluminum:titanium 0,2 1,0.

6. The method according to p. 5, characterized in that the use of catalyst comprising a product of the interaction obtained with the use of a complex of titanium tetrachloride with simple aliphatic ether formed in the presence of an inert carrier.

 

Same patents:

The invention relates to a catalyst containing product ways, including:

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

The invention relates to components of catalysts for the polymerization of olefins, the catalysts obtained them, and their use in polymerization of olefins such as ethylene, propylene and mixtures thereof
The invention relates to the production of polyethylene of low and medium density, containing in the chain a small number of parts of butene-1

The invention relates to methods for CIS-butadiene rubber SKD and can be used in the synthetic rubber industry, and the product is used in tire, rubber, cable and other industries

FIELD: organic chemistry, chemistry of polymers.

SUBSTANCE: invention relates to two new compounds of the formula (1) and formula (11) that are used for destruction of polypropylene. Also, invention relates to a composition used for destruction of polypropylene in preparing polyacrylates comprising compounds of formulae (1) and (11). Invention provides preparing effective initiating agents for preparing low-molecular acrylate resins.

EFFECT: improved preparing method, valuable properties of compounds.

3 cl, 2 tbl, 8 dwg, 9 ex

FIELD: polymerization processes and catalysts.

SUBSTANCE: inventors claim organometallic catalytic system for production of elastomer stereoblock polypropylene via polymerization of propylene, which system contains octahedral hexafluorine-substituted bis-acetylacetonate complex of formula (CF3COCHCOCF3)2MCl2, where M represents Ti or Zr, and, as organoaluminum compound, AlR3, where R represents ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl, and; additionally, organomagnesium compound MgR2 or MgRX, where R is alkyl radical with 1-4 carbon atoms and X = Cl, Br, or I, M/Mg/Al molar ratio being 1.0:2.0:(100-500). Claimed is also a method for production of elastomer stereoblock polypropylene via polymerization of propylene in presence of homogenous catalyst system at transition metal complex concentration 10-3-10-5 mole/L.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 22 ex

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to the catalyst component used in polymerization of olefins comprising Mg, Ti, halogen and at least two electron-donor compounds wherein indicated catalyst component and at least one of electron-donor compounds repenting in the amount in the range from 20 to 50 mole% with respect to the complete amount of donors are chosen from succinic acid esters that are not extractable by above 25 mole% and at least one additional electron-donor compound that is extractable by above 35 mole%. Indicated components of catalyst provides preparing polymers possessing good insolubility level in xylene, high content level of stereoblocks and broad MWD value that is suitable for preparing polymers used in the region using bi-oriented polypropylene films. Also, invention relates to catalyst used in polymerization of olefins, methods for preparing propylene polymers and propylene polymer.

EFFECT: improved preparing method, valuable properties of catalyst.

24 cl, 3 tbl, 17 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to mixtures of propylene polymers with improved properties comprising propylene polymers and seed charge-forming agents of crystallization wherein propylene polymers are represented by propylene homopolymers with melt indices from 0.05 to 15 g/10 min at 230°C/2.16 kg or propylene block-copolymers comprising from 90.0 to 99.9 wt.-% of propylene links and from 0.1 to 10 wt.-% of α-olefin links with 2 or 4-18 carbon atoms, melt indices from 0.05 to 20 g/10 min at 230°C/2.16 kg or their mixtures wherein propylene homopolymers or propylene block-copolymers are represented by propylene polymers with seed charge-forming agents of crystallization in β-form. Propylene homopolymers with seed charge-forming agents of crystallization in β-form have value IRτ ≥0.98, elasticity modulus at stretching ≥1500 MPa at +23°C and impact viscosity by Sharpy ≥3 kJ/m2 at -20°C with incision and propylene block-copolymers with seed charge-forming agents of crystallization in β-form have value IRτ of propylene homopolymer block ≥0.98, elasticity modulus at stretching ≥1100 MPa at +23°C and impact viscosity by Sharpy ≥6 kJ/m2 at -20°C with incision. Also, invention discloses a method for preparing mixtures of propylene polymers with seed charge-forming agents of crystallization in β-form that involves propylene homopolymers or propylene copolymers in melt with 0.0001-2.0 wt.-% of seed charge-forming agents of crystallization in β-form at temperatures in the range from 175 to 250°C. Such mixtures of propylene polymers are characterized by the presence of high rigidity and good resistance against impact charges and can be used in making the molded articles for pipeline nets, such pipes, fittings, man holes and so on.

EFFECT: improved and valuable properties of polymers.

5 cl, 5 ex

FIELD: polymer chemistry.

SUBSTANCE: invention relates to mono- or multilayered pipes and parts thereof made of propylene-based polymers for pipelines comprising propylene homopolymer having flow melt index from 0.05-8 g/10 min at 230°C/2.16 kg or propylene block-copolymer containing 90.0-99.9 mass % of propylene units and 0.1-10.0 mass % of C2- or C4-C18 α-olefin units having flow melt index from 0.05-8 g/10 min at 230°C/2.16 kg or mixtures thereof, wherein propylene polymers or propylene block-copolymers represent propylene polymers with crystal-nucleating agents in β-form hawing IRτ >=0.97. Pipelines made of propylene homopolymers with crystal-nucleating agents in β-form have fast crack spreading with critical temperature from -25 to 0°C and critical pressure of >=3 bar below critical temperature; and pipelines made of propylene block-copolymers with crystal-nucleating agents in β-form have fast crack spreading with critical temperature from -5 to +40°C and critical pressure of >=3 bar below critical temperature. Also disclosed is method for pipe production from propylene homopolymers or propylene block-copolymers by extrusion or injection molding. Pipelined of present invention are useful in conveyance of fluid media and fluid media under pressure.

EFFECT: pipes of improved cracking resistance.

4 ex, 3 cl

FIELD: rigid pipes.

SUBSTANCE: multi-layered pipe comprises at least one layer made of propylene homopolymer having melting index ranging from 0.05 to 10 g/10 min at 230°C/2.16 kg or propylene block copolymers containing 90.0-99.9 % (in mass) of links of propylene and from 0.1 to 10.0 % (in mass) of links of α-olefins having 2 or 4-18 atoms of carbon with melting indices ranging from 0.05 to 15 g/10 min at 230°C/2.16 kg.

EFFECT: expanded functional capabilities.

12 cl

FIELD: chemical industry; the methods and installations for production of the oxidized atactic polypropylene.

SUBSTANCE: the invention is pertaining to production of the oxidized atactic polypropylene with the molecular mass of 5500-38000 and the polar functional groups, which may be used as the component of the various composite materials, the multipurpose additives for lubricants, anticorrosion coatings. For production the above-indicated oxidized atactic polypropylene they use the industrial atactic polypropylene with the molecular mass of 20000-40000 and the oxidization conduct at least in two stages with the adjustable temperature drop from 250 to 150°С within 1-6 hours at the air consumption of 0.6-1.9 l/(minute·kg). The installation for the method realization contains at least two in series connected reactors supplied with the electric heater at the ratio of the height of the reactor to its diameter laying within the limits of 2.0-5.0, the device for the air supply is made in the form of the vertical pipe with the air supply through its upper part and in the lower part it is supplied with the nozzle with the slits arranged along the perimeter of the lower edge. At that the diameter of the nozzle with respect to the diameter of the reactor is chosen within the limits of 0.25-0.5.

EFFECT: the invention ensures production of the oxidized atactic polypropylene with the molecular mass of 5500-38000 and the polar functional groups, which may be used as the component of the various composite materials, the multipurpose additives for lubricants and the anticorrosion coatings.

5 cl, 1 dwg, 4 ex

FIELD: polymerization processes.

SUBSTANCE: invention relates to a process of gas-phase polymerization of olefins conducted in a separate horizontally arranged reactor and describes gas-phase (co)polymerization of propylene in reactor with piston-driven two-phase stream wherein at least one monomer stays in contact with catalytic system including: magnesium halide-supported titanium component; organoaluminum component wherein components of catalytic system are added through inlet ports located axially along the reactor; and two external electronodonor components, in particular organosilicon compounds. Subject-matter of invention consists in that addition of the first external electronodonor component to reactor is accomplished through axially arranged inlet port located near the inlet port for component comprising supported Ti-containing component and addition to reactor of at least one second external electronodonor component showing higher stereo-controlling ability than first component is accomplished through axially arranged inlet port located downstream of the inlet port for the first external electronodonor component. A gas-phase process of propylene (co)polymerization in cylindrical horizontal reactor with piston-driven two-phase stream essentially in fluidized bed is described, wherein at least one monomer stays in contact with catalytic system including: titanium component supported by magnesium halide; organoaluminum component, and at least one external silicon-containing silicon-containing electronodonor component, in which process catalytic system components are added through inlet ports arranged axially along reactor, addition of the first external electronodonor component to reactor is accomplished through inlet port located axially near the inlet for supported transition metal-containing component and addition of at least second external silicon-containing electronodonor component, showing higher stereo-controlling ability than first component is accomplished through a port located at a distance constituting at least 25% the length of reactor and downstream of the inlet port for the first external electronodonor component.

EFFECT: enabled preparation of high-stereoregular propylene homopolymers and propylene-based copolymers.

10 cl, 2 tbl, 3 ex

FIELD: polymer production.

SUBSTANCE: invention describes process of producing propylene-based polymer via polymerization of monomer in hydrocarbon solvent at 20-80°C and excessive pressure 1 to 30 atm in presence of catalyst and hydrogen as polymer molecular mass regulator, said catalyst being a product obtained by preliminary treatment of titanium trichloride and diethylaluminum chloride with propylene carried out at weight ratio Et2AlCl/TiCl3 = 1 to 10 determined by density of layer of initial TiCl3 particles within the following limits: 1-2 at density below 0.46 g/cc, 3-5 at density 0.46-0.50 g/cc, 6-10 density above 0.50 g/cc. When polypropylene is obtained, preliminary treatment of titanium trichloride and diethylaluminum chloride with propylene is carried out to achieve conversion 2.0-3.0 g polymer per 1 g TiCl3 and, when propylene/ethylene copolymer is obtained, treatment is carried out to achieve conversion 3.0-4.0 g polymer per 1 g TiCl3. After termination of pretreatment of titanium trichloride and diethylaluminum chloride with propylene and before measuring out pretreatment product into principal polymerization reactor, weight ratio Et2AlCl/TiCl3 is adjusted to fall into range 6-10 through additionally dosing calculated quantity of diethylaluminum chloride.

EFFECT: prevented breaking of catalyst particles, preserved high activity and stereospecifity thereof, and increased productivity of process.

2 cl, 2 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention refers to crystalline propylene polymers with high stereoregularity, specifically high content of isotactic pentalogies, improved processability in molten state and to production method. Propylene polymer is produced with the following properties: isotactic pentalogies content, measured by nuclear magnetic resonance (NMR), is higher than 98%, chain-length distribution expressed by ratio is from 6 to 11, and value of ratio is equal or lower than 5.5. Specified polymer is produced with special combination of solid components of Zigler-Natt catalyst and highstereoregular electron-donor compounds. Film or plate is made of propylene polymers having said properties. Sandwiched laminated product comprises specified film or plate. Films and plate are characterized by good homogeneous thickness, as well as high ultimate elongation and high ultimate tensile strength.

EFFECT: propylene polymers are more easily recycled.

9 cl, 4 tbl, 8 ex

FIELD: metalloorganic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to class of metallocene compounds of the general formula (I) wherein Y means fragment of the formula (II) wherein A means sulfur or selenium atom; B means carbon atom; D means carbon atom; R1, R2, R3, R4 and R5 mean hydrogen atom or hydrocarbon groups; Z is taken among fragment of the formula (II) and fragment of the formula (III) wherein R6, R7, R8 and R9 mean hydrogen atom or hydrocarbon groups; L means bivalent bridge group; M means zirconium atom; X means halogen atom; p = 2. Above described metallocenes are useful especially for polymerization of propylene.

EFFECT: improved preparing method, valuable properties of metallocenes.

15 cl, 5 tbl, 18 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst is prepared by mixing hydrocarbon solutions of titanium tetrachloride, triisobutylaluminum-diphenyl oxide complex, and 1,3-pentadiene at Al/Ti molar ratio from 0.9:1 to 1.2:1 and at temperature form -70 to +20°C, after which mixture of paraffin, aromatic, and naphthene hydrocarbons is added, in particular industrial or transformer oil in amount 0.05 to 2% on the weight of catalyst suspension.

EFFECT: increased catalytic activity and reduced dosage of catalyst in polymerization process, which allows production of rubber with reduced titanium compound level without increasing intensity of washing away titanium compounds.

2 cl, 1 tbl, 11 ex

FIELD: polymer production.

SUBSTANCE: invention provides homogenous catalytic system for synthesis of copolymers and terpolymers of olefinic monomers, which system contains dialkyl bridge-type bis(indenyl)metallocene complexes with group IVB metals and trialkylaluminum at Al-to-metal ratio between 50 and 500. Catalytic system enables carrying out polymerization process at rates significantly exceeding ethylene or propylene homopolymerization rate.

EFFECT: significantly accelerated copolymerization process and achieved fractional and compositional homogeneity of ethylene/α-olefin and propylene/α-olefin copolymers.

1 tbl, 16 ex

FIELD: chemical industry; production of catalytic compounds for polymerization of monomers.

SUBSTANCE: the invention is dealt with the field of polymerization of the monomers and with the methods of production of catalytic compounds and compounds, which are applied at polymerization of at least one monomer. The offered methods contain: 1) a treated solid oxide compound produced due to a contact at least of one solid oxide with at least of one compound having an electron-seeking anion; 2)a metallocenes compound of a metal from IVA group; 3) an organoaluminum compound. The technical result: production of a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

EFFECT: the invention allows to produce a heterogeneous catalytic compound ensuring production of practically uniform particles of a polymer.

71 cl, 99 ex, 13 tbl

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