The method of obtaining the (co)polymers of olefin (co)polymers of olefins

 

(57) Abstract:

The invention relates to a method of gas-phase polymerization of olefins of the formula CH2= R, where R is hydrogen, alkyl or aryl with 1 to 8 carbon atoms. The method is carried out in one or more reactors, in which a fluidized or mechanically mixed layer, using a catalyst obtained by the reaction of titanguard or haloalcohols and possibly electron-donating compounds deposited on the active dihalogenide magnesium, aluminiumalloy connection and possibly electron-donating compound. The method includes the stages of: a) contacting catalyst components in the presence of the olefin; (b) terpolymerization propylene or mixtures of propylene with small amounts of ethylene and-olefin obtaining propylene polymer with a degree of insolubility in xylene of at least 60 wt.% in the amount of 0.5 to 1000 g of the solid catalytic component, and (C) polymerization of one or more olefins CH2= CHP in the gas phase in the presence of system prepolymer-catalyst, obtained in stage b), while maintaining in the gas phase molar concentration of alkane relative to olefin within merisalo maintain high specific productivity and/or quality of the polymer. 2 C. and 8 C.p. f-crystals, 1 Il.

The invention relates to a method of gas-phase polymerization of olefins of the formula CH2= CHR, where R is a hydrogen atom or an alkyl or aryl radical with 1-8 carbon atoms, which is carried out in one or more reactors with a fluidized or mechanically mixed layer in the presence of a highly active catalyst comprising a titanium compound, located on the active dihalogenide magnesium.

Known continuous polymerization of one or more olefins, in particular ethylene or propylene in the gas phase in the reactor with a fluidized or mechanically mixed layer in the presence of a catalyst based on transition metal compounds belonging to the group IV, V or VI of the Periodic table of elements, in particular in the presence of a catalyst of the type Ziegler-Natta or a catalyst based on chromium oxide.

Polymer particles contained in the fluidized bed and/or stirred condition in a gaseous reaction mixture comprising the olefin (alpha-olefin). Into the reactor continuously or intermittently introducing the catalyst with simultaneous continuous or periodic removal from the reactor the polymer that education is from the gaseous reaction mixture during its passage through the heat exchange means before returning to the reactor. In addition, to improve the process of heat transfer in gas-phase reactor, you can enter the fluid stream.

In the case where the process gas-phase polymerization of alpha-olefin is carried out in the presence of catalysts of high activity, such as those formed from the reaction product aluminiumkilled compound with a titanium compound deposited on the active dihalogenide magnesium, due to the weak capacity of the gas phase to the heat transfer increases the problem of heat removal.

It was noted that small variations in the course of the polymerization process, resulting, for example, due to small fluctuations in the quality of the catalyst or olefins, which are used for the reaction, can cause changes in behavior and catalytic activity of polymer particles and to provide a particularly undesirable effect, because such small variations can cause an unexpected increase in the amount of heat released from the reaction, which cannot be quickly and efficiently removed the gaseous reaction mixture passing through the layer. As a result, the layer can be hot spots and agglomerates of molten polymer.

Odnako in the case if the reaction conditions are corrected early enough, which is achieved by reducing the polymerization temperature or pressure, or by reducing the feed rate of catalyst into the reactor, to avoid unwanted effects of unexpected over-activity, to a certain extent, it is possible to reduce the number and sizes of the formed agglomerates. However, in this period there is no possibility to prevent the drop of the speed of the polymer and reduce the quality of the resulting polymer.

To avoid these disadvantages, the basic conditions of polymerization is usually chosen close to secure the border so that if this were not formed hot spots and agglomerates. For example, for this purpose, use catalysts with reduced activity. However, compliance with such conditions entail any significant reduction in performance or quality degradation of the polymer.

To eliminate the above drawbacks in the description of the European patent application 359444 A 1 prompted to enter in a polymerization reactor, the moderator, in particular, a polymerization inhibitor or a catalytic poison, which is able to lower the rate of polymerization of refinetti on the melt index, the rate of melt flow and/or stereoregularity polymer, and may also cause a decrease in performance of the process.

Moreover, during the course of gas-phase process, the formation of electrostatic charges. Thus, there is a tendency of sticking to the walls of the reactor, catalyst and polymer particles, which is the result of electrostatic forces of attraction. If the polymer remains in the reaction medium over a long period of time, excessive temperatures can lead to melting of the particles and the formation of sheets or layers of thin fused agglomerates entering into the granulated product. The occurrence of electrostatic charges caused by many reasons, including their generation due to friction of heterogeneous materials, limited static scattering, falling in the process small quantities of agents that promote the formation of static charges excess of catalytic activity and the like. Between education sheet particles and the presence of excessive electrostatic charges (both negative and positive) there is a close relationship. This podtverjdau the atmospheric temperature of the wall of the reactor. Temperature changes indicate that the adhesion of particles, which causes a thermal effect and a decrease in the heat transfer layer. The outcome is usually a violation of the regime of fluidization, may be a break in the flow of catalyst, as well as the blockage removal system product.

As described in the U.S. patent 4532311, in the technique there are various ways to reduce or prevent the formation of electrostatic charges. To be acceptable for use in fluidized bed conditions include (1) the use of additives to increase the conductivity of the particles, thereby creating a path for electrical discharge, (2) placement in the fluidized bed grinding devices, (3) the ionization of the gas or particle electric discharge to generate ions for neutralizing electrostatic charges on the particles, and (4) the use of radiation sources with the aim of creating a radiation generating ions, which neutralizes electrostatic charges on the particles. However, the application of such techniques in polymerization processes in industrial reactors of the type in which a fluidized bed, not iavleaetesi additives, generating in the reactor may be either positive or negative charges and served in the reactor in amounts of a few parts per million parts monomer to prevent the formation of undesirable positive or negative charges. These chemical additives are alcohols, oxygen, nitric oxide and ketones. However, in this case also observed a decrease in the quality of the polymer and decrease the performance of the reactor.

These shortcomings are compounded when the process gas-phase polymerization is carried out with the use of a highly active catalyst, designed to produce spherical polymers having attractive morphological characteristics (high and bulk weight, flowability and mechanical strength). In this case, to obtain polymer particles having the above desired properties, it is possible only when almost full control of entire polymerization process. This is especially true when gas-phase process used in the manufacture of ethylene polymers, where the issue is exacerbated by the high kinetics of the polymerization of ethylene.

In the description to the application for a European patent is wow polymerization process carried out in at least two reactors using a catalyst based on titanium halide, printed on an active magnesium chloride. The description says with the possibility of pre-entry pre-prepared catalyst in contact with small quantities of olefin before carrying out the main stage of polymerization, which is carried out in the liquid or gaseous phase.

Currently set to uniform and reliable process gas-phase polymerization overcome or significantly reduce the above drawbacks of the conventional technologies without prejudice to specific performance and/or reduce the quality of the polymer.

Thus, in particular, it was found that ethylene and propylene polymers can be obtained in the form of engineering spherical particles of high bulk density using catalysts spherical shape with high activity (the term "spherical shape" applicants mean almost spheroid or spherical particles).

Thus, the implementation of the method of the present invention, particularly in regard to the use of super active catalysts with specific activity of 10 - 100 kg/h of polymer per 1 g of the solid catalytic component with dimensions casuistic methods gas-phase polymerization, gives the possibility to obtain polymers spherical shape. Such polymers spherical shape can be put on sale without granulation, i.e. without surgery, which is expensive from the point of view of energy consumption.

Moreover, the ability to carry out the process of gas-phase polymerization with high specific capacity helps to visibly reduce the volume of the reactor.

Another advantage of the proposed method due to the nature of the prepolymer used, as with the commissioning of the gas-phase reactor occurs without the need for any "polymer layer" or the source of the dispersion layer, which is common in the implementation of known methods of gas-phase polymerization.

Method for continuous polymerization of the present invention includes the following stages:

a) contacting the catalyst components in the absence of the polymerized olefin or possibly in the presence of the indicated olefin in an amount up to 3 g per gram of solid catalyst component with obtaining catalyst for stereospecific polymerization acceptable polymer is foremost which in xylene comprises at least 60 wt.%;

b) terpolymerization using the above catalyst, propylene or mixtures of ethylene and/or other alpha-olefins of the formula CH2= CHR, where R is alkyl with 1 to 8 carbon atoms, in particular butene-1, hexene, 4-methylpentene-1, to obtain the propylene polymer, the degree of insolubility which in xylene greater than 60%, preferably greater than 90%, in an amount of 5 g polymer/g solid catalyst component up to 10 wt.% from the final output on the used catalyst,

c) polymerization of one or more olefins in the gas phase in one or more reactors with a fluidized or mechanically mixed layer in the presence of forprimary catalytic system obtained in stage b), while circulating in the reactor or reactors alkane, the molecule of which contains 3 to 5 carbon atoms, in a molar concentration in the gas phase, 20 - 90% of the total amount of gases.

Quite unexpectedly it was found that pre-treatment of the catalyst, prepolymerisation processing catalyst and the presence of alkane in the gas phase in the above molar concentrations is possible to strictly regulate the process of gas-phase polimerizacii a) forming the catalyst components are introduced into contact with a liquid inert hydrocarbon solvent, in particular propane, n-hexane or n-heptane, at a temperature below approximately 60oC, preferably about 0 to 30oC, for a period of time from about 6 to 60 minutes

Forming the catalyst components used in stage a), include:

1) Solid material, which is a titanium compound in the molecule of which has at least one link of the titanium - halogen atom deposited on the active dihalogenide magnesium. This solid material contains an electron-donor compound (internal donor), when by itself, the catalyst does not have sufficient stereospecifically to get on stage b) propylene polymers with characteristics insolubility in xylene, which are listed in the description of stage b). In the art it is known that the use of internal donor can improve stereospecificity catalysts deposited on active dihalogenide magnesium. In the case of application of the catalytic component in the preparation of catalysts for stereoregular polymerization of propylene, butene-1 and the like alpha-olefins, when to obtain polymers with a measure of stereoregularity that exceeds 90, predpone connection.

3) an Electron-donor compound (external donor), which may be identical or different from what is included in the solid component 1). During the process of gas-phase polymerization to obtain stereoregular polymers, such as propylene polymers with a high rate of stereoregularity, with the aim of making the catalyst requires a high capacity for stereoregular polymerization using an external donor. However, in the case when the internal donor is used ethers of this type, as specified in the description of European patent application EP-A - 344755, characteristics of stereoregularity catalyst itself quite enough to no longer need to use an external donor. If by itself, the catalyst shows the ability to stereoregular polymerization, sufficient to get at the stage b) of the propylene polymer with a degree of insolubility in xylene specified for this stage in the polymerization of ethylene with the aim of obtaining HDPE (high density polyethylene), LLDPE (linear low density polyethylene) and similar polymers used by the external donor.

Use in stage b) thereore specified in the description of stage b), have a high characteristic viscosity, i.e. the viscosity of greater than 1 DL/g, which is very important to make the prepolymer of the desired morphological properties.

The catalyst obtained in stage a), continuously or periodically sent to stage b).

Stage b) can be performed in liquid or gas phase. The preferred option should be accomplished in the liquid phase or on the use of the propylene as a liquid environment, or using a hydrocarbon solvent, particularly n-hexane, n-heptane, cyclohexane or low-boiling alkane, in particular propane, butane (held in the liquid state under the conditions that create on stage b)).

The polymerization of propylene at the stage b) is carried out at a temperature of approximately 0 - 80oC, preferably about 5 - 50oC. In the polymerization of propylene or mixtures of propylene with ethylene and/or other alpha - olefins, in particular with butene-1, hexene-1, 4-methylpentene-1, receive polymers, the degree of insolubility which century xylene exceeds 60%. The amount of the prepolymer is in the range from about 5 grams of polymer per gram of catalytic component on the catalyst. The final output of the catalyst can be determined by analysis of catalytic residues, for example, the content of titanium and/or magnesium or material balance.

Stage b) can be performed continuously or periodically. In the case of continuous process, when carried out gas-phase reaction obtain ethylene polymers include appropriate separation system for unreacted propylene, before being fed into the gas-phase reactor system the prepolymer-catalyst in stage (b).

In the case when conducting the process of obtaining HDPE with a wide range of MMP (molecular weight distribution), before serving in the gas-phase reactor system the prepolymer-catalyst may be convenient to remove the external donor.

Gas-phase polymerization in stage C) is carried out in accordance with known technology using one or more reactors, placed in cascade, each of which provides a fluidized or mechanically mixed layer. The process is carried out at a temperature below the sintering temperature of the polymer particles. Typically, the temperature is about 50 - 120oC, preferably about 70 is e (reactors), the gas phase contains inert alkane C3-C5in the amount of 20 to 90 mol.% in terms of the total amount of gases. The class of suitable alkane comprises propane, butane, isobutane, n-pentane, isopentane, cyclopentane or CYCLOBUTANE. The preferred alkanol is propane.

Alkane is sent to the reactor either monomer or separately and returned to the process in conjunction with the recirculating gas, i.e. a gas stream which does not react in the layer and which divert from the polymerization zone, preferably by passing it through a zone of lower velocity above the layer where captured by the flow of particles appears favorable opportunity to fall in the layer. Then the recirculated gas is compressed, and then passed through a heat exchanger in which it is released from the heat of the reaction, followed by a return to the layer (see, for example, describe to the American patents NN 3298792 and 4518750, offering gas-phase reactors and technology).

Quite unexpectedly it was found that the above advantages can be achieved through the use of alkanes, whereas the inert gas, in particular nitrogen, is ineffective. In fact, the use of nitrogen does not prevent the formation of large aggregates ("ComC the m reaction of polymerization should be conducted in at least two reactors, installed in cascade, the first of which, where is formed the original amount of the polymer, the concentration of alkane support at a level greater than its concentration in the second reactor (or reactors). It is usually preferable to alkane circulated only in the first reactor, which produces 5 - 60% of the total polymer. On the contrary, in cases of sequential polymerization of propylene with obtaining high-impact copolymers of propylene by 1) homopolymerization propylene and 2) copolymerization of mixtures of ethylene with propylene, the process is preferably carried out with the creation in different reactors almost the same concentration of alkane.

In order to ensure full fluidization returned to the process gas and, when this is desirable, some or all of the amount of freshly gas return to the reactor at a point below the layer. The gas distribution plate is mounted above the point of return, provides the appropriate distribution, and supports the resin layer, when the flow of the gas flow is terminated.

To regulate the molecular weight of the polymer as transfer agent of the circuit can be used hydrogen.

A typical simplified technologist who icia, indicated by the numeral 1 indicates a vessel prior contact. The reactor circulation 2 is an apparatus for terpolymerization (terpolymerization). Positions 4 and 6 indicated gas-phase reactors, and positions 3, 5 and 7 - separators systems solid/gas.

In the vessel 1 in the direction of the arrows And serves catalytic components and the diluent (propane). The prepared catalyst is directed into the reactor with a circulation of 2 along the line indicated by the arrow C. On the line indicated by the arrow E, in a reactor with a circulation of injected propylene. Formed as a product of the catalyst-prepolymer is sent to the separator 3, and then in the gas-phase reactor 4, where along the line indicated by the arrow C, and then along the line to the recirculated gas also serves monomer, hydrogen and propane. The polymer discharged from the reactor 4, after passing through the separator 5 is introduced into the reactor 6, where along the line indicated by the arrow D, also serves monomer, hydrogen and propane. Obtained in the form of a part of the polymer product away from the reactor 6 and is directed to the separator 7.

Used as a carrier for catalysts of the Ziegler-Natta active dihalogenide magnesium are presented in detail in patent literature dealing with the 5338.

Manydeveloping forming a carrier for the catalytic components used to implement the method of the present invention, are characterized by X-ray spectrogram, which is missing the most intense line, which appears in the spectrum of active halide, but instead there is a halo with the maximum intensity shifted towards smaller angles relative to the angle of the most intense line, or the line is still present, but it seems wider.

Titanium compounds, it is acceptable to obtain a solid catalytic component, cover titanguard, in particular titanium tetrachloride, which is the most preferred titanium trichloride and haloalcohols, in particular trichlorophenoxyacetic and tricarboxylate.

These titanium compounds may be used as mixtures with other compounds of transition metals, in particular halides and kaleidoscopically vanadium, zirconium and hafnium.

Acceptable internal electron donors include ethers, esters, amines, ketones and simple diesters of General formula

,

where each of RIand RIIthat is the Ohm, and each of RIIIand RIVwhich are identical or different, is used to denote an alkyl radical with 1 to 4 carbon atoms. Preferred are alkalemia, cycloalkyl and arrowie esters of polycarboxylic acids, in particular phthalic and maleic acids, and simple diesters of the formula

,

where the symbols RIand RIIdefined above. Examples of such compounds include di-n-butylphthalate, diisobutylphthalate, di-n-octylphthalate, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2 - isobutyl-1,3-dimethoxypropane, 2,2-Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

The internal donor is usually found in molar proportions relative to the magnesium in the range of from 1:8 to 1:14. A titanium compound in terms of titanium contained in the amount of 0.5 - 10 wt.%.

The solid catalytic components can be obtained in accordance with the above descriptions to the U.S. patents NN 4748221 and 4801251. In that case, if stereoregularity of the obtained catalyst is not high enough to achieve the objectives of the present invention, it can easily be increased, as described above, in accordance with well known technology.

Note the European patent EP-A - 344755, allows to obtain polymers spherical shape with an average particle diameter of 300 to 5000 μm, and in the case of ethylene and propylene polymers, their bulk density greater than 0.45 g/cm3.

As examples aluminiumtechnik compounds that are used as acetalization upon receipt of the catalyst in stage (a), there can be mentioned aluminiumrail, in particular triethylamine, triisobutylaluminum, 1-tri-n-butylamine, tri-n-octylamine. You can also use a mixture of aluminization with aluminiumbyggande or aluminiumelektrolysen, in particular AlET2Cl and Al2ET3Cl3. In obtained in stage a) catalyst ratio between aluminum and titanium greater than 1, and typically the value of this ratio is within a 20 - 800.

The external donor may be the same or different from the electron-donor compound, which serves as internal donor.

In the case when the internal donor is used ether polycarboxylic acid, in particular a phthalate, the preferred external donor is a silicon compound of the formula R1R2S(OR)2where each of R1and R2- alkyl, cycloalkylcarbonyl, diphenylimidazole and tert. butyldimethylsilyl.

The solubility in xylene propylene polymer obtained in stage b), is determined by dissolving 2 g of polymer in 250 ml of xylene at 135oC while stirring. On the expiration of 20 minutes the solution is allowed to cool to 25oC. After 30 min, the precipitated precipitated material is filtered off, the solution evaporated in a nitrogen atmosphere and the residue is dried in vacuum at 80oC. Thus calculate the percentage of polymer soluble in xylene at room temperature and, therefore, the percentage of polymer insoluble at room temperature.

As indicated above, the implementation of the method of the present invention enables to obtain olefin polymers of a large number of different varieties, for example, high density polyethylene (HDPE; with a density of more than 0,940), including the homopolymers of ethylene and copolymers of ethylene with alpha-olefins, the molecules of which contain 3 to 12 carbon atoms; linear low density polyethylene (LLDPE; with density below 0,940) and linear polyethylene is very low and ultra low density (LEONP and LPASS; with a density of less 0,920 and just 0,880), which consist of sapolil content, links, educated the actual ethylene, more than 80 wt. %; elastomeric terpolymer ethylene, propylene and dienes and elastomeric copolymers of ethylene and propylene, in which the content of the links, actually educated ethylene is in the range of about 30 to 70 wt.%; isotactic polypropylene and crystalline copolymers of propylene and ethylene and/or other alpha-olefins, in which the content of the links, actually educated propylene exceeds 80 wt.%; impact-resistant polymers of propylene obtained by the sequential polymerization of propylene and mixtures of propylene with ethylene, containing up to 30 wt.% ethylene units; copolymers of propylene with butene-1, in which the content of the links formed itself butene-1, is within 10 to 40 wt.%.

As stated above, the proposed method is especially suitable for producing ethylene polymers, when high kinetics of polymerization of ethylene requires tight regulation of the process in order to resolve problems of a technological nature, which are characteristic of previously known methods of gas-phase polymerization, in particular in those cases when the process is carried out with a high specific capacity.

As mentioned above, in SL who eat stereoregular polymers required high catalyst stereoregularity polymerization. Catalyst high stereoregularity (acceptable for obtaining propylene homopolymers with a measure of stereoregularity above 90) prefer to receive only at the stage b). If necessary, stereoregularity can be modified to a greater extent by the introduction into a polymerization reactor appropriate quantity of electron-donor compounds.

The invention is illustrated in more detail by the following examples. In all cases, except as specifically stated, quantities of materials are expressed in mass units.

The General procedure.

The solid catalytic component used in the experiments the following examples is prepared as follows.

In an inert atmosphere in a reaction vessel equipped with a stirrer, download 28.4 g of magnesium dichloride, a 49.5 g of anhydrous ethanol, 10 ml of paraffin oil POL OB/30, 100 ml of silicone oil whose viscosity 350 CST, and maintained at 120oC to dissolve the magnesium dichloride. Then this hot reaction mixture is transferred into a vessel with a capacity of 1500 ml equipped with a stirrer Ultra Turrax T-45 N, containing 150 ml of vaseline oil and 150 ml of silicone oil. The temperature of the support the court, equipped with stirrer, containing 1,000 ml of anhydrous n-heptane cooled to a temperature of 0oC, and stirred at a speed of 6 m/s for 20 min, maintaining at the same time the temperature at 0oC. the Resulting particles are filtered, washed with 500 ml of the aliquot of n-hexane and gradually heat up, increasing the temperature from 50 to 100oC for a period of time sufficient to reduce the alcohol content from 3 mol to that indicator which is shown in the various examples.

Into a reaction vessel equipped with a stirrer and containing 625 ml of titanium tetrachloride, at a temperature of 0oC and with stirring load of 25 g of the adduct with different content in each case of alcohol specified in each example. Then its weight was incubated for 1 h at 100oC. When the temperature reaches 40oC add diisobutylphthalate in such numbers, in which the molar ratio between the magnesium and phthalate is 8. Then the contents of the vessel is maintained at 100oC for 2 h with simultaneous stirring, then allowed to precipitate a solid material. Through siphon remove hot liquid, dobavleniem. Stirring is then stopped, giving settling of solid material. Through siphon remove the hot liquid. The solid material is washed with an aliquot of n-hexane at 60oC and then at room temperature.

Example 1. To obtain the LLDPE used semi-industrial installation of continuous operation. This setting represents the reaction vessel in which to obtain the catalyst are mixed to form a catalyst components, reactor circulation, which serves the catalyst, obtained in the previous phase and in which direct liquid propylene and propane, and two reactor with pseudocyesis layer, placed in series, the first of which put the prepolymer obtained in the previous stage and which is directed to the second reactor polymer. For this purpose, use the reactors of this type, as suggested in the description to the us patent N 4518750.

The experiment is carried out by feeding the solid catalyst component obtained in accordance with the General procedure described above, using the adduct of magnesium dichloride and ethanol containing 35 wt.% alcohol, n-hexane solution of triethylaluminum (TEAL) and methylcyclohexanecarboxylic is 4, and the molar ratio TEAL/titanium equal to 120, the activation vessel, which constantly maintain the temperature of the 5oC. In the vessel in the form of inert polymerization medium also serves propane. Duration of stay in the reaction zone is approximately 15 minutes

The product withdrawn from this vessel, sent to terpolymerization circulation, which support continuously the temperature of the 27oC. Duration of stay in the reactor with a circulation of approximately 140 minutes with a small amount of propylene and a high degree of conversion is virtually complete conversion of liquid propylene to solid polymer (in terms of solid catalytic component comprising about 100 g/g of solid component). Thus, the number of propylene, which enters the gas-phase reactor, can be considered negligible.

The first reactor, which receives the prepolymer produced in the previous phase, operates at 80oC, and the reaction pressure support level 2 mgpa.

The average length of stay of the resulting polymer inside the reactor is Preben,

hydrogen as molecular weight regulator,

the propane.

Preliminary contact

Temperature oC - 5

Length of stay, min - 15

Stage terpolymerization

TemperatureoC - 27

Length of stay, min - 140

1st gas phase reactor

TemperatureoC - 80

Pressure, mgpa - 2,0

Length of stay, min - 80

The ethylene mol.% - 32,13(**)< / BR>
Hydrogen, mol.% - 9,46(**)< / BR>
Butene, mol.% - to 6.43(**)< / BR>
Propane, mol.% - 47,50(**)< / BR>
the 2nd gas phase reactor

TemperatureoC - 80

Pressure, mgpa - 1,5

Length of stay, min - 60

The ethylene mol.% - 52,00(**)< / BR>
Hydrogen, mol.% - 15,60(**)< / BR>
Butene, mol.% - 11,33(**)< / BR>
Propane, mol.% - 13,50(**)< / BR>
Characteristics of the finished product

The actual density, kg/l (in the form of pellets) - 0,9181

The melt index "E", g/10 min (in the form of pellets) - 0,84

The poured density of material, kg/l - 0,351

The density of the compacted material, kg/l - 0,388

The particle sizes

more than 2000 μm, wt.% - 53,7(*)< / BR>
more than 1000 μm, wt.% - 42,5(*)< / BR>
more than 500 μm, wt.% - 3,6(*)< / BR>
less than 500 mcmamara:

(*)the symbol indicated the particle diameter of the spherical shape of the obtained product.

(**)missing up to 100% of the amount accounted for by other inert materials (ethane, butane, and the like) included in the original monomers.

Example 2. HDPE get with the use of a facility of this design, which is described in example 1.

The experiment is carried out by the introduction of catalytic components in the activation vessel, in which a constant temperature of 20oC. the Product is withdrawn from this vessel, sent to terpolymerization circulation, which also serves liquid propylene and propane as inert environment).

Duration of stay in the reaction medium, when terpolymerization approximately 82 min, and the temperature is kept at 20oC.

Fluid which is contained in this terpolymerization the reactor is in a liquid state.

Liquid propylene is almost completely subjected to conversion in the solid polypropylene with output relative to the solid catalytic component approximately 400 g of polypropylene per 1 g of catalyst. The residual quantity of propector insignificantly small amount of propylene.

The first reactor, which receives the prepolymer produced in the previous phase operates at 75oC and under a reaction pressure, which is supported at the level of 1.8 mgpa.

The average length of stay of the resulting polymer inside the reactor is about 96 minutes

In this reactor serves the following reaction monomers and gases:

ethylene,

hydrogen as molecular weight regulator,

the propane.

Preliminary contact

Temperature oC - 20

Length of stay, min - 15

Stage terpolymerization

TemperatureoC - 20

Length of stay, min - 82

1st gas phase reactor

TemperatureoC - 75

Pressure, mgpa - 1,8

Length of stay, min - 96

The ethylene mol.% - 23(**)< / BR>
Hydrogen, mol.% - 29(**)< / BR>
Propane, mol.% - 40(**)< / BR>
the 2nd gas phase reactor

TemperatureoC - 80

Pressure, mgpa - 1,5

Length of stay, min - 83

The ethylene mol.% - 23(**)< / BR>
Hydrogen, mol.% - 30(**)< / BR>
Propane, mol.% - 37(**)< / BR>
Characteristics of the finished product

The actual platnost compacted material, kg/l - 0,450

the particle sizes:

more than 2000 μm, wt.% - 77,1(*)< / BR>
more than 1000 μm, wt.% - 22,2(*)< / BR>
more than 500 μm, wt.% - 0,4(*)< / BR>
more than 500 μm, wt.% - 0,3(*)< / BR>
Ultimate productivity (kg of PE/g of solid catalytic component 40

Note:

(*)the symbol indicated the particle diameter of the spherical shape of the obtained product

(**)missing up to 100% of the amount accounted for by other inert materials (ethane, butane, and the like), which may be part of the initial monomers.

Example 3. The experiment is carried out with the flow of the catalyst obtained as described in example 1, and the mass terpolymerization with propylene, directly in a single gas phase reactor.

The temperature in the gas-phase reactor is 80oC and the pressure is equal to mgpa.

In the reactor serves the following gas components:

ethylene and butene,

hydrogen as molecular weight regulator,

the propane.

First, before submitting terpolymerization catalyst in the gas-phase reactor, the concentration of propane in the gas phase is maintained at a level of approximately 60 mol.%. Even about the.% leads to the formation of large aggregates due to the very high reaction rate inside the gas-phase reactor.

During uniform test experiment is carried out in the following conditions.

Terpolymerization catalyst

Productivity (kg PP/g of solid catalytic compounds) - 0,050

1st gas phase reactor

TemperatureoC - 80

Pressure, mgpa - 2,0

The ethylene mol.% - 52(*)< / BR>
Hydrogen, mol.% - 7

Butene, mol.% - 6,5(*)< / BR>
Propane, mol.% - 32(*)< / BR>
Note:

(*)missing up to 100% of the amount accounted for by other inert materials (ethane, butane, and the like) included in the original monomers.

Comparative example 1. The challenge with obtaining a linear low density polyethylene carried out as follows:

stage activation of the catalyst,

stage vapor-phase polymerization.

Stage terpolymerization exclude to study the influence of this stage as to regulate the morphology of the polymer, and on the feasibility of the process.

The activation vessel operates at 30oC, and the length of stay in constant equal to 15 minutes

The solid catalytic component obtained according to the procedure of example 1), socialization (TEAL) and iCustom added propane as inert environment), that allows you to either modify or simplify the regulation length of stay in the reaction zone.

Remote product is then sent to the first polymerization reactor, in which a constant temperature of 75oC and a pressure of 1.8 mgpa.

After about 30 min of the experiment is stopped due to the formation of a certain number of large aggregates (lumps) which disrupt the normal operation of the system.

After removal of gases and purge internal inspection of gas-phase reactor shows the presence of this gas-phase reactor lumps and formed large crusts.

To stop gas-phase reactor in the system, the material is characterized by the composition shown in the following table (where specified conditions for this experiment).

Stage activation

TemperatureoC - 20

Length of stay, min - 15

Stage 1 gas-phase reactions

TemperatureoC - 75

Pressure, mgpa - 1,8

Length of stay, min - No data

The ethylene mol.% - 5(*)< / BR>
Hydrogen, mol.% - 1,5(*)< / BR>
Butene, mol.% - 0,5(*) the reactor.

Example 4. The experiment is carried out in the installation with the following stages:

stage activation

stage terpolymerization,

stage vapor-phase polymerization (polymerization is carried out with the use of two gas-phase reactors installed in series).

This experiment is carried out by the preliminary injection into contact with the solid catalytic component, triethylaluminum and methylcyclohexylamine ratio, similar to the above example 1, within the activation vessel, which constantly maintain the temperature of the 40oC. Catalytic component prepared from minidiary-ethanol adduct, which comprises 50 wt.% spirit.

In this vessel as the inert reaction medium also serves propane, and the resulting length of stay is approximately 13 minutes

The product withdrawn from this vessel, sent to terpolymerization, which also serves propylene and propane as inert environment).

Length of stay in terpolymerization area of approximately 2 min, and the temperature was constantly keep it at 20oC.

The first reactor, which receives the prepolymer obtained in the previous phase, operates at 80oC and under a reaction pressure, which is maintained at the level of 2.4 mgpa.

In the reactor serves the following reaction monomers and gases:

propylene,

hydrogen as molecular weight regulator,

the propane.

The test conditions are summarized in the following table.

Stage activation

TemperatureoC - 40

Length of stay, min - 13

Stage terpolymerization

TemperatureoC - 20

Length of stay, min - 2

1st gas phase reactor

TemperatureoC - 80

Pressure, mgpa - 2,4

Length of stay, min - 54

Propylene, mol.% - 50,5(**)< / BR>
Hydrogen, mol.% - 6,4(**)< / BR>
Propane, mol.% - 41(**)< / BR>
the 2nd gas phase reactor

TemperatureoC - 80

Pressure, mgpa - 2,4

Length of stay, min - 66

Propylene, mol.% - 78,2(**)< / BR>
Hydrogen, mol.% - 10,4(**)< / BR>
Propane, mol.% - 5,5(**)< / BR>
Characteristics of the finished product

The poured density of material, kg/l - 0,SUP>< / BR>
more than 1000 μm, wt.% - 66,3(*)< / BR>
more than 500 μm, wt.% - 10,2(*)< / BR>
less than 500 microns, wt.% - 1,6(*)< / BR>
Finite capacity, kg PP/g of solid catalytic component is 21.2

Note:

(*)the symbol indicated the diameter of the particles of the product of the spherical shape

(**)missing up to 100% of the amount accounted for by other inert materials (methane, ethane, and the like) included in the original monomers.

In all experiments of examples carried out in accordance with the present invention, semi-industrial installation works evenly combined total regulation of all working conditions.

In the variants described above can, of course, to make any changes without departing from the scope of the present invention.

1. The method of obtaining the (co)polymers of olefins continuous gas-phase polymerization or copolymerization of olefins of the formula

CH2= CHR,

where R is hydrogen, C1-C8-alkyl,

by using a catalyst comprising a reaction product of the following components: titanium compound the molecule of which contains at least titansiloxanes communication and which enabled trialkylsilyl connection and possibly with electron-donor compound, characterized in that it includes the following stages:

a) contacting the catalyst components in the absence of polymerizable olefins or possibly in the presence of the indicated olefin in an amount up to 3 g per 1 g of the solid catalytic component with the formation of the catalyst for stereoregular polymerization, capable of polimerizuet propylene in the conditions of stage (b), to obtain the propylene polymer, the degree of insolubility which in xylene comprises at least 60 wt.%;

b) terpolymerization with the participation of the catalyst obtained above propylene or mixtures of propylene with small amounts of ethylene and/or alpha-olefin with 4 to 8 carbon atoms, resulting in a propylene polymer, the degree of insolubility which in xylene greater than 60 wt.%, in an amount of from 5 g of polymer per 1 g of the solid catalytic component to 10 wt.% from the final output on the catalyst;

c) polymerization of one or more olefins of the formula CH2= CHR in the gas phase in one or more reactors having pseudocyesis or mechanically mixed layer, using forprimary catalytic system obtained in stage b), pricelearn alkane concentration relative to the total amount of gases is approximately 20 - 90%.

2. The method according to p. 1, characterized in that in its implementation the polymerization is carried out in two reactors, the first of which get 5 to 60 wt.% of the total number of the obtained polymer and in which the alkane concentration higher than the concentration in the second reactor.

3. The method according to PP. 1 and 2, characterized in that the catalyst obtained in stage a), contains both internal and external electron-donor compounds.

4. The method according to p. 3, characterized in that the internal donor is an ester of phthalic acid, and the external donor is dimethoxymethyl or alkylalkoxysilane.

5. The method according to p. 1 or 2, characterized in that the catalyst obtained in stage b), as an internal donor contains simple fluids formulas

< / BR>
where each of R' and R" are identical or different, alkyl, cycloalkyl or aryl radical containing from 1 to 18 carbon atoms.

6. The method according to p. 4 or 5, characterized in that in its implementation using the catalyst of the spherical shape, the specific activity of which is 10 to 100 kg/h per 1 g of the solid catalytic component, and the average particle diameter is in the range of 30 to 150 μm.

< p. 1 or 2, characterized in that the catalyst is prepared using an external donor and the solid component of the spherical shape, which has an internal donor, and the alkane is a propane.

9. The method according to p. 1 or 2, characterized in that the catalyst is obtained from the solid component of the spherical shape containing as an internal donor simple fluids formulas

< / BR>
where each of R' and R" are identical or different, alkyl, cycloalkyl or aryl radical with 1 to 18 carbon atoms,

where the alkane is a propane.

10. Copolymers of olefins of the formula

CH2= CHR,

where R is hydrogen or an alkyl group containing 1 to 8 carbon atoms,

obtained by the method according to any of paragraphs. 1 to 9.

 

Same patents:
The invention relates to methods of producing stabilized polypropylene and can be used in the plastics industry

The invention relates to catalysts for (co)polymerization of olefins and method () polymerizatio olefins

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

The invention relates to a method for producing polyolefins by polymerization or copolymerization of an olefin of the formula Ra- CH=CH - Rbwhere Raand Rbthe same or different and represent a hydrogen atom or a hydrocarbon residue with 1 to 14 carbon atoms, or Raand Rbrelated atoms may form a ring, at a temperature of from -60 to 200oC, a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gaseous state in the presence of a catalyst containing metallocene as the compound of the transition metal and socialization

The invention relates to techniques for polymerization of isobutylene, and the obtained product is used as a thickening additive for lubricating oils for the manufacture of sealants, adhesives and many other purposes

The invention relates to a method of polymerization of ethylene, which allows to obtain polyethylene having a density of about 0,93 and less

The invention relates to a component of the catalyst or catalyst, which is suitable for use in the reaction stereoregular polymerization or copolymerization of alpha-olefins and particularly relates to a magnesium-containing, titanium containing catalyst component on the substrate or catalyst suitable for receiving homopolymer or copolymer of alpha-olefin

The invention relates to a continuous method for the polymerization of alpha-olefin having from 2 to 12 carbon atoms, which is held in gas-phase polymerization reactor by contacting the gaseous reaction mixture with a catalyst based on chromium oxide associated with a granular substrate and activated by heat treatment, in which the polymerization reactor is introduced (A) alpha-olefin, and (C) the catalyst at a constant speed

FIELD: polymerization catalysts.

SUBSTANCE: invention describes metallocene catalytic component of catalytic system for production of polyolefin with isotactic or syndiotactic/isotactic block structure with length of monomer unit up to C10, said component having general formula R"(CpR1R2R3)(Cp'R1R2')MQ2, where Cp represents cyclopentadienyl ring substituted by at least one substituent; Cp' is substituted fluorenyl ring; R" structural bridge imparting steric rigidity; R1 optional substituent in cyclopentadienyl ring located at a distance to bridge and including a bulky group XR*3 wherein X is selected from group IVA elements and R*, the same or different, are hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms; R2 optional substituent in cyclopentadienyl ring, nearest to bridge and not vicinal to remote substituent, which substituent has formula YR# wherein Y is selected from group IVA elements and R#, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R3 optional substituent in cyclopentadienyl ring, nearest to bridge and being hydrogen or having formula ZR$ wherein Z is selected from group IVA elements and Rs, the same or different, are hydrogen or hydrocarbon radical containing 1 to 7 carbon atoms; R1' and R2' are independent substituents in fluorenyl ring, one of them having formula AR3’’’ wherein A is selected from group IVA elements and each of R’’’ represents independently hydrogen or hydrocarbon radical containing 1 to 20 carbon atoms and the other being hydrogen or second group AR3’’’; M is transition metal from group IVB or vanadium and each Q is either hydrocarbon radical with 1-20 carbon atoms or halogen.

EFFECT: enabled preparation isotactic or syndiotactic/isotactic block polymer with length of monomer unit up to C10.

30 cl, 13 dwg, 2 tbl, 10 ex

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