Method for polymerisation of olefin-based polymers

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing olefin-based polymers. Described is a method of producing olefin-based polymers, which involves polymerisation of at least one monomer in a gas phase in the presence of at least the following components: A) a catalyst which contains metals Mg, Ti, Hf and optionally Zr; B) a co-catalyst which is trialkylaluminum; C) a composition containing at least one compound selected from compounds of formula (1) and at least one compound selected from compounds of formula (II): (R1CO₂)₂AlOH (1), (R2)_xN(R3OH)_y (II); where R1 is a hydrocarbon radical containing 13-25 carbon atoms; R2 is a hydrocarbon radical containing 14-26 carbon atoms; R3 is a hydrocarbon radical containing 1-4 carbon atoms, and x+y=3, and x equals 1 or 2. Described also is a method of producing olefin-based polymers, which involves polymerisation of at least one monomer in a suspension process, in the presence of at least the following components: A) a catalyst which contains metals Mg, Ti, Hf and optionally Zr; B) a co-catalyst which is trialkylaluminum; C) a composition containing at least one compound selected from compounds of formula (1) and at least one compound selected from compounds of formula (II): (R1CO₂)₂AlOH (I), (R2)_xN(R3OH)_y (II); where R1 is a hydrocarbon radical containing 13-25 carbon atoms; R2 is a hydrocarbon radical containing 14-26 carbon atoms; R3 is a hydrocarbon radical containing 1-4 carbon atoms, and x+y=3, and x equals 1 or 2. Described is a method of producing olefin-based polymers, which involves polymerisation of at least one monomer in the presence of at least the following components: A) a Ziegler-Natta catalyst which contains metals Mg, Ti, Hf and optionally Zr; B) a trialkylaluminum compound; C) a composition containing at least one compound selected from compounds of formula (1) and at least one compound selected from compounds of formula (II): (R1CO₂)₂AlOH (I), (R2)_xN(R3OH)_y (II); where R1 is a hydrocarbon radical containing 13-25 carbon atoms; R2 is a hydrocarbon radical containing 14-26 carbon atoms; R3 is a hydrocarbon radical containing 1-4 carbon atoms, and x+y=3, and x equals 1 or 2.

EFFECT: providing prolonged continuous reactor operation without formation of a polymer layer on walls and agglomerates when producing high-molecular weight olefin-based polymers.

17 cl, 12 tbl, 6 dwg, 14 ex

References to related applications

This application claims the benefit of provisional application U.S. No. 61/017986, filed December 31, 2007 and fully incorporated herein.

The invention relates to the improved production of polymers based on olefins with very high molecular weight in gas-phase polymerization reactors.

The invention also relates to additional regulation of the molecular mass distribution of polymers produced with the catalysts of mixed type metal-catalyst of the Ziegler-Natta in gas-phase polymerization reactors, is not dependent on changes in the composition of the catalyst.

Background of invention

Catalysts which provide a wide molecular weight distribution and high molecular weight tails, desirable for use in both the processes of polymerization in suspension and gas phases with obtaining superior products, especially HDPE resin for blow molding, where it is important swelling resin (caused by high-molecular chains). However, the production of these polymers with factions resin with very high molecular weights is difficult due to problems of health reactor associated with very high levels of static electricity (which can cause adhesion of fine particles to the surfaces, n is Evodia to poor regulation and the inevitable formation of a polymer layer on the walls of the reactor), the formation of agglomerates in the reactor and contamination of the entire system.

To provide products with improved properties such catalysts (especially catalysts, which contain several components, one of which enables the achievement of very high molecular weight)must be solved problems of continuous operation of the reactor and the formation of agglomerates. The static problem of "fit" is further exacerbated when the catalytic system has a positive activation energy, which further increases the tendency to form a polymer layer on the walls of the reactor and the formation of agglomerates, thereby forcing premature to stop the reactor.

It was found that the use of a mixture of two solid agents that improve the continuity of the reactor is introduced into the reactor simultaneously, separately from the catalyst, provides a more continuous operation without the formation of a polymer layer on the walls and agglomerates, which requires stopping the reactor. It was unexpectedly found that the activity of the catalyst, in General, does not deteriorate when the injected agent, to improve the continuity, within a specified ratio to the mass of the reaction layer. Confirmed also the ability to adjust the level of static charge. Removing agent, improve the continuity of work, leads to massive contamination of the reactor and having to stop his work, even if there are no such symptoms as static charge. Agents improve continuity (Continuity Aid or SA) operate in the presence of alkylamines of socialization, which are usually required to achieve full activity of catalysts of the type catalysts, Ziegler. Similar methods were evaluated with catalysts reciperestore type, such as metallocene and post-metallocene catalysts that are typically used without socializaton. These methods were not considered as applicable to catalytic systems, which provide for the filing of socialization in the reactor.

There is a need in the production of high molecular weight resins, particularly resins with high molecular weight fractions > 10⁶g/mol, and preferably as high as 10⁷g/mol or more, in quantities greater than two percent by weight, more preferably four to five percent by weight. The production of polymers of data types, with high molecular weight fractions in the fluidized bed gas-phase reactors are typically considered more difficult due to agglomeration and formation of a polymer layer on the walls of the reactor, causing the shutdowns of the reactor. There are many methods that can improve is endency to the formation of sheets/pieces starting from the mode of condensation, with the addition of an antistatic agent or working at temperatures sufficiently low, in which the polymer melting cannot occur. However, all these methods have drawbacks. The mode of condensation requires high levels of agent-induced condensation, and work with high efficiency of the production of the polymer, which can make the reactor more sensitive to the conditions of formation of the polymer layer on the walls of the reactor. In addition, the exclusion or higher static capacity does not necessarily correlate with good long-term performance properties of the reaction system. Thus, the mere exception of the static charge does not guarantee that will not happen formation of the polymer layer on the walls of the reactor, the formation of agglomerates or other manufacturing defects.

In the level there are numerous opinions about anti-static agents, but the mere mention of the compounds as antistatic agent does not mean that a particular compound will act in the reactor, polymerization of olefins. Indeed, many antistatic agents, which are commercially available, based on the water content. However, water is a strong poison for all known catalytic with the systems of the Ziegler.

Publication of patent application U.S. No. 20070073012 relates to a method of processing additive layer before carrying out the polymerization reaction (for example, the polymerization reaction of olefins with improved continuity of reaction. This publication discloses a method in which at least one additive to improve continuity and the seed layer is pre-injected into the reactor. Examples of additives that improve the continuity of the reactor include metallic stearates and amines.

European patent EP V discloses a method of delivery of the catalyst for the introduction of the catalytic system on the media based on the volume of the ligand metallocene-type reactor for the polymerization of one or more olefin(s). In particular, the catalytic system of the metallocene type on the media is introduced into the polymerization reactor with or in the presence of a solution of a carrier containing an antistatic agent and a liquid diluent. Antistatic agents include various amine compounds and other compounds.

U.S. patent 6111034 discloses the addition of water to the reactor gas-phase polymerization of olefins in amounts exceeding 3 mln by volume, which improves the level of condensed gas and accelerates the operation of the reactor at elevated dew point by improving electrostatic phenomena react in the re. This patent discloses the polymerization with controlled static charge and several antistatic agents include ethoxylated amines of fatty acids, synthesis of Quaternary salts, hromsoderjashchaya compounds and salts of fatty acids and alkali and alkaline earth metals. Great attention is paid to the use of water as a component in the methodology of regulation static charge.

U.S. patent 6022935 discloses the use of an antistatic agent introduced into the reactor together with metallocene catalysts. See also European patent application No. ERW.

Publication of the U.S. No. 20020065374 relates to a method of polymerization of the monomers in the gas-phase reactor with recirculation system. This patent discloses the use of antistatic and protivoshokovymi coatings on the end of the tube for introduction of the catalyst, especially for use with liquid polymerization catalysts.

U.S. patent 6359083 discloses a method of producing polyolefins, where the solids are transported by the gas in the polymerization process with improved serviceability. This patent, in General, reveals that the antistatic agents can be introduced into the polymerization reactor, or the catalyst and that they can be solid. No specific examples are not provided.

PA is UNT USA 5731392 discloses the use of two different agents, water and silicates, as a means to control static charge in the polymerization reaction system with an emphasis on silicates.

U.S. patent 6548610 relates to a method and device for controlling static charge in the fluidized bed reactor polymerization of olefins. The method includes monitoring charges inside layer and the introduction of agent control static charge in the reactor in an amount to provide create and maintain a neutral charge in the layer.

Publication of the U.S. No. 20020103072 relates to a catalyst for polymerization including bulk ligand. This patent discloses methods of control of static charges by using metallocene catalysts of the type with bulky ligand.

There are other ways that can provide a reduced number of entities polymer layers/agglomerates, but they all affect the efficiency of the process. One way is that it is done at very low partial pressure of ethylene, so that even in the presence of stagnation zones in the reactor, the amount of reagent sufficient to cause the formation of polymeric layers/agglomerates. The obvious disadvantage of this method is that the overall efficiency of the catalytic system will be significantly reduced. Simultaneously with this reduced efficiency rolled atora will decrease the size of the polymer particles, leading to a higher content of fine fractions and additional performance. Thus, it is necessary to operate the reactor at a reduced speed or to submit significantly more catalyst. Any approach is economically disadvantageous.

Another method provides for the operation of the reactor at low temperature, further increasing the gap between the reaction temperature and the melting point or a stumbling block production of the polymer. So for example, you can implement the operation of the reactor at 50°C instead of the more desirable high temperatures. It also forces you to work at lower speeds, again leading to low technical and economic indicators of the process and, if the catalyst is not particularly durable, greatly complicating the many aspects of reactor operation.

Another method provides for the operation of the reactor in mode condensation, but even this does not guarantee that will not happen formation of polymer layers/agglomeration, especially when the mode of condensation, i.e., when the rate of polymerization increases, the energy flow in the polymerization layer should be increased, leading to the possible formation of polymer/agglomerates before the polymerization rate will increase enough to achieve RA is Otsego mode of condensation. Additionally, high levels of static charge does not usually increase until, until you reach a significant percentage of condensation. You also need to add a very large number of agent-induced condensation, in fact, with a decrease in temperature adhesion of the polymer, which further increases the probability of formation of the polymer layer and agglomerates.

Another possible solution consists in washing the resulting catalyst with removal of at least some of the compounds that have a tendency to create a static charge. However, this entails adding a few extra steps in the process of preparation of the catalyst, which typically increases the cost and complexity of the process of preparation of the catalyst, increasing the potential volatility of the catalyst and, as will be shown in the examples, does not prevent the formation of a polymer layer on the walls of the reactor and lumps in the course of obtaining the resin with a very high molecular weight fractions.

None of these alternative methods do not provide the polymer with recommended for industrial reactors speeds. As discussed, there is a need not only to regulate the static charge, but also to obtain high molecular weight polymer with high speeds polymer clay is Itachi, using effective methods of polymerization, without the formation of agglomerates in the reactor. The way to implement these and other needs are developed in the following invention.

In addition, it is highly desirable to be able to regulate the molecular-mass distribution in the system for the polymerization of olefins. General methods of modification of the molecular mass distribution is known in this area, but they usually include control variables associated with the actual receipt of the catalytic system. Variables control the polymerization process allows you to change the number of molecular mass distribution, but it is limited to technical and economic parameters (i.e. too low reaction temperature leads to poor performance), physical factors (temperature of the reaction, for example, may be a limiting parameter, if the polymer becomes soft/sticky) and limitations of the process, such as total pressure, the solubility of the monomer in the polymer, etc. the Ability to adjust the properties of the polymer, such as DFID, using this component as a co-feedstock or socialization, it would be highly desirable.

European patent ERA discloses a solid component of catalyst, which includes magnesium, halogen and titanium obtained (i) by dissolving dialkylamino the first connection, the silicon halide and the optional alkylhalogenide in an inert organic solvent and maintaining contact until, until you precipitate granular solid substance; (ii) the implementation of the interaction of granular solids with a titanium halide, alkoxide or halogen alkoxide to obtain a solid catalytic component, and (iii) the activation of this solid component by contacting it with alkylhalogenide, if at stage (ii) used the titanium alkoxide or halogen-alkoxide. The highest aluminiumgie as tri-n-hexylamine proposed as agents that increase the ratio of velocity of the melt flow.

U.S. patent 4368305 discloses a method of producing polyolefins, particularly polyethylene, which are high molecular weight or which have a broad molecular weight distribution and are, therefore, suitable for extrusion or blow molding, the method comprises the polymerization of olefins such as ethylene, using a catalytic system, which consists of a solid catalytic component obtained by mixing or interaction of the oxygen-containing ORGANOMETALLIC compounds or halides of vanadium and (b) hafnium, or a solid catalytic component obtained by mixing or interaction of oxygen is containing ORGANOMETALLIC compounds or halides (A) vanadium, (C) hafnium and (C) titanium and (D) alyuminiiorganicheskikh connection.

U.S. patent 6054406 reveals polymetallic catalyst component on the carrier, comprising a solid carrier activated anhydrous MgCl₂that processed at least once, at least two halogen-containing transition metal compounds, one is a halogen-containing compound of titanium metal and is one halogenated compound of a transition metal, but not titanium, optionally, in the presence of an electron donor, and method for producing the component. The catalyst was prepared by the interaction of this catalytic component on the carrier with ORGANOMETALLIC socialization, optionally in the presence of an electron donor.

U.S. patent 7348383 reveals the catalytic composition of the Ziegler-Natta comprising a solid mixture formed by halogenoalkanes A1) catalyst precursor spray drying, comprising the product of the interaction of compounds of magnesium, nepetalactone compound of titanium and at least one nepetalactone compounds transition metal other than titanium, A2) halogenation agent-based alyuminiiorganicheskikh of halide; a method of obtaining precursors for use in the polymerization processes of olefins with them what ispolzovaniem.

There is a need to adjust the characteristic molecular weight distribution of the polymer by changing the composition of socializaton added to the polymerization reactor. Also there is a need to change the properties of the polymer without the need to change the composition of the catalyst. Data and other needs are addressed by the present invention.

Summary of the invention

The invention relates to a method for producing polymers based on olefins comprising the polymerization of at least one monomer in the gas phase, in the presence of at least the following components:

A) at least one catalyst;

C) at least one socializaton;

(C) a composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

The invention relates to a method for producing polymers based on olefins, which includes the t polymerization, at least one monomer in a suspension process, in the presence of at least the following components:

A) at least one catalyst;

C) at least one socializaton;

(C) a composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

The invention also relates to a method for producing polymers based on olefins, which comprises the polymerization of at least one monomer in the presence of at least the following components:

A) catalyst type Ziegler-Natta, comprising at least two transition metal;

In connection trialkylamine;

C) optional composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 p is ecstasy hydrocarbon radical, containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

Brief description of drawings

Figure 1 shows the change in the static potential on the wall of the reactor (volt-time) during polymerization of the copolymer of ethylene/1-hexene without the addition of adjuvants to increase continuity of operation of the reactor.

Figure 2 shows the change in the static potential on the wall of the reactor (volt-time) during polymerization of the copolymer of ethylene/1-hexene without the addition of adjuvants to increase continuity of operation of the reactor.

Figure 3 shows the change in the static potential on the wall of the reactor (volt-time) during polymerization of the copolymer of ethylene/1-hexene without the addition of adjuvants to increase continuity of operation of the reactor.

Figure 4 shows the change in the static potential on the wall of the reactor (volt-time) during polymerization of the copolymer of ethylene/1-hexene with the addition of adjuvants to increase continuity of operation of the reactor.

Figure 5 depicts the effect of the filing of auxiliary additives to increase the continuity of the operation of the associated reactor (the top of the Yaya line represents the static charge (volts) at the G-7 and the lower line represents the static charge (volts) on G-1.

The figure 6 presents the dependence of the performance of the polymerization process (settlement) in time.

Detailed description of the invention

The invention relates to a method for producing polymers based on olefins, which comprises the polymerization of at least one monomer in the gas phase, in the presence of at least the following components:

A) at least one catalyst;

C) at least one socializaton;

(C) a composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

The invention also relates to a method for producing polymers based on olefins, which comprises the polymerization of at least one monomer in the gas phase, in the presence of at least the following components:

A) at least one catalyst;

C) at least one socializaton;

(C) a composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

In one embodiment of the invention for a method, characterized by novelty items, gas-phase polymerization proceeds, at least in the same reactor.

The invention also relates to a method for producing polymers based on olefins, which comprises the polymerization of at least one monomer in a suspension process, in the presence of at least the following components:

A) at least one catalyst;

C) at least one socializaton;

(C) a composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon RA is hiccuping, containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

The invention also relates to a method for producing polymers based on olefins, which comprises the polymerization of at least one monomer in a suspension process, in the presence of at least the following components:

A) at least one catalyst;

C) at least one socializaton;

(C) a composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

In one embodiment of the method according to the invention, the polymerization proceeds, at least in the same reactor.

In one embodiment of the method according to the invention for formula (I) ((R1CO₂)₂AlOH) R1 represents a hydrocarbon radical containing from 13 to 20 carbon atoms and preferably from 13 to 17 atom is in carbon.

In one embodiment, the new method according to the invention for formula (II) ((R2)_xN(R3OH)_y) R2 represents a hydrocarbon radical containing from 14 to 20 carbon atoms, preferably from 14 to 17; R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms and x+y=3, and x has a value of 1 or 2.

In one embodiment of the method according to the invention a composition component further includes an inert hydrocarbon media, such as isopentane, hexane or mineral oil.

In one embodiment of the method according to the invention a composition component further includes mineral oil.

In one embodiment of the method according to the invention, the composition component is at least one compound selected from compounds of formula (I)at least one compound selected from compounds of the formula (II) and inert hydrocarbon media, such as isopentane, hexane or mineral oil. In another embodiment of the invention, the mass ratio "of compounds selected from compounds of formula (I)", "compound selected from compounds of the formula (II)is about 1 to 1.

In one embodiment of the method according to the invention the composition of the component consists of at least one soybean is inane, selected from compounds of formula (I)at least one compound selected from compounds of the formula (II), and mineral oil. In another embodiment of the invention, the mass ratio "of compounds selected from compounds of formula (I)", "compound selected from compounds of the formula (II)is about 1 to 1.

In one embodiment of the method according to the invention, the component includes at least one compound selected from compounds of formula (I)at least one compound selected from compounds of the formula (II), and the mass ratio "of compounds selected from compounds of formula (I)", "compound selected from compounds of the formula (II)is about 1 to 1.

In one embodiment of the method according to the invention the polymer-based olefin, and preferably a polymer based on ethylene, contains a fraction of at least two weight percent (calculated on the total weight of the polymer), which has a molecular mass greater than 10⁶g/mol, defined by respective portions of either traditional or LS (light dispersion) GPC curve of the polymer. In another embodiment of the invention corresponding parts of the area are related to traditional GPC curve. In another embodiment of the invention corresponding share of the area belong to the Cree is Oh GPC LS.

In one embodiment of the method according to the invention the polymer-based olefin, preferably a polymer based on ethylene, contains a fraction of at least four weight percent (calculated on the total weight of the polymer), which has a molecular mass greater than 10⁶g/mol, defined by respective portions of either traditional or LS (light dispersion) GPC curve of the polymer. In another embodiment of the invention corresponding parts of the area are related to traditional GPC curve. In another embodiment of the invention corresponding share of the area belong to the GPC curve with LS.

In one embodiment of the method according to the invention the component fed into the reactor separately from the catalyst and socializaton.

In one embodiment of the method according to the invention the component is fed directly into the reactor.

In one embodiment of the method according to the invention the component is initially fed into the reactor simultaneously with the beginning of the filing of the catalyst.

In one embodiment of the method according to the invention the component is solid at the feed to the reactor.

In one embodiment of the method according to the invention the component is a suspension in the feed to the reactor.

In one embodiment of the method according to the invention the component includes Saedinenie and compound II, each of which is a solid form when submitting to the reactor. In another embodiment of the invention the component is a suspension.

In one embodiment of the method according to the invention, the component includes a connection I, which is in solid form when submitting to the reactor. In another embodiment of the invention the component is a suspension.

In one embodiment of the method according to the invention, the component includes a compound II, which is in solid form when submitting to the reactor. In another embodiment of the invention the component is a suspension.

In one embodiment of the method according to the invention the catalyst is a catalyst of Ziegler-Natta. In another embodiment of the invention, the catalyst comprises a metal of Mg, Ti, Hf and optionally Zr. In another embodiment of the invention each of the metals contained as the halide.

In one embodiment of the method according to the invention the catalyst is a catalyst of Ziegler-Natta. In another embodiment of the invention the catalyst comprises metals of Mg, Ti and Hf. In another embodiment of the invention, each metal contained in the form of a halide.

In one embodiment of the method according to the invention, the catalyst obtained by spray drying plants is ora, including an active metal catalyst in an alcohol solvent, followed by halogenoalkanes active metals.

In one embodiment of the method according to the invention the polymer-based olefin polymerized, at least one reactor. In another embodiment, the invention polymer-based olefin polymer is ethylene.

In one embodiment of the method according to the invention the polymer-based olefin obtained in the two reactors. In another embodiment of the invention the first polymer obtained in the first reactor, and the first polymer is transferred to the second reactor, where they earn a polymer with a lower molecular weight in the presence of the first polymer with the formation of polymer-based olefin. In another embodiment, the invention polymer-based olefin polymer is ethylene. In another embodiment of the invention the catalyst is served only in the first reactor.

In one embodiment of the method according to the invention the catalyst is served only in the first reactor. In another embodiment, the invention polymer-based olefin polymer is ethylene.

In one embodiment of the method according to the invention the polymer-based olefin has a molecular weight distribution greater than or equal to 3. In the other the embodiment of the invention the polymer-based olefin polymer is ethylene.

In one embodiment of the method according to the invention the polymer-based olefin has a molecular weight distribution less than or equal to 5. In another embodiment, the invention polymer-based olefin polymer is ethylene.

In a preferred embodiment of the method according to the invention the polymer-based olefin polymer is ethylene. In another embodiment, the invention is a polymer based on ethylene copolymer is ethylene/α-olefin. In another embodiment of the invention α-olefin selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene, 1-hexene and 1-octene, and more preferably from 1-butene and 1-hexene.

In one embodiment of the method according to the invention the polymer has a melt index under high load (I21) is less than or equal to 2 g/10 min In another embodiment, the invention polymer-based olefin polymer is ethylene.

The method according to the invention can include a combination of two or more embodiments of the invention, as described in this document.

Polymer-based olefin of the method according to the invention can include a combination of two or more embodiments of the invention, as described in this document.

In one embodiment, is sushestvennee of the invention the catalyst, used in the invention can be described as the composition of the catalyst precursor and the composition of the final catalyst. The catalyst precursor composition includes spray drying, obtained by dissolving compounds of magnesium, titanium compounds, the compounds of hafnium and/or zirconium compounds in an alcohol solvent in the presence of filler/filling agent. In another embodiment of the invention the filler or filling agent has an average particle size of not more than 25 percent from the average particle size of the final catalyst precursor. The transition metal compounds can be halides, alkoxides, mixed alkoxide/2,4-pentanedionate and mixtures thereof. The only requirement is that the solubility in an alcohol solvent. Particularly preferred titanium compounds are TiCl₃(restored either hydrogen or aluminum) and Ti(2,4-pentanedionate)₂(OR)₂where R may be ethyl, isopropyl, n-propyl or n-butyl. Preferred compounds of Zr or Hf are the chlorides or alkoxides (for example, atoxic, propoxide, piperonyl). Preferred magnesium compounds are MgCl₂and ethylcarbonate magnesium. The composition of the catalyst precursor halogenous by the end of the active catalyst used in the invention. The composition of the catalyst does not have or has very low activity in the absence of socializaton. It is established that the characteristic molecular weight distribution of this catalytic system can be changed by varying the composition of socializaton introduced into the polymerization reactor. This ability allows you to vary the properties of the polymer without changing the composition of the catalyst. Socialization is the connection trialkylamine, especially triethylaluminum, triisobutylaluminum, tert-n-hexylamine, tri-n-butylamine and tri-n-octylamine or mixtures thereof. Socialization choose to increase or decrease the width of the molecular mass distribution, regardless of the composition of the catalyst. Socialization injected into the polymerization reactor separately, although in one embodiment of the invention it can be mixed with a catalytic raw material when both are entered directly in the polymerization reactor. When two reactors are connected in series, and catalytic raw material is supplied only to the first reactor, socialization does not need to be filed only in the first reactor or the other acetalization can be introduced into the second reactor.

Thus, the invention also relates to a method for producing polymers based on olefins, which comprises the polymerization of at least one monomer in the presence at least the following components:

A) catalyst type Ziegler-Natta, comprising at least two transition metal;

In connection trialkylamine;

C) optional composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

The invention also relates to a method for producing polymers based on olefins, which comprises the polymerization of at least one monomer in the presence of at least the following components:

A) catalyst type Ziegler-Natta, comprising at least two transition metal;

In connection trialkylamine;

C) optional composition comprising at least one compound selected from compounds of formula (1), and/or at least one compound selected from compounds of the formula (II):

(R1CO₂)₂AlOH (I)

(R2)_xN(R3OH)_y(II);

where R1 represents pleva rodny radical, containing from 13 to 25 carbon atoms;

R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;

R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and

x+y=3, and x has a value of 1 or 2.

In one embodiment of the method according to the invention, at least one polymerized monomer gas-phase method. In another embodiment of the invention, the polymerization proceeds, at least in the same reactor.

In one embodiment of the method according to the invention, at least one monomer is suspension polymerized way. In another embodiment of the invention, the polymerization proceeds, at least in the same reactor.

In one embodiment of the method according to the invention, the polymerization proceeds, at least in the same reactor.

In a preferred embodiment of the method according to the invention the component is present during the course of polymerization.

In a preferred embodiment of the method according to the invention the ratio of the velocity of the melt flow (MFR) of the polymer-based olefin change, regardless of the reaction conditions, trialkylaluminium connection. In another embodiment of the invention the ratio of the velocity of the melt flow of the polymer-based olefin change, regardless of the reaction conditions, trialkylaluminium compound and its concentration in the reactor. In an additional embodiment, the invention polymer-based olefin polymer is ethylene.

In one embodiment of the method according to the invention the catalyst comprises a metal of Mg, Ti, Hf and optionally Zr. In another embodiment of the invention, each metal present in the form of a halide.

In one embodiment of the method according to the invention the catalyst comprises a metal of Mg, Ti and Hf. In another embodiment of the invention, each metal present in the form of a halide.

In one embodiment of the method according to the invention, the catalyst obtained by spray drying a solution comprising an active metal catalyst in an alcohol solvent, followed by halogenoalkanes active metals.

In one embodiment of the method according to the invention the polymer-based olefin polymerized, at least one reactor. In another embodiment, the invention polymer-based olefin polymer is ethylene.

In one embodiment of the method according to the invention the polymer-based olefin obtained in the two reactors. In another embodiment of the invention the first polymer obtained in the first reactor, and the first polymer is transferred to the second reactor, which produce a polymer with a lower molecular weight in risotti first polymer, obtaining polymer-based olefin. In another embodiment, the invention polymer-based olefin polymer is ethylene. In another embodiment of the invention the catalyst is served only in the first reactor.

In one embodiment of the method according to the invention the connection trialkylamine selected from tri-n-hexylamine, triethylamine or triisobutylaluminum. In another embodiment of the invention the connection trialkylamine is tri-n-hexylamine.

In a preferred embodiment of the method according to the invention the polymer-based olefin polymer is ethylene. In another embodiment, the invention polymer-based olefin copolymer is an ethylene/α-olefin. In another embodiment of the invention α-olefin selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene, 1-hexene and 1-octene, and more preferably 1-butene and 1-hexene.

In one embodiment of the method according to the invention the polymer based on ethylene is the standard I₂₁from 25 to 45, and the ratio of the velocities of the melt (I₂₁/I₂) changes by +/-15% due to changes in trialkylaluminium. In another embodiment, the invention is a polymer based on ethylene copolymer is ethylene/α-Ola is in. In another embodiment of the invention α-olefin selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene, 1-hexene and 1-octene, and more preferably 1-butene and 1-hexene.

In one embodiment of the method according to the invention the polymer based on ethylene has an index of melt flow under high load, I₂₁are less than 100 and the ratio of velocity of the melt current, I₂₁/I₂that is more than 30, preferably greater than 40. In another embodiment, the invention is a polymer based on ethylene copolymer is ethylene/α-olefin. In another embodiment of the invention α-olefin selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene, 1-hexene and 1-octene, and more preferably 1-butene and 1-hexene.

In one embodiment of the method according to the invention the polymer based on ethylene has an index of melt flow under high load, I₂₁that is less than 60 and the ratio of velocity of the melt current, I₂₁/I₂, over 35, more preferably 45. In another embodiment, the invention is a polymer based on ethylene copolymer is ethylene/α-olefin. In another embodiment of the invention α-olefin selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene, 1-hexene and 1-octene, and more preferably 1-butene and 1-hexene.

In one embodiment of the method according to the invention the polymer based on ethylene has an index of melt flow under high load, I₂₁, less than 40 and the ratio of velocity of the melt current, I₂₁/I₂more than 40, preferably greater than 50. In another embodiment, the invention is a polymer based on ethylene copolymer is ethylene/α-olefin. In another embodiment of the invention α-olefin selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene, 1-hexene and 1-octene, and more preferably 1-butene and 1-hexene.

In one embodiment of the method according to the invention the polymer based on ethylene has a bulk density (or apparent density) of 24 lb/ft³(0.39 g/cm³) to 34 lb/ft³(0.55 g/cm³), preferably from 26 lb/ft³(0,41 g/cm³) to 34 lb/ft³(0.55 g/cm³), as determined according to ASTM D-1895. In another embodiment, the invention is a polymer based on ethylene copolymer is ethylene/α-olefin. In another embodiment of the invention α-olefin selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, preferably 1-butene, 1-hexene and 1-octene, and more preferably 1-butene and 1-hexene.

In one embodiment of the method according to the invention component Spadiut into the reactor separately from the catalyst and socializaton.

In one embodiment of the method according to the invention the component is solid at the feed to the reactor.

In one embodiment of the method according to the invention the component is a suspension in the feed to the reactor.

In one embodiment of the method according to the invention, the component includes a compound I and compound II, each of which is a solid form when submitting to the reactor. In another embodiment of the invention the component is a suspension.

In one embodiment of the method according to the invention, the component includes a connection I, which is in solid form when submitting to the reactor. In another embodiment of the invention the component is a suspension.

In one embodiment of the method according to the invention, the component includes a compound II, which is in solid form when submitting to the reactor. In another embodiment of the invention the component is a suspension.

In one embodiment of the method according to the invention for formula (I) ((R1CO₂)₂AlOH) R1 represents a hydrocarbon radical containing from 13 to 20 carbon atoms and preferably from 13 to 17 carbon atoms.

In one embodiment of the method according to the invention for formula (II) ((R2)_xN(R3OH)_y) R2 represents a hydrocarbon radical, containing the t 14 to 20 carbon atoms, preferably from 14 to 17; R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and x+y=3, and x has a value of 1 or 2.

In one embodiment of the method according to the invention a composition component further includes an inert hydrocarbon media, such as isopentane, hexane or mineral oil.

In one embodiment of the method according to the invention a composition component further includes mineral oil.

In one embodiment of the method according to the invention, the composition component is at least one compound selected from compounds of formula (I)at least one compound selected from compounds of the formula (II), and the inert hydrocarbon media, such as isopentane, hexane or mineral oil. In another embodiment of the invention, the mass ratio "of compounds selected from compounds of formula (I)", "compound selected from compounds of the formula (II)is about 1 to 1.

In one embodiment of the method according to the invention, the composition component is at least one compound selected from compounds of formula (I)at least one compound selected from compounds of the formula (II), and mineral oil. In another embodiment, the image is placed the mass ratio of "connections, selected from compounds of formula (I)", "compound selected from compounds of the formula (II)is about 1 to 1.

In one embodiment of the method according to the invention, the component includes at least one compound selected from compounds of formula (I)at least one compound selected from compounds of the formula (II), and the mass ratio "of compounds selected from compounds of formula (I)", "compound selected from compounds of the formula (II)is about 1 to 1.

In one embodiment of the method according to the invention the polymer-based olefin, and preferably a polymer based on ethylene, contains a fraction of at least two weight percent (calculated on the total weight of the polymer), which has a molecular mass greater than 10⁶g/mol, defined by respective fractions of square or traditional curve, or curve LS (light dispersion) GPC of the polymer. In another embodiment of the invention corresponding parts of the area are related to traditional GPC curve. In another embodiment of the invention corresponding parts of the area belong to the GPC curve with LS.

In one embodiment of the method according to the invention the polymer-based olefin, preferably a polymer based on ethylene, contains a fraction of at least four weight percent (in RA is couple on the total weight of the polymer), which has a molecular mass greater than 10⁶g/mol, defined by respective fractions of square or traditional curve, or curve LS (light dispersion) GPC of the polymer. In another embodiment of the invention corresponding parts of the area are related to traditional GPC curve. In another embodiment of the invention corresponding parts of the area belong to the GPC curve with LS.

The method according to the invention can include a combination of two or more variants of its implementation, as described in this document.

Polymer-based olefin method according to the invention can include a combination of two or more variants of its implementation, as described in this document.

Agents that increase the continuity of equipment

Unexpectedly, it was found that the types of agents that increase the continuity of the equipment, which inhibit the occurrence of static charge and prevent the formation of polymer layers on the walls of the reactor and agglomerates, will contribute to the production of polymers with very high molecular weight fractions, i.e. more than 10⁶and preferably such high as 10⁷or more, in quantities of more than one, preferably more than two weight percent and more preferably more than four or five mass percent is now per weight of the polymer.

Agents that improve the continuity of the equipment (SA), work particularly well in catalytic systems, which have a so-called positive activation energy, i.e. those in which the polymerization activity is positively influenced by the increase of reaction temperature. The invention also works especially well with catalysts, which have a very low rate of deactivation, i.e. with a rate constant of deactivation of the first order (K_d)<0.5 hour¹and especially <0.2 h^-1. These distinctive properties, although which is desirable for high output catalyst, especially unfavorable if the system is prone to the formation of a layer of polymer on the walls of the reactor and agglomerates. Any weak area of liquefaction or stagnation will then become the main area of occurrence of "hot spots", the formation of polymer layers on the walls of the reactor and agglomerates, as localized temperature will increase, further increasing the activity of the catalyst in the stagnation zone, leading to melting of the polymer and the need to shut down the reactor.

Determined that agents that increase the continuity of the reactor, provide smooth, trouble-free operation of the systems of polymerization in the gas phase and the fluidized bed and obtaining polymers with factions with full-time the high molecular weight of one or more United reactors. Data additives are preferably solids, or solid form at a temperature of injection into the reactor and consist of compounds of the General formula:

(R1CO₂)₂AlOH, formula (I)

where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;

(R2)_xN(R3OH)_ythe formula (II)

where R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms; R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, x+y=3, and x has a value of 1 or 2.

It was unexpectedly found that these supplements are even in the presence of acetalization (usually compounds trialkylamine)that are usually required to achieve full activity of the catalysts ziperovich type, despite the presence of functional groups that are usually reactionary to socialization, for example, carbonyl, hydroxyl and amine.

Specific types of catalyst Ziegler discussed in patent application U.S. US20070060725 (introduced in this document by reference), along with the options that will be considered further in this document. In a preferred embodiment of the invention a particular characteristic common to the catalysts used in the invention is the inclusion of active centers Zr and/or Hf with obtaining high molecular weight part of the polymer, and portovye solvents, used to produce catalytic solids.

Connection forms ROH also known as precursors static agents, so that the use of ROH compounds as solvents in the process of preparation of the catalyst additionally increases the potential of a high level of static charge. Resin with very high molecular mass also known as substances forming elevated levels of static charge in the production process in gas-phase reactors and fluidized bed reactor. Thus, although the resins are highly desirable, the production of these materials is much more difficult because of the aforementioned features of the catalytic system and the specific resin. It was found that the introduction of additives that increase the continuity of work in the polymerization reactor provides a smooth continuous processes with minimal formation of agglomerates and the almost complete exclusion of the formation of polymer layers on the walls of the reactor and pieces.

The exact mechanism of action of these additives that increase the continuity of the equipment, is not entirely clear. Based on a series of measurements it is concluded that they minimize the formation of static charge, however, a simple minimization of static charge (that is, cogenerative static charge in the fluidized bed is close to zero) insufficient to prevent the formation of agglomerates/polymer layers on the walls of the reactor, because the mere cessation of feed additives that improve the continuity of the equipment (SA), even with minimal voltage static charge can lead to the rapid formation of a polymer layer on the walls of the reactor and the reactors are shut down. Thus, as discussed above, the use of SA allows continuous production of polymers.

As discussed above, CA is usually a mixture of two components, both of high molecular weight compounds containing amino and/or hydroxyl functional groups. CA compounds are preferably solids or waxes. Preferred hydroxyl functionality is introduced in the form of compounds of formula(RCO₂)₂Al-OH), where R represents a hydrocarbon radical with the carbon atoms is from 13 to 25. Amine functionality is introduced in the form of compounds of the formula (R₂)_xN(R₃OH)_ywhere R2 again represents a hydrocarbon radical with the number of carbon atoms from 14 to 26, and R3 represents a hydrocarbon radical, for example methyl, ethyl, n-propyl, n-butyl or ISO-propyl radical. Especially preferred compounds are distearate aluminum and AS-990 (available commercially stearylamine).

In one embodiment, is sushestvennee inventions SA should represent a mixture of these two components in the ratio [(RCO ₂)₂Al-OH) (R₂)_xN(R₃OH)_y] from 0.5 to 1 to 2 to 1, preferably from 0.5 to 1 to 1 to 1 by weight. In another embodiment of the invention the mixture is fed directly into the layer of the polymerization reactor. Especially preferred ratio is approximately 1:1.

In one embodiment of the invention these components are injected in the form of a suspension of two solid components [(RCO₂)₂Al-OH) and (R₂)_xN(R₃OH)_y]. The preferred media for SA are based solvents mineral oils, such as Hydrobrite 380, Kaydol, and materials of similar viscosity. Submission of this SA must be maintained at a sufficiently low temperature so that both components remained solid before introduction into the reactor.

The preferred injection site SA is above the distribution plate and in the lower 1/3 part of the polymerization layer, i.e. in the area where most likely the formation of polymeric layers. An effective amount of this material is injected into the reactor to facilitate the good work and minimize the formation of polymer layers and agglomerates in the reactor. If there is a successive operation of the reactor, that is, if the content of the first gas-phase reactor is diverted to the second gas-phase reactor, the SA is usually administered only in the PE the first reactor in the sequence.

The SA and the catalyst is preferably introduced at various places in the reactor, i.e. at a certain vertical distance separating these two places, or if the submission is on the same level in pseudogenes layer, the injection point should preferably be separated by an amount of at least π/2 radians. The SA and the catalyst should not be physically mixed. Socialization also preferably injected directly into the fluidized bed, but it is more of a security process. When injection layer socialization must be separated from SA, preferably at least π/2 radian (with injection at the same level) or vertically offset from CA. Socialization and SA also should not be introduced in the form of a mixed stream.

Preferred catalysts

The expression "catalyst" or "catalyst composition"used herein refers to compounds of transition metals or their mixtures, which are used to accelerate polymerization of the monomers of the addition polymerization, usually in combination with one or more acetalization or activator compounds. The preferred catalysts are mixtures or complexes nepetalactone compounds of transition metals and of magnesium compounds, such as compounds floridamania, in the alternative case, called catalysts, Ziegler-Natta or type catalysts Ziegler-Natta.

In particular, the preferred catalytic compositions include magnesium dichloride or magnesium compound, which can be galogenirovannami to magnesium dichloride, and put on it the mixture of metals of group 4, especially the mixture of chlorides titanium chlorides of zirconium and hafnium chlorides, and combinations thereof, and compounds of titanium, zirconium and hafnium, which can be galogenirovannyie to the corresponding chlorides. Although it may be made by impregnating an inert carrier, the preferred method of obtaining is spray drying a solution comprising a magnesium compound and a mixture of metal compounds 4 groups in the primary diluent, especially a diluent comprising one or more C2-C6 alcohols, and the subsequent halogenoalkane formed of solid particles. The preferred halides of transition metals are a mixture of trichloride titanium (which can be obtained in the form of a complex with AlCl₃), zirconium tetrachloride and hafnium tetrachloride.

Preferred compounds that can be galogenirovannyie to the corresponding chlorides, are

magnesium-ethylcarbonate magnesium (Mg(C₂H₅CO₂)₂

hafnium-Hf(OR)_4-xCl_ywhere x is equal to the value from 0 to d is 2 and R is methyl, ethyl, isopropyl, isobutyl or butyl

titanium-Ti(OR)_4-xR1_xwhere x is a value from 0 to 2 and R represents methyl, ethyl, isopropyl, isobutyl or butyl, R1 represents a chelate forming ligand, such as a particularly preferred 2,4-pentandiol or Cl,

zirconium-Zr(OR)_4-xCl_xwhere x is equal to the value from 0 to 2, and R represents methyl, ethyl, isopropyl, isobutyl or butyl. The basic requirement is that the subsequent material (spray drying or substrate) was dry and loose to ensure subsequent operations.

The preferred halogenation agents are alyuminiiorganicheskikh halides, especially sesquichloride alkylamine, such as sesquichloride ethylaluminum (Al₂(C₂H₅)₃Cl₃). The relative amount of magnesium dichloride, halides of transition metals and used halogenation agent, as well as the halogenation agent - all this affects the relative operating parameters of the resulting catalytic composition.

Data are the preferred catalysts for use in the invention also have a few additional attributes, such as the following: (a) they provide for the production of polymers with high molecular weight fractions greater than 10⁶g/mol, (b) they have a relatively low rate of decomposition, t which has a constant first order decay less than 0,8 h ^-1, (C) distribution of the catalyst particles in size range "(d90-d10)/d50 less than or equal to 2, and (d) they provide resins with high installed bulk density.

Preferred catalysts are also very active at low levels of added socializaton, with excellent polymerization activity, reflected in the molar relationship Al/Ti, is added (with the introduction of socializaton) in the reactor is less than the 35/1 and such low as 20/1, although can be used in higher quantity. When used in the systems of several reactors preferred catalysts can save complete polymerization activity in the subsequent reactor(s), even in the absence of the submission of additional socializaton.

Preferred catalysts obtained by dissolution of the magnesium compounds, titanium compounds, the compounds of hafnium and/or zirconium compounds in an alcohol solvent in the presence of filler/filling agent, if the composition is spray dried on a medium such as a highly porous silica gel, if the catalyst is physically contained within the pores of the mentioned media. The transition metal compounds can be halides, alkoxides, mixed alkoxide/2,4-pentanedionate and mixtures thereof. It is only necessary to dissolve the cost in an alcohol solvent. Particularly preferred titanium compounds are TiCl₃(restored either hydrogen or aluminum) and Ti(2,4-pentanedionate)₂(OR)₂where R may be ethyl, isopropyl, n-propyl or n-butyl. Preferred compounds of Zr and Hf are the chlorides or alkoxides (for example, atoxic, propoxide, piperonyl). Preferred magnesium compounds are MgCl₂and ethylcarbonate magnesium.

Additional optional components of the composition used to produce the precursors of catalysts spray drying include the following:

a) one or more fillers or filling agents;

b) one or more internal electron donor and/or

C) one or more compounds of the secondary solvent selected from the group consisting of siloxanes, polyalkylene glycols, simple C1-4 alilovic or phenyl esters, or derivatives of simple diesters of alkylene glycols and crown ethers.

Any thin-dispersed solid material, which is inert to the other components of the catalytic system and subsequent polymerization, can be used as filler or filling agent for the compositions of the present invention. It is desirable that the filler was added volume and strength of the resulting solid particles of the spray is Oh drying, prevention of destruction of particles in the formation and drying of the particles. Suitable fillers may be organic or inorganic. Examples include silicon dioxide (especially fuming silicon dioxide, boron nitride, titanium dioxide, zinc oxide, polystyrene and calcium carbonate. It is preferable Smoking, hydrophobic, surface-modified silicon dioxide, because it imparts high viscosity of the suspension and good durability particles spray drying. The filler should not contain absorbed water and preferably also be surface-modified. Surface modification, such as treatment with silane, removes the reaction of hydroxyl or other functional groups from the surface of the filler.

The filler is not used to provide inert carrier for deposition thereon of the catalytic composition. Accordingly, fillers with a high specific surface area are not essential or desirable for the application. In the ideal case, the filler should have a specific surface area of less than 20 m²/g, more preferably less than 10 m²/, Suitable fillers should have an average particle size (D50) of not more than 50 μm, preferably not more than 10 μm. A sufficient amount of filler is preferably used to produce a slurry suitable for spray drying, i.e. mixtures vkluchaya the primary diluent, which is liquid under normal atmospheric conditions, but is easily evaporated at reduced pressure or elevated temperature. Desired, the suspension contains a filler in an amount of from 0 percent by weight to 15 percent by weight, preferably from 2.5% by weight to 10 percent by weight. When spray drying the formed droplets form a discrete catalyst particles after evaporation of the main diluent. Desirable, the amount of filler contained in the formed catalyst particles is from 0 to 50 percent, preferably from 10 to 30 percent based on the total weight of the composition. The catalyst particles of the spray drying, the thus obtained usually have an average particle size (D50) of 5 to 200 μm, preferably from 10 to 30 microns.

Connection of secondary diluent preferably used to obtain particle spray drying, having a high degree of uniformity in particle size and sphericity. The resulting catalytic composition spray drying have high homogeneity and excellent catalytic activity, with reduced formation of the fine fraction. In addition, some of the above secondary diluents can also act as internal electron donors, when the p component in the desired manner should be included in the composition. In a preferred embodiment of the invention the connection of the secondary diluent selected from siloxanes, polyalkylene glycols, simple C1-C4 alilovic or phenyl esters or derivatives of simple diesters of alkylene glycols and crown ethers.

Preferred polyalkylene glycols include polyethylene glycol containing from 2 to 5 alkalinising duplicate links. Siloxanes and crown ethers are particularly preferred secondary diluents, because they can provide improvements in the morphology of the particles, as well as increased activity, compared with polymerization reactions conducted in the absence of data siloxanes or crown ethers. Preferred siloxanes include hexamethyldisiloxane, hexaethyldisiloxane and hexaphenyldisilane. The preferred crown ethers include simple 18-crown-6-ether and a simple 15-crown-5-ether. Secondary diluent preferably is contained in the catalytic composition in an amount in the range from zero to 10 percent, based on the total weight of the catalytic composition.

Materials that can be used as carriers, if the catalytic composition thus obtained, are crushed solid porous materials, which are inert to the other components of the catalytic system and inert the subsequent polymerization. Suitable materials for the carrier include inorganic materials such as oxides of silicon and/or aluminum. Typically these materials have an average particle size from about 10 microns to about 250 microns, preferably from about 10 microns to about 150 microns, and a specific surface area of at least 3 square meters per gram, preferably at least 50 square meters per gram. The polymerization activity of the catalyst can be improved through the use of media on the basis of silicon dioxide having an average pore size of at least 80 angstroms, preferably at least 100 angstroms. The material of the medium should be dry and not contain absorbed water. Drying of the material of the object can be heated, for example, at a temperature of at least 600°C, when the media use silicon dioxide. Alternatively, when using silicon dioxide, it may be dried at a temperature of at least 200°C and do not necessarily processed from about one weight percent to about eight weight percent of one or more such compounds, as alkylamine, halide alkylamine or alkylzinc. Suitable compounds have the formula M(R₄)_zX_ywhere M is either Al or Zn;y is zero, if M denotes Zn, and z is 2; and when M is Al, z+y=3 and z has a value of 2 and 3. R4 may represent methyl, ethyl, isobutyl or n-hexyl. Ethyl group are particularly preferred.

Appropriate composition of the precursor, which is impregnated carrier contains from about 3 percent by weight to about 50 percent by weight, preferably from about 15 percent by weight to about 40 percent by weight of the component of Mg/Ti/Hf/Zr catalyst.

Spray drying can be conducted by any known method, spray drying, known in this area. One example of a suitable method, spray drying involves the atomization of the composition of the catalyst, optionally while heating, and drying the formed droplets. The sputtering is carried out using any suitable spray device by obtaining the individual drops, which after drying to form particles of spherical or nearly spherical shape. The sputtering is preferably carried out, passing the slurry composition of the catalyst through the spray device together with an inert drying gas, i.e. gas, which is a research considers non reactive under the conditions used during spraying, and helps to remove volatile components. For holding the spray can be used to spray the tion nozzle or a high-speed centrifugal disk, resulting in a spray or dispersion of droplets of the mixture. The volumetric flow of drying gas, if used, is preferably significantly greater than the volume flow of the suspension from carrying out spraying of the suspension and/or evaporation of the liquid medium. Typically, the drying gas is heated to such a high temperature as 200°C to accelerate the atomization and drying of the suspension, however, if the volumetric flow of drying gas is maintained at a high enough level, you can use a lower temperature. Suitable pressure spray from 1 to 200 psi (100 to 1.4 MPa). In the alternative case can be applied negative pressure in the section of the outlet of the spray dryer to effect the formation of solid particles. Some examples of methods spray drying, suitable for use with catalytic composition of the present invention, include those disclosed in U.S. patent 5290745, U.S. patent 5652314, U.S. patent 4376062, U.S. patent 4728705, U.S. patent 5604172, U.S. patent 5306350, U.S. patent 4638029, patent SSA and patent application U.S. 20070060725, each of which is introduced herein by reference.

By adjusting the speed of the atomizing wheel and the size of the holes of the spray used during spray drying, it is possible to obtain particles having a desired average size of the piece is, for example, 5-200 μm. By adjusting the composition of the raw material supplied to the spray affect the continuity of the catalyst particles (i.e. the volume of internal cavities), which would also affect bulk density of the final polymer. Correct regulation of both parameters: conditions of spraying and composition of raw materials ensures that the particles of the catalyst precursor, which has a narrow distribution of particle size, low spread and provide resins with a high bulk density.

The preferred composition of the precursor will have the formula (in moles) of Mg_xTiHf_yZr_zwhere x is the value from 1 to 20, y is a value from 0 to 10, and z is a value from 0 to 10, provided that y+z is >0. Particularly preferred ranges are as follows: x from 3 to 10, y from 0 to 2 and z is from 0 to 2.

Impregnation can be carried out using methods disclosed in U.S. patent 5068489 and references therein; each of which is introduced herein by reference.

Immediately after the formation of the catalyst precursor (a composition comprising a Mg/Ti/Hf/Zr) halogenous, preferably by alkylamidoamines (AlR_3-xCl_xwhere x is equal to the value from 1 to 2) or boron chloride (i.e. RBCl₂or BCl₃). Time, temperature and concentration of the halogenation agent - all can Ulitina final catalyst properties and performance. As mentioned earlier, the resulting catalyst product after the halogenation can be washed with the removal of the products of the reaction or, preferably, used directly. Typical methods of halogenation is given below.

Dried mineral oil is loaded into a clean mixing container in a quantity sufficient to obtain a uniform suspension of powder catalyst precursor, usually from 20 to 35 percent by weight of the suspension.

Once the powder is dispersed, add the halogenation agent. Material type with such speed, that did not leak excessive reaction in the mixing tank. The number of added material depends on the desired level of halogenation predecessor. Usually by the reaction of alkylhalogenide (one of the preferred halogenation agents) with a residual alcohol in powder predecessor will be released gas. Stirring is continued for a time sufficient to disperse the reagents. Then, if the temperature in the mixing tank is still lower than the desired final temperature of the reaction, bring the heat to reach this temperature and then maintain it for a period of time to complete reactions. In the alternative case can be made cooling at all stages, e is whether the desired temperature of the halogenation below, than the temperature, which reaches o adiabatically the reaction mixture. Then the catalyst was unloaded and stored until use in an atmosphere of inert gas.

Another alternative method is suitable for use with the compositions of the precursor or the media, or spray drying. Under halogenation completed using a light hydrocarbon diluent, such as isopentane or hexane. Then the suspension can be either filtered or desantirovanie with the removal of light hydrocarbons. Optional the filter cake may be washed with additional removal of any reaction products of the halogenation. Finally, the composition of the halogenated precursor may be either dried to a granular solid catalyst, or again dispersed in the diluent on the basis of mineral oil for suspension filing.

Other alternative methods of halogenation can use a linear system, essentially rigid flow, such as that disclosed in U.S. patent 6187866 or U.S. patent 6617405, each of which is introduced herein by reference. In this embodiment of the invention, the powder catalyst precursor is first dispersed in mineral oil, mixed with reagents and pump line into the reactor, polymerizati is. Suitable methods of heating and cooling is used to regulate the actual temperature of the catalyst, and time flowing reaction is given as the time spent in the different zones (in practice, or small containers with a minimum of back mixing or pipe/tubing large length). Then the catalyst is injected directly into the polymerization reactor.

The conditions used at the stage of halogenation (required for activation of the catalyst precursor), also determines the amount of high-molecular fraction, formed by the catalyst, the characteristic polymerization activity of the catalyst using a standard set of conditions, the particle size of the final polymer and bulk density of the polymer. Too high concentration of halogenation agent can inhibit the activity part of the catalyst, which forms a very high molecular weight tail that is too low leads to insufficient catalytic activity. Preferred levels of halogen residual alkoxide functionality (meaning that it includes free alcohol remaining in the particles of the catalyst precursor, and alkoxides, which can either be formed by the reaction of the components of transition metals with an alcoholic solvent, or contained as part of the transition metal, and are measured rest the rhenium compounds predecessor in the aquatic environment, so all the alkoxides are converted in the preceding alcohols, and subsequent gas chromatographic determination) lie in the range from 0.5 to 4 moles of Cl contained in the halogenation agent, per mole of alkoxide, with a preferred range of 1 to 3.

Socializaton represent those typical of Ziegler catalysts, for example, trialkylaluminium connection and dialkylaminoalkyl. Preferred socializaton include trimethylaluminum, triethylaluminum, tri-n-hexylamine and three-ISO-butylamine.

Preferred polymers

The preferred polymers are those in which the presence of high molecular weight "tail" is predominant, that is, resin, designed for molding blown film, tubes, inflatable films, etc. that require a higher degree of swelling of the resin or melt strength for efficient processing. The method is applicable to the production of polymers, which contain a measurable share of very high-molecular fragments with a molecular mass greater than 10⁶with mass fractions greater than 1% by mass, more preferably 2 percent by mass, and more preferably greater than 4 percent by weight. The polymers produced by this method are disclosed in which in the process of simultaneous consideration of the provisional application U.S. No. 61/017947.

Paul is Marisela

The catalytic composition may be used for any reaction for which usually apply polymerization catalysts of the type Ziegler-Natta, especially for suspension, dilution, dispersion, and gas-phase polymerization of olefins. These reactions can be carried out using known equipment and reaction conditions, and is not limited to any particular type of reaction system. This polymerization can be performed periodically by the way, in a continuous way or by using a combination of both. Usually suitable temperature polymerization of olefins are in the range from 0°C to 200°C, and the polymerization process is carried out at atmospheric pressure, the pressure below atmospheric or greater than atmospheric pressure.

Preferably gas-phase polymerization is carried out at elevated pressure in the range from 1 psi to 1000 psi (7 kPa to 7 MPa) and at a temperature in the range from 30°C to 130°C. Particularly suitable for use are gas-phase system with mixing or fluidized bed. Traditional gas-phase process in the fluidized bed is carried out, passing a stream containing one or more olefinic monomers continuously through a reactor with a fluidized bed, under the reaction conditions, sufficient for polymerization of the monomer(s), in the presence of an effective quantity is the number of catalytic compositions and activating socializaton, at a speed sufficient to maintain a layer of solid particles in a suspended condition. A stream containing unreacted monomer, is continuously withdrawn from the reactor, compressed, cooled, optionally fully or partially condense, as disclosed in U.S. patent 4543399, U.S. patent 4588790, U.S. patent 5352749 and U.S. patent 5462999 (each of which is introduced in this document by reference), and sent for recycling to the reactor. The product away from the reactor and add an additional monomer in the recirculation flow. In addition, can be used fluidizing additive such as carbon black, silica, kaolin or talc, as disclosed in U.S. patent 4994534 (introduced in this document by reference). Suitable systems are gas-phase reactions are also disclosed in U.S. patent 5527752 (introduced in this document by reference).

DEFINITION

All digital intervals herein include all values from the lower value and the upper value, in increments of one unit provided that there is no separation of at least two units between any lower value and any higher value. For example, if it is alleged that a compositional, physical or other property, such as, for example, molecular weight, and the melt index, ranges from 100 to 1000, it is assumed that all individual values, such as 100, 101, 102, etc. and potentially, such as 100-144, 155-170, 197-200, etc. clearly expressed in this description of the invention. For intervals that contain values that are less than one or contains a proportion of more than 1 (for example, of 1.1, 1.5, and so on), one unit is considered 0,0001; of 0.001, 0.01 or 0.1, respectively. For intervals containing one meaningful number less than ten (for example, from 1 to 5), one unit is usually considered to 0.1. These are just examples of what is meant exactly, and all possible combinations of digital values between the lowest value and the highest value should be considered to be clearly specified in the application. Digital intervals specified, as discussed herein with reference to the density, melt index, the mass percentage of component and other properties.

The term "polymer" is used herein to refer to homopolymer, copolymer or ternary copolymer. The term "polymer"used herein includes copolymers, such as, for example, those obtained by copolymerization of ethylene with C3-C10 alpha-olefin, or propylene with ethylene and/or C4-C10 alpha-olefins.

The term "copolymer"used herein refers to polymers, the polymer is in securitization, at least two monomers of different types. The General term "copolymer" includes, therefore, the copolymers used to refer to polymers derived from two monomers of different types, and the term also includes polymers derived from more than two monomers of different types.

The term "polymer-based olefin used herein, refers to a polymer that includes at least the basic mole percent of the olefin, for example ethylene or propylene, or the like (based on the total number of polymerized monomer and optionally one or more additional comonomers. As is well known in this field, the polymer contains olefin polymerized form.

The term "polymer based on ethylene", used herein, refers to a polymer that includes at least a primary molar percent ethylene (based on the total number of polymerized monomer and optionally one or more additional comonomers.

The term "copolymer of ethylene/α-olefin used herein, refers to a copolymer based on ethylene, which includes at least basic mole percent ethylene (based on the total number of polymerized monomer), α-olefin and optionally one or more additional the different comonomers.

The term "inert gas"used herein refers to any gas inert to the catalyst and reactants. Usually this term refers to nitrogen and helium, but can also refer to directionspanel aliphatic hydrocarbons.

The term "static charge" and "chart of static charge"used herein respectively refer to static pressure in the layer of the reactor and the physical appearance of traces of static electricity.

TEST METHODS

Density

The density of the resin was measured by the method of displacement by Archimedes, ASTM D792-00, method B, in isopropanol. Measurements were performed on samples within one hour after molding, after conditioning in the bath with isopropanol at 23°C for 8 minutes to achieve thermal equilibrium before measurements. The samples were extruded according to the standard ASTM D-4703-00, Annex a, with the five-minute initial period of heating at a temperature of approximately 190°C. and at a cooling rate for the procedure With 15°C/min, the Sample was cooled to 45°C in the press in continuous cooling to a state of "cold touch".

The rate of flow of the melt in extrusion plastomer

Measuring the speed of the melt flow of the polymer based on ethylene were conducted according to ASTM D-1238-04, condition the conditions of 190°C/2,16 kg, condition 190°C/5 kg and condition 190°C/21,6 kg, which is known as the I₂, I₅and I₂₁, respectively. The rate of flow of the melt obratnoproportsionalno molecular weight of the polymer. Thus, the higher the molecular weight, the lower the flow velocity of the melt, although the dependence is not linear. The ratio of the velocities of the melt (MFR) is the ratio of the flow rate of the melt (I₂₁) to rate melt flow (I₂), unless otherwise specified.

Helpanimals chromatography (GPC)

The molecular weight of the polymer was characterized by high-temperature gel chromatography with a three-dimensional detector (3D-GPC). The chromatographic system consisted of a high temperature 150°C chromatograph Waters (Milford, MA)equipped with a detector low-angle laser light scattering Precision Detector (Amherst, MA), model 2040, and a detector 4-capillary differential viscometer, model 150R from Viscotek (Houston, TX). Light-scattering detector with an angle of 15° was used for calculation purposes. The concentration was measured by an infrared detector IR4) from Polymer Char, Valencia, Spain.

Data collection was performed using Viscotek TriSEC, version 3, and 4-channel devices in the organization and storage of data Viscotek Data Manager DM400. Solvent media was 1,2,4-trichlorobenzene (TCB). The system was equipped with linear device Degas the tion of solvent from Polymer Laboratories. Carousel unit worked at 150°C and the column block worked at 150°C. the Columns were four 30-theantimicrobial column caliber 20 microns from Polymer Laboratories Mixed-A. Standard solutions of polymer were prepared in the TCB. The samples according to the invention and comparative samples were prepared in decline. Samples were prepared at a concentration of 0.1 gram of polymer in 50 ml of solvent. Chromatographic solvent (TCB) and the solvent for preparation of samples (TCB or decalin) contained 200 mln butylacetamide of hydroxytoluene (EIT). Both sources solvent was purged with nitrogen. Samples of polyethylene was carefully shaken at 160°C for 4 hours. The volume of injection was 200 μl and the flow rate was 1.0 ml/min

The preferred set of columns is the particle size of 20 microns and gel "mixed" porosity for the division of fractions with the largest molecular weight, in accordance with the invention.

The calibration set GPC columns was carried out on 21 polystyrene standards with narrow molecular weight distribution. Molecular weight standards were in the range from 580 to 8400000 g/mol and were arranged in 6 "cocktail" mixtures, at least, with the separation between individual molecular weights on the order.

Molecular weight standards polystyrene peaks was counted in molecular mA is su polyethylene, using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968).

M_PE=A×(M_polystyrene)^In$$$$(1A)

where M is the molecular weight, And has cited the value 0,4316 and is 1.0. Alternative value And, in this document referred to as "q" or "q factor"was determined using a predetermined mass-average molecular weight linear ethylene homopolymer with a wide molecular weight distribution (Mw~115000 g/mol, Mw/Mn~3,0). Called the mass-average molecular mass was obtained in accordance with the publication Zimm (Zimm, B.H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The response factor, K_LSlaser detector was determined using the certified values mass-average molecular weight of NIST 1475 (52000 g/mol). Method of obtaining alternative "q factor" is described in more detail below.

A polynomial of the fourth order was used for the selection of the appropriate equivalent polyethylene calibration points obtained by the equation 1A, they observed elution volumes. Valid polynomial selection was derived to relate the logarithm of equivalent molecular mass polyethylene with the observed volumes of e is investing (and associated forces) for each polystyrene standard.

The total number of theoretical plates set of GPC columns used for Eicosane (obtained at a concentration of 0.04 g in 50 ml of TCB and dissolved within 20 minutes with gentle shaking). The number of theoretical plates and the symmetry was measured on 200-Microlitre injection according to the following equations:

The number of theoretical plates=5,54*(RV the height/width of the peak at half-height))²$$$$(2A),

where RV represents the amount of deduction in milliliters and the width of the peak in milliliters.

Symmetry=(width of the rear of the peak at one-tenth the height of the RV on the maximum peak)/(RV maximum peak-Width of the front of the peak at one-tenth the height)$$$$(3A)

where RV is the volume retention in milliliters and the width of the peak in milliliters.

The number of theoretical plates for chromatographic system (based on Eicosane, as discussed above) should be more than 22000 and symmetry must be between 1.00 and 1.12 in.

To identify each deviation detector used a systematic approach in accordance with the publication Balke, Mourey, et al (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), using data from the three detectors, the analysis of linear polite novogo of homopolymer with a wide molecular weight distribution (of 115,000 g/mol) and narrow polystyrene standards. A systematic approach was used for the optimization of each deviation detector results on the molecular mass, probably close to what was observed when using the traditional method of GPC. The total concentration of injection used to determine the molecular weight and the characteristic viscosity was obtained by space infrared spectrum of the sample and the calibration of infrared detector (or mass constant) linear polyethylene homopolymer with a molecular weight of 115,000 g/mol. Chromatographic concentration took low enough to exclude an appeal to the 2nd virial coefficient (influence of the concentration effects on the molecular weight).

Calculations of Mn, Mw and Mz on the results of GPC using detector IR4 (traditional GPC) and narrow standards calibration, was performed according to the following equations:

Where IR_iM_PE,iimagine the response, adjusted for baseline infrared spectrum and molecular weight polyethylene traditional calibration for i-th part of the IR response, double the data set on the volume of elution. Equation 4A, 5A, 6A and 7A are derived from polymers obtained in solutions of decline.

"q-factor", discussed above, was obtained by selecting "q" or As in equation 1A, while Mw is the mass-average molecular mass, aschiana using equation 5A, and the corresponding polynomial volume retention is not consistent with independently defined by the value of Mw obtained in accordance with Zimm for a broad linear polyethylene homopolymer (of 115,000 g/mol).

The mass percentage of polymer fractions with molecular weights > 10⁶g/mol was calculated by summing the IR responses, adjusted for baseline IR_ifor parts of volumes of elution, whose calculated molecular mass M_PE,iexceeded 10⁶g/mol, and expressing this partial sum as a fraction of the sum of all IR responses, adjusted for baseline, from all parts of the elution volume. A similar method was used to calculate the weight percent of polymer fractions with absolute molecular weights >10⁶and 10⁷g/mol. The absolute molecular weight was calculated using the signal from the laser light scattering angle of 15° and IR concentration detector, M_PE,I,abs=K_LS*(LS_i)/(IR_iwhen using the same calibration constants K_LSthat equation 8A. The combined data set of the i-th part of the IR response and LS response was selected, using a certain offset, as discussed in a systematic approach.

In addition to the above calculations, was also calculated an alternative set of values of Mw, Mz and M_z+1[Mw(abs), Mz(abs), Mz(BB) and M_z+1(BB)] method, etc is glazhennym Yau and Gillespie, (Yau and Gillespie, Polymer, 42, 8947-8958 (2001)), and dened by the following equations:

where K_LS=LS-MW - calibration constant. As explained above, the response factor, K_LSlaser detector was determined using the certified values mass-average molecular weight of NIST 1475 (52000 g/mol).

where LS_irepresents the signal light scattering at an angle of 15 degrees and M_PE,Iinvolves the use of equations 1A and linearization LS detector such as that described above.

To monitor deviations in time, which may contain the component elution (caused by chromatographic changes) and the velocity (caused by changes in pumping), you usually use the last narrow peak elution as "peak marker velocity". The marker velocity, therefore, is based on technologo token flow, dissolved in blueroom the sample obtained in the TCB. This token velocity used for the introduction of linear amendment velocity for all samples by shifting dejanovich peaks. For samples dissolved in decline, dekalogy the solvent gives a huge splash on the curve of elution, which covers the detector IR-4, so no deck is new peak can not be used as a marker velocity. To minimize the effect caused by changing the flow rate, used rheological properties of linear polyethylene homopolymer (of 115,000 g/mol), obtained in the TCB with the Dean as a marker velocity, as the same rheological properties of solutions of samples obtained in the experiment with decaline on the same carousel.

Experimental part

The following examples are provided to illustrate the present invention and not to limit.

The mixture agent that increases the continuity of the equipment

To 800 grams of deaerated mineral oil (Kaydol available from Crompton) was added 100 grams of distearate aluminum (solid) and 100 grams of commercially available ethoxylated of stearylamine, AS-990 (solid). Both compounds was previously dried under vacuum for 24 hours in nitrogen atmosphere. The resulting suspension was used as such.

Obtaining catalyst

The catalyst precursor was obtained by dissolving the components on the basis of transition metals and compounds of magnesium in an alcohol solvent. A typical composition may be obtained by spray drying. The term "relationship target metals" refers to x, y and z described above. Thus, the catalyst described as 5/1/1/0, will have the following molar ratio metal: 5 moles Mg, 1 mol Ti, 1 mol Hf is the absence of Zr.

Some examples of formulations of the catalyst are presented in table 1.

Then the raw material was subjected to spray drying in a spray dryer NIRO "diameter by 4 feet with a spray wheel FS-10. The maximum speed of the atomizing wheel was 24000 rpm Conditions for spray drying are presented in table 2. The dried powder of the precursor was then halogenerator. Explanatory halogenoalkane shown below.

Table 2 Conditions the spray is more drying
	Catalyst	Catalyst	Catalyst
	Example 1	Example 2	Example 3
The pace. at the entrance, With	165,3	163,9	163,3
The pace. output	101$$\to$$105	101	110
The outlet temperature from the condenser,	5	-1	-2
The velocity of the gas, lb/HR	574	582	577
The speed of the raw material, lb/HR	30	36	34,5
Oxygen, mlnc	0	0	0
Sprayer speed, % of the maximum	95	95	70
Analysis of predecessor
mol Mg/g	of 2.21	2,33	to 2.06
mol Ti/g	0,43	0,43	0,42
mol Hf/g	0,44	0,23	0,42
mol Zr/g	0	0,21	0
Mg/Ti	5,14	5,42	4,90
Mg/Hf	5,02	10,13	4,90
Mg/Zr		11,10
Mass. % residual ethanol	26,7	19,5	5,9
Mass. % residual butanol			26,8
D10	the 13.4	13,9	19,6
D50	25,5	26,1	37,5
D90	47,4	48,7	68,0
Scatter	1,33	1,33	1,3

Illustrative example of the method of periodic chlorination

All operations were carried out in the atmosphere of inert gas (nitrogen), containing less than 5 mln moisture and oxygen.

In a clean mixing container was loaded 2500 ml of dry mineral oil, and the temperature controller was set at 20°C. the Stirrer was switched on 50 percent of its maximum speed (~35 rpm). The powder precursor (typically 300-700 grams) was loaded into the vessel and the contents were stirred for 30 minutes with dispersion predecessor.

Halogenation agent, sesquichloride ethylaluminum (EASC), was diluted to 50 percent by weight of dry mineral oil and loaded according to the recipe within approximately a ten-minute period to prevent foaming su is bedstvie selection of ethane. The introduction of the reagent was stopped if there was excessive foaming or if the temperature rises above the desired end temperature of the reaction. Introduction resumed after the suppression of foaming and reduce the temperature to less than the desired final reaction temperature. Excessive temperature rise was defined as within 5°C from the desired end temperature of the reaction. Thus, if the final temperature was 35°C, and the internal temperature reached 30°C, the introduction of the reagent was stopped to cool the mixture.

The mixture was stirred for another 60 minutes, and the temperature was raised to the final temperature of the reaction (as shown in the examples) during this time. Thereafter, the catalyst was ready for use and kept in a nitrogen atmosphere prior to use.

Obtaining catalyst 4

The results of the catalyst precursor are shown in table 3

The spray drying conditions were essentially the same as that used in example 1 catalyst, except that the sprayer speed was 90 percent of the maximum. Cooperated predecessor spray drying with 2.0 mol Cl per mole of ethoxide or shared alkoxide, measured in the catalyst. The source of Cl was sesquichloride ethylaluminum (EASC).

The balance of the mass - Concentration suspensions Ti (in suspension)=0,0804 mm/gram

The balance mass is the Ratio of Al/Ti=13,2.

The final reaction temperature was 35°C, and the temperature of the reaction mixture maintained at this temperature for 60 minutes. The EASC solution was loaded during the time span of 45 minutes. The ethane formed by the reaction of groups ethylaluminum with ethoxide, were periodically taken. Then used the catalyst in the form in which it was received.

Polymerization

All experiments used the standard gas-phase reactor with a fluidized bed, as described in U.S. patent 617866, introduced in the present document by reference.

Example 1 polymerization (comparative)

The reactor was run using pre-dried seed layer, in accordance with the following method. The reactor is a gas-phase, fluidized bed discussed in U.S. patent 6187866 and U.S. patent 6617405, each of which is represented by reference.

The reactor was pre-dried by purging with nitrogen until the water content is less than 20 mlnc Then the reactor was loaded to approximately 120 pounds of seed layer (gas-phase reactor before starting the loaded granular "seed" layer for accelerating the dispersion of the catalyst). Plastic seed layer was obtained when using catalyst UCAT G-500 (available from Univation Technologies) and he had the I₂₁~30 and density 0,950 g/cm³.

The reactor was dried at low pressure up until the moisture content was below 10 mlnc when using the temperature in the jacket of the heat exchanger 90°C. the pressure in the reactor increased with N₂up to 150 psi. Triisobutylaluminum (TIBA) (1400 cm³; 2.5 wt.% in isopentanol solvent) was loaded in one hour and provided its circulation for an additional one hour (two hours) at 90°C and 150 psi at closed valve. The pressure in reacto the e down to 10 psi and was twice purged with nitrogen high pressure.

To the reactor was added an additional 600 cm³25 wt.% TiBA (all at once), and in the reactor were created the conditions of polymerization as follows (C6=1-hexene, C2=ethylene).

Polymerization initiated within two hours from the beginning of the filing of the catalyst and slowly increased to the desired level from 30 to 35 pounds/hour. Reaction conditions are given in table 4. As soon as the reaction d is Steagall act of stable mode, observed that the absolute level of the static voltage is uniformly increased, as shown in figure 1. The formation of a polymer layer on the walls of the reactor and clogging due to system lock unloading of the product was less than 24 hours after fixing a high level of statics. Product properties are presented in table 5.

Example 2 polymerization (comparative)

The reactor was re-launched using a method similar to the one described above. The conditions were the same as above, except that the partial pressure of ethylene was initially set at 75 psi and slowly lowered it to 30 psi after reaching steady state of the reaction. Supported the concentration of isopentane 15-16 molar percent. The flow of catalyst started at 4.0 cm³per hour, and the reaction was observed within one hour from the beginning of the filing of the catalyst. Reaction conditions were set to obtain a polymer that meets the requirements of the specifications. Reaction conditions shown in table 6, and the product properties are shown in table 7.

It is noted that the static charge was increased to high levels, and stopping the reaction the ora was due to block discharge of the product within 12 hours since the establishment of the high level of static charge. This result is shown in figure 2.

Static charge, especially when it is negative at levels less than -1000 volts, usually leads to the formation of a layer of polymer on the walls of the reactor. In this case, the observed values below -3000 (sensor interval ranged from +3000 to -3000 volts).

Example 3 polymerization (invention)

The reactor was run, using a technique similar to that used in example 2. In this polymerization agent that increases the continuity of the reactor (SA, consisting of 10 wt.% distearate aluminum and 10 wt.% AS-990, dispersed in mineral oil) (20 cm³), pre-loaded to run a layer of 100 lb seed layer before the supply of raw materials. Received several samples polymerized at different reaction conditions and using different socialization. Reaction conditions in the process are given in table 8. Once the reactor is successfully started, the supply SA continued with such speed that the formation of a polymer layer on the walls did not occur due to excessive levels of static charge. Supply SA supported with such speed that ~35-70 mlnc by weight, based on the speed at which imerissia, kept in the fluidized bed. This level of content of the additive provided the continuous operation of the reactor.

When using agent improve continuity of equipment supported the stability of the reactor. This is illustrated in figure 3 (covers polymerization 3(1)-3(7)). Work was normal, without shutdowns and lasted for 4.5 days without operational problems. The data of table 8 include polymerization processes, depicted in figure 3.

The polymerization processes 3(1)-3(4) illustrate the regulation MFR (I21/I2) composition of socializaton. Socializaton based triisobutylaluminum give unexpectedly shorter MFR (measured at I21/I5 / I21/I2) in comparison with triethylaluminium.

The polymerization processes 3(5)-3(6) show the effect of the concentration of aluminium MFR. In the polymerization process 3(7) reaction conditions were set so as to increase the velocity of the polymer melt to a closer analogue of example 3(5). You should note that the MFR is still higher than for the main event.

The influence of the composition of socializaton on the MFR was evaluated by comparing the polymerization processes 3(4) 3(8). This difference in the values of MFR (45 vs. 55) indicates an increase in high molecular weight parts of the resin obtained in the presence of a catalyst. nelogichny the result is visible when comparing polymerization processes 3(9) and 3(5).

The influence of the type of socializaton on the properties of the resin and MFR additionally observed when comparing polymerization processes 3(13) 3(14). Depending on the desired properties, a simple change in socializaton can change the value of MFR formed polymer, without modifying the catalyst. It is essential for the industrial process, because the change of socializaton (input in the form of a solution or in the form of pure alkylamine) simply requires changing the filing of one raw material to another. Change catalysts requires cessation of catalyst and is accompanied by a loss of valuable production time.

The second set of samples was obtained with the use of TnHAL as socializaton. As can be seen from figure 4 (covers polymerization processes 3(8)-3(12)), the work was supported over a long period of time due to the use of SA. Technological data for this period of time is also given in table 8 (polymerization processes 8-12). Finally, SA was disabled at the time of obtaining a polymer with a low index of flow. The work continued for approximately two days, and then the reactor was shut off and examined. All surfaces have been contaminated by a polymer layer of a thickness of less than 0.25 inches, which can be removed only by a scraper or other mechanical methods. The exception stood the Lyali thermocouple, probes static voltage and injection pipes, all of which were covered with a thick layer of polymer. The reactor was completed within a short period of time due to blocking of the discharge unit, which was driven by growing deposits. The importance of the introduction of the SA demonstrated by the following example.

Example 4 polymerization (invention)

The reactor worked when using the catalyst obtained according to the method discussed earlier, with the following changes. Used the catalyst precursor of example 3, as described above. Attended ethanol due to the fact that ethanol was used as solvent in the section of the scrubber spray drying. Temperature chlorination was 50°C instead of 35°C. the Molar ratio of Cl/alkoxide was 2.0, and the halogenation agent was sesquichloride ethylaluminum.

The reactor, which was successfully launched by using the methods of example 3, operated at a temperature of 83°C, molar ratio of hexene/ethylene 0,012, the molar ratio of hydrogen/ethylene 0.2 and a partial pressure of ethylene of about 70 psi. Agent-induced condensation of isopentane contained in the amount of approximately 22 mole percent in the recirculating gas. The suspension of catalyst was injected at a rate of about 9-10 cm³per hour, giving a level of ostatok the CSOs Ti 3,5-4 mln Triethylaluminium the catalyst was injected at a rate of about 75 cm³per hour in the form of a one percent solution in isopentane. The total pressure in the reactor was maintained at 300 psi. Supply agent business continuity equipment is initially maintained at a 6 cm³per hour, then reduced Paladino to 3.2 cm³per hour, 2 cm³per hour, and finally the flow stopped. The obtained resin had an index of current from 0.4 to 0.5 DG/min and density 0,937 g/cm³. The reactor was covered inside with a layer of polymer in less than five hours from the end of the feed SA. However at this time there was no increase or decrease in static pressure. Figure 5 shows the effect of SA submission on the operation of the associated reactor.

During this time all the contents of the first reactor (G1) moved into the second reactor (G7). SA was applied only in the first reactor. Marks on figure 5 indicate when changes were made in the supply of SA in the first of two connected reactors. Thus, it is clear that SA acts not only as an antistatic agent. SA is a critical element in the production of polymers, as discussed in this document. The catalysts used in the invention, also showed a slower rate of deactivation and formation of polymer particles with a narrow distribution p is smarm.

Example 5 polymerization

Got the catalyst using the composition of the catalyst precursor of example 2, following the standard method of chlorination above. Chlorination was performed using the EASC at the final reaction temperature of 50°C for 60 minutes. The molar ratio "chlorine to ethanol", added to the solid composition predecessor, was two.

The reactor, which worked in the equilibrium mode, intentionally subjected to disconnect from the filing of the catalyst. Supply SA maintained at a level sufficient to provide ~ 20 mln SA in the reactor. The temperature in the reactor was maintained at 84°C, molar ratio H2/C2 ranged from 0.19 to 0.20 and the molar ratio C6/C2 ranged from 0,0065 to 0,0068. The partial pressure of ethylene was maintained at a level of from about 58 to 61 psi. Acetalization was TEAL, and isopentane was added to the reactor to maintain the dew point at the inlet from 74°to 76°C. the Initial ratio Al/Ti was approximately 50. Supply socializaton continued after the introduction of the catalyst at a rate that ensured the total content of TEAL in the reactor is essentially constant and equal to ~ 150 mln Performance was calculated by the energy balance in the polymerization reactor. The constant decomposition was calculated using a linear regression model, the determined value of < 0.1 h^-1. The figure 6 presents the dependence of the calculated performance time. In figure 6 Log(calc. production)= 3,2053439-0,0906087 time; (Performance)=Constant*exp(-Kd*time); and Kd=~0.09 h^-1. The constant is determined by the method of selection, and it allows you to calculate the rate of decomposition.

Data used are presented in table 9. The partial pressure of ethylene obtained from the analysis of the composition of the recirculated gas. Both parameters: dew point at the inlet and the performance was calculated using standard thermodynamic models (dew point) and the calculation of energy balance, well-known experts in this field.

Example 6 polymerization (invention)

The catalyst was obtained from the composition of the catalyst precursor of example 2. The final reaction temperature was 50°C for 60 minutes. Chlorination was performed using the EASC when the molar ratio of Cl:atoxic" 2:1. Received polymer with an extremely high bulk density and ultrasonic is their distribution of particle sizes without technological difficulties, feed SA. The reactor was successfully launched, and submission SA maintained at a level sufficient to prevent the formation of a polymer layer on the walls of the reactor/education agglomerates, i.e. at the level of content in the layer is from about 10 to 30 mln In this example, connected the two reactors, and the entire product from the first reactor is transferred to the second reactor. The catalyst was applied only in the first reactor. The polymerization conditions are given in table 10.

Example 7 polymerization (invention)

The precursor of example 1 a catalyst was converted into the catalyst. Used an alternative method. The powder precursor was first dispersible in isopentane, then added the EASC when the molar ratio of Cl to ethoxide" of 2.0. The suspension was mixed at 35°C for one hour, and then allow solid matter to settle. The upper layer was decanted, was added an additional amount of isopentane and the stage was repeated two more times. Then add mineral oil Hydrobrittle 380 obtaining suspension halogenated catalyst precursor. Before use, the suspension was evacuated for approximately one hour with additional evaporation of isopentane.

Then the catalyst used in the reactor in conditions which, essentially the same as the conditions described in example 6. The reactor was carried out in equilibrium before adding a new catalyst. SA contained in the fluidized bed at a concentration of ~ 20 mln mass before replacing the catalyst. Although the washing of the catalyst resulted in higher activity of the catalyst, but the use of the SA remained necessary to prevent the formation of a polymer layer on the walls of the reactor/corking. When filing SA was discontinued, the reactor was covered with a layer of polymer on the walls within 12 hours.

Example 8 polymerization (comparative)

The catalyst was obtained in the same way as that in example 6. Enter SA was mixed directly with the input catalyst at the point of injection to the reactor, and not located in a separate location. Blending streams SA and the catalyst was < 30 seconds. The catalyst activity was extremely low, and the reactor was covered with a layer of polymer on the walls in less than 2 hours of work.

Example 9 polymerization (invention)

The catalyst was prepared using the composition of the precursor according to example 2 of the catalyst and following the standard method of chlorination, above. Chlorination was performed using the EASC at the final reaction temperature of 50°C for 60 minutes. The molar ratio of chlorine to ethanol PR is added to the composition of the solid catalyst was two. The reactor was run, using the same technique as in example 1 with the following changes.

2000 cm³solution triethylamine concentration of 2.5 wt.% were loaded into the reactor instead of triisobutylaluminum.

Second Addendum alkylamine lowered.

Did not pre-loading of the agent increases the continuity of the operation.

The filing agent to increase continuity of the equipment was started simultaneously with the start of the feed of the catalyst. SA consisted of 10 wt.% distearate aluminum and 10 wt.% AS-990, dispersed in mineral oil. Supply SA first supported on the level of consumption of 0.4 cm³/h/cm³enter suspension of the catalyst, and then gradually reduced to ~0.3 cm³/h/cm³the insertion of the catalyst. The flow of catalyst was increased from 50% of feed required to achieve the desired polymerization rate, up to 100% over a period of approximately 6 hours.

The reactor temperature was maintained at 84°C, molar ratio H2/C2 ranged from 0.19 to 0.20, and then the molar ratio C6/C2 ranged from 0,0065 to 0,0068. The partial pressure of ethylene was maintained at approximately 58-61 psi. Acetalization was TEAL, and isopentane was added to the reactor to maintain the dew point at the inlet from 74°to 75°C. the Final balance Ti ranged from 3 to 3.5 mln, and productivity is alnost averaged from 30 to 35 pounds/hour.

After an initial period, the feed rate of SA was slowly lowered so that its content in the fluidized bed was approximately 10 to 15 mln No education polymeric layer on the walls of the reactor or occlusion was not observed.

Comparison of different compounds trialkylamine

The polymerization processes using different connections trialkylamine shown below in tables 11 and 12. Supply SA maintained at the level necessary to maintain the measured value of the static voltage essentially at a neutral level. This value decreases with the state of purity of the source material and the molecular weight of the resulting resin. The levels of CA in the resin varied from ~10 mln 30 mln mass.

As shown in examples b and C, socialization TEAL gives a much better index of the melt, however, even at higher melt index MFR is higher, which indicates a broader molecular weight distribution MWD. Comparison of sample D and sample E additionally indicates the possibility of increasing the MFR (or MWD) due to changes socializaton.

Although the invention is described in some detail through the preceding specific embodiments of the invention, this item refers to the main purpose of explanation of the invention. Many changes and modifications can be made by a person skilled in the art without deviating from the essence and scope of the claims of the invention, as described in the following claims.

Additional example

The polymerization was carried out in gas-phase reactor (diameter of the reactor is 14 inches)

As can be seen from table 1, in the polymerization of 1", which uses the CA and the catalyst containing Mg, Ti and Hf, unexpectedly low static range of 17.5 Volts. In A polymerization", which uses the CA and the catalyst containing Mg and Ti, significantly higher than the static is the range 522,5 Volts. Also, in the polymerization of 1" by using less CA, but with a sharp decrease in the static range. Thus, the polymerization of 1 indicates continuous operation of the reactor and more stable polymerization with the least possibility of formation of films on the walls of the reactor and agglomerates.

1. A method of producing polymers based on olefins comprising the polymerization of at least one monomer in the gas phase, in the presence of at least SL is blowing components:
A) a catalyst comprising metals of Mg, Ti, Hf and optionally Zr;
B) socializaton representing trialkylaluminium;
C) a composition comprising at least one compound selected from compounds of formula (I), and at least one compound selected from compounds of the formula (II):


where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;
R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;
R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and
x+y=3, and x has a value of 1 or 2.

2. A method of producing polymers based on olefins comprising the polymerization of at least one monomer in a suspension process, in the presence of at least the following components:
A) a catalyst comprising metals of Mg, Ti, Hf and optionally Zr;
B) socializaton representing trialkylaluminium;
C) a composition comprising at least one compound selected from compounds of formula (I), and at least one compound selected from compounds of the formula (II):


where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;
R2 represents a hydrocarbon radical, containing the s from 14 to 26 carbon atoms;
R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and
x+y=3, and x has a value of 1 or 2.

3. The method according to claim 1 or 2, where the component fed into the reactor separately from the catalyst and socializaton.

4. The method according to claim 1 or 2, where the component is a solid when the feed to the reactor.

5. The method according to claim 1 or 2, where the catalyst is a catalyst of Ziegler-Natta, including metals Mg, Ti, Hf and optionally Zr.

6. The method according to claim 5, where each metal are presented in the form of a halide.

7. The method according to claim 1 or 2, where the catalyst is obtained by spray drying a solution comprising an active metal catalyst in an alcohol solvent, and then halogenoalkanes active metals.

8. The method according to claim 1 or 2, where the polymer-based olefin polymer is ethylene.

9. The method of claim 8, where the polymer based on ethylene copolymer is ethylene/α-olefin.

10. The method according to claim 1 or 2, where the composition component further includes mineral oil.

11. The method according to claim 1 or 2, where the composition of component C contains at least one compound selected from compounds of formula (I)at least one compound selected from compounds of the formula (II), and mineral oil.

12. The method according to claim 1 or 2, where the composition component includes at least one compound selected from compounds fo the formula (I), and at least one compound selected from compounds of the formula (II), and where the mass ratio of compounds selected from compounds of formula (I) compound selected from compounds of the formula (II) is 1:1.

13. A method of producing polymers based on olefins comprising the polymerization of at least one monomer in the presence of at least the following components:
A) catalyst type Ziegler-Natta, including metals Mg, Ti, Hf and optionally Zr;
B) compounds trialkylamine;
C) a composition comprising at least one compound selected from compounds of formula (I), and at least one compound selected from compounds of the formula (II):
,
;
where R1 represents a hydrocarbon radical containing from 13 to 25 carbon atoms;
R2 represents a hydrocarbon radical containing from 14 to 26 carbon atoms;
R3 represents a hydrocarbon radical containing from 1 to 4 carbon atoms, and
x+y=3, and x has a value of 1 or 2.

14. The method according to item 13, where the ratio of the velocities of the melt (I21/I2) of polymer-based olefin is regulated, regardless of the reaction conditions, compound trialkylamine.

15. The method according to any of PP and 14, where each metal are presented in the form of a halide.

16. The method according to item 13, where the catalyst obtained resplit the through-drying of a solution, including an active metal catalyst in an alcohol solvent, followed by halogenoalkanes active metals.

17. The method according to item 13, where the polymer-based olefin polymer is ethylene.