Use of quaternary ammonium salts as antistatic agent in olefin polymerization

Abstract

The invention relates to the use of quaternary ammonium salts as an antistatic agent and to a method for polymerizing olefins using said agent. The salts according to the present invention constitute antistatic agents or antistatics and are compounds belonging to the class of quaternary ammonium salts and / or mixtures thereof with components of a different nature. The proposed antistatic agents exhibit effective antistatic properties in a polymerization reactor in low-concentration doses (up to 20 ppm).

Description

[0001] USE OF QUATERNARY AMMONIUM SALTS AS AN ANTISTATIC AGENT (VARIANTS) AND A METHOD FOR POLYMERIZING OLEFINS USING SAID AGENT The field of the invention relates to the use of components used in the (co)polymerization of olefins and added to the (co)polymerization reactor to reduce static charge. According to the present invention, the said components are antistatic agents and are compounds whose structure simultaneously contains at least two functional groups: a quaternary ammonium cation and an amide group. The invention also relates to a mixture of the said antistatic agents with other commercially available antistatic agents of various natures. As a result of such mixing, homogeneous mixtures are formed, thereby increasing the effectiveness of the antistatic properties of these commercially available antistatic agents in olefin polymerization processes.State of the Art: Due to their chemical nature, most polymers are insulators. However, their common drawback is that due to their insulating properties, polymers accumulate static electricity, which cannot be quickly dissipated due to low surface conductivity, or, in other words, high resistivity. During the production of polymer raw materials, static charge accumulation can occur as early as the (co)polymerization stage, negatively impacting process convenience and causing production delays due to the need to clean equipment. This also leads to adhesion on internal equipment surfaces, which in turn can lead to the shutdown of the entire polymer synthesis process.When using end products prone to static electricity accumulation, undesirable consequences may also arise, such as extensive surface contamination, sparks, and possible subsequent ignition of dust accumulated on the surface. There are two main approaches to suppressing, or at least reducing, the effects of static electricity on the surface of a material. Both of these approaches rely on influencing the polymer structure (called internal action) and influencing the material surface (called external action). Examples of the first approach include adding special components during the polymerization stage, while the second approach involves increasing the humidity of the environment or treating the resulting polymer granules to increase the surface conductivity. The magnitude of static charge or voltage is inversely proportional to relative humidity and directly proportional to surface resistivity.Components added to a polymerization reactor to reduce static charge or stress caused by the mutual attraction of oppositely charged particles, as well as the mutual repulsion of like-charged particles, which results in polymer fouling on process equipment, have various designations. In the polymerization field, these components are referred to as antifouling agents, antistatic inhibitors, or simply antistatic agents, antistatics / antistatic agents, etc. Typically, the primary function of reducing static charge in such components is performed by polar functional groups such as acid and ester groups, amide groups, hydroxyl groups, or ether groups.Examples of compounds with antistatic properties include polysulfone copolymers, polyhydric alcohols, hydroxyesters of polyhydric alcohols, alkyl aryl sulfonic acid salts, polysiloxanes, polyglycol ethers, and others. The prior art discloses various formulation options and methods for reducing static charge. However, key characteristics of antistatic agents should be considered, in particular, demonstrated antistatic properties at levels below 20 ppm based on the weight of the olefin during polymerization and effective operation, the absence of a deactivating effect from the catalytic system used, the stability of the active functional groups of the agent under polymerization conditions (temperature and pressure), and the lack of toxicity for the use of polymer products in everyday life.For example, US Patent 5410002 describes a polymerization method in which antistatic compounds are used to eliminate or reduce the buildup of polymer particles on the walls of gas-phase polymerization reactors. These antistatic compounds are capable of selectively inhibiting polymerization on polymer particles smaller than 850 µm, the latter being responsible for problems of fouling and polymer sheeting. One class of these antistatic / antifouling compounds are N-alkyl diethanolamines, such as Atmer 163, manufactured by Croda. US Patent 6111034 describes a method for controlling static charges in a gas-phase olefin polymerization reactor by adding water in quantities exceeding 3 ppm by volume. However, a disadvantage of these additives, used in olefin polymerization to reduce static charges, is their negative impact on catalytic systems.BEP describes a method for the gas-phase polymerization of olefins in a fluidized bed reactor, in which fouling is prevented and / or polymer flowability is improved by using an auxiliary additive containing at least one component selected from (1) a glycerol ester of a fatty acid, (2) a sorbitan ester of a fatty acid, (3) an alkylamine carboxylate, (4) hydrogen peroxide and / or water, (5) a salt. The above-described components are catalyst poisons and their use is often severely limited by negative effects in the form of a decrease in the activity of the catalyst system and an unpredictable change in the characteristics of the polymer. BEP 0782587 and EP 1012195 describe a process method for solving the problem of the formation of polymer agglomerates due to electrostatic charges in the polymerization device.However, any technological, non-formulaic solutions require significant modifications to standard technology, which entails additional costs and complicates the equipment base. Therefore, the objective of the present invention was to overcome the aforementioned disadvantages of the prior art by using an antistatic agent for olefin polymerization that exhibits improved antistatic action at low dosages and exhibits less deactivating effects on the catalyst. Disclosure of the invention: The objective of the present invention was to propose a new antistatic agent for olefin polymerization that helps reduce static charge on the surface of polymerization equipment and the polymer itself.The technical result of the present invention is to provide a new antistatic agent used in gas-phase or suspension polymerization of olefins and exhibiting effective antistatic properties at low concentrations (less than 20 ppm). The antistatic agent proposed in the present invention is a compound of formula (I) or a mixture containing a compound of formula (I) and other antistatic agents, in particular selected from the group consisting of aliphatic and aromatic hydrocarbons, ethoxylated amines, polyesters and quaternary ammonium salts. An additional technical result of the present invention is to increase the antistatic activity of the components included in the mixture with the antistatic agent of formula (I).An additional technical result of the present invention is the provision of a new antistatic agent characterized by a negligible effect on the activity of the catalyst system during polymerization and simultaneously enabling the production of special polymer grades suitable for use in the civil (food industry) and medical applications. Accordingly, the first object of the invention is the use of a compound of formula (I): where is selected from the group of aromatic radicals (aryls) that contain at least 6 carbon atoms and may contain heteroatoms (nitrogen, oxygen, sulfur) and hydrogen and R are independently of one another selected from hydrogen and a group comprising alkyl cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogen, oxygen, nitrogen or sulfur denotes alkyl takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, as an antistatic agent. The compound of formula (I) is preferably benzyldimethyl[3(myristoylamino)propyl]ammonium chloride, dimethyl[3(myristoylamino)propyl]ammonium chloride, dibenzylmethyl[3(myristoylamino)propyl]ammonium chloride or cycloalkyldimethyl[3(myristoylamino)propyl]ammonium chloride. The compound of formula (I) preferably exhibits antistatic activity at concentrations of 5 parts. / million in the polymerization process. The second object of the invention is the use of a compound of formula (I):. wherein R is selected from the group of aromatic radicals (aryls) that contain at least 6 carbon atoms and may contain heteroatoms (nitrogen, oxygen, sulfur) and hydrogen, and R is independently selected from hydrogen and a group comprising alkyl, cycloalkyl, and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen, or sulfur, and denotes alkyl, which takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, as an antistatic agent in a mixture with other antistatic agents, in particular those selected from the group comprising aliphatic and aromatic hydrocarbons, ethoxylated amines, polyesters, and quaternary ammonium salts to increase the antistatic activity of other antistatic agents in the process of olefin polymerization.The compound of formula (I) is preferably benzyldimethyl[3(myristoylamino)propyl]ammonium chloride, dimethyl[3(myristoylamino)propyl]ammonium chloride, dibenzylmethyl[3(myristoylamino)propyl]ammonium chloride or cycloalkyldimethyl[3(myristoylamino)propyl]ammonium chloride. The compound of formula (I) preferably exhibits antistatic activity at concentrations of 5 ppm during polymerization. A third aspect of the invention is the use of a compound of formula (I):. wherein R is selected from the group of aromatic radicals (aryls) that contain at least 6 carbon atoms and may contain heteroatoms (nitrogen, oxygen, sulfur), and hydrogen, and R is independently selected from hydrogen and a group comprising alkyl cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen or sulfur. R denotes alkyl, takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, as an additive for increasing the antistatic activity of other antistatic agents, in particular selected from the group comprising aliphatic and aromatic hydrocarbons, ethoxylated amines, polyesters and quaternary ammonium salts.The compound of formula (I) is preferably benzyldimethyl[3(myristoylamino)propyl]ammonium chloride, dimethyl[3(myristoylamino)propyl]ammonium chloride, dibenzylmethyl[3(myristoylamino)propyl]ammonium chloride or cycloalkyldimethyl[3(myristoylamino)propyl]ammonium chloride. The compound of formula (I) preferably exhibits antistatic activity at concentrations of 5 ppm during the polymerization. These other antistatic agents are low-efficiency antistatic agents, in particular selected from the group consisting of aliphatic and aromatic hydrocarbons, ethoxylated amines, polyethers, quaternary ammonium salts and other components exhibiting weak antistatic properties. According to this aspect of the present invention, the compound of formula (I) can be used in a composition or mixture with other antistatic agents or added separately to the polymerization reactor. The fourth object of the invention is the use of a compound of formula (I):. where is selected from the group of aromatic radicals (aryls) that contain at least 6 carbon atoms and may contain heteroatoms (nitrogen, oxygen, sulfur), and hydrogen and R are independently selected from hydrogen and a group comprising alkyl cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen or sulfur denotes alkyl, takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, as an antistatic agent in the polymerization of two or more olefins in the presence of a catalytic system. The compound of formula (I) is preferably benzyldimethyl[3(myristoylamino)propyl]ammonium chloride, dimethyl[3(myristoylamino)propyl]ammonium chloride, dibenzylmethyl[3(myristoylamino)propyl]ammonium chloride or cycloalkyldimethyl[3(myristoylamino)propyl]ammonium chloride.The compound of formula (I) preferably exhibits antistatic activity at concentrations of 5 ppm during polymerization. A fifth object of the invention is the use of a compound of formula (I):. where R is selected from the group of aromatic radicals (aryls) that contain at least 6 carbon atoms and may contain heteroatoms (nitrogen, oxygen, sulfur), and hydrogen and R are independently selected from hydrogen and a group comprising alkyl cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen or sulfur, denotes alkyl, takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, in a mixture with other antistatic agents, in particular selected from the group comprising aliphatic and aromatic hydrocarbons, ethoxylated amines, polyesters and quaternary ammonium salts, as an antistatic agent in the polymerization of two or more olefins in the presence of a catalytic system.The compound of formula (I) is preferably benzyldimethyl[3(myristoylamino)propyl]ammonium chloride, dimethyl[3(myristoylamino)propyl]ammonium chloride, dibenzylmethyl[3(myristoylamino)propyl]ammonium chloride or cycloalkyldimethyl[3(myristoylamino)propyl]ammonium chloride. The compound of formula (I) preferably exhibits antistatic activity at concentrations of 5 ppm during polymerization. A sixth aspect of the invention is a process for the polymerization of olefins using the compound of formula (I) or the mixture described above, comprising contacting at least one olefin with a catalyst system by adding the compound of formula (I) to the polymerization reactor. In one embodiment, the invention provides a process for the polymerization of olefins using the compound of formula (I) in a gas phase polymerization of olefins.According to the invention, an antistatic agent is fed directly into the polymerization zone of the reactor in the presence of various olefin polymerization catalysts (organochromium catalysts, metallocene catalysts, and classic Ziegler-Natta catalysts). The antistatic agent proposed in the invention effectively reduces and prevents the accumulation of static charge within the reactor, significantly reducing the likelihood of polymer buildup on the internal surfaces of the reactor equipment, while not affecting the performance of the catalyst or the resulting polymer. Industrial gas-phase polymerization is typically carried out in continuous fluidized-bed reactors, where a mixture of various hydrocarbons is fed from the bottom up through a special distribution grid, directly above which the catalyst system components and the antistatic agent are fed.The antistatic agent according to the present invention is a compound of formula (I) or a mixture containing a compound of formula (I) and other antistatic agents, in particular selected from the group consisting of aliphatic and aromatic hydrocarbons, ethoxylated amines, polyesters and quaternary ammonium salts. It is important to emphasize that the additional components must dissolve the compound of formula (I) in order to prevent their precipitation. The compound of formula (I) and mixtures based on it are preferably fed to the reactor as a solution in any solvent compatible with the given gas-phase polymerization process and allowing the compound of formula (I) to be fed to the polymerization reactor in liquid form. As a rule, such solvents are aliphatic and aromatic hydrocarbons. The optimal dosage of the antistatic agent is from 1 to 100 ppm based on the weight of the main monomer.It should be noted that, according to experimental data, the minimum effective dosage of the antistatic agents proposed in the invention is lower than that of the tested analogs serving as comparison samples. Currently, there is no single, generally accepted theory describing the process of charge generation and dissipation during olefin polymerization. It is likely that long alkyl and / or aryl fragments in the antistatic agent ensure sufficient solubility in the hydrocarbon medium and distribution on the surface of the resulting polymer particles, while the presence of polar groups ensures sufficient conductivity on the particle surface, which increases the rate of charge dissipation of the polymer particle. The presence of polar groups is ensured by the structural organization of the hydrocarbon chain, which includes one of the key elements of this structure, (myristoylamino)propyl, which has a significant impact on the effectiveness of the antistatic agent at low dosages.Brief description of graphic materials Fig. 1 shows a histogram for comparing the effectiveness of antistatic agents. Fig. 2 shows photographs of post-polymerization reactors with and without antistatic agents, wherein Fig. 2 shows a photograph of the reactor after polymerization without using an antistatic agent, Fig. 3 shows a photograph of the reactor after polymerization using component No. 1 in an amount of 5 parts per million, Fig. 4 shows a photograph of the reactor after polymerization using component No. 2 in an amount of 10 parts per million, Fig. 5 shows a photograph of the reactor after polymerization using antistatic agent No. 1 in an amount of 30 parts per million, Fig. 6 shows a photograph of the reactor after polymerization using antistatic agent No. 2 in an amount of 30 parts per million. A photograph of the reactor after polymerization using mixture No. 1 in an amount of 60 parts per million is shown. Fig. A photograph of the reactor after polymerization using mixture No. 1 in an amount of 10 parts per million is shown. / million, Fig. shows a photograph of the reactor after polymerization using antistatic agent No. in an amount of 60 ppm, Fig. shows a photograph of the reactor after polymerization using antistatic agent No. in an amount of 60 ppm and Fig. shows a photograph of the reactor after polymerization using component No. in an amount of 30 ppm. Detailed Description of the Invention All references to the Periodic Table of the Elements in this specification are to the Periodic Table of the Elements as published and approved by IUPAC. Unless otherwise indicated, all parts and percentages are by weight. The term "comprising" and its derivatives does not imply the exclusion of the presence of an additional component, step, or operation, whether or not such component, step, or operation is disclosed herein.To avoid any doubt, all compositions described in the present description and claims using the term "comprising" may include any additional additive and / or excipient, unless otherwise indicated. In contrast, the term "essentially consisting" excludes from the scope of any subsequent listing any other component, any other step, or any other operation, except those that do not affect the feasibility of carrying out the invention. The term "consisting of" excludes any component, any step, or any operation that is not specifically defined or listed. The conjunction "or," unless otherwise indicated, refers to the listed elements individually as well as in any combination.Any numerical range specified in the present description and claims covers all values ​​from the smallest inclusive to the largest inclusive increments of one unit, provided that there is a separation of at least 2 units between any smallest value and any largest value. Thus, for example, if an amount of a component or a value of a structural or physical property, such as the amount of a component in a mixture, softening point, melt flow index, etc., is specified to be in the range from to 100, then it is meant that all individual values ​​such as 1, 2, 3, etc., and all sub-ranges such as from 1 to 20 from 55 to 70 from 97 to 100, etc., are unambiguously listed in this description. For values ​​less than one, the unit (step) is considered to be 0.0001, 0.001, 0.01 or 0.1, if necessary.These are only examples of what is specifically intended, and all possible combinations of numerical values ​​between the lowest value and the highest value given should be considered as expressly indicated in this description. In other words, any numerical range given in this description covers any value or any subrange within the given range. The term "polymer" as used in this description means a macromolecular compound containing repeating structural units that are monomers. The polymer includes homopolymers and copolymers. The term "polymerization" means the process of producing a polymer. The term "olefin" as used in this description means an alkene. The term "olefin-based polymer" or "polyolefin" means a polymer containing, in polymerized form, a major weight percentage of an olefin, such as ethylene or propylene, based on the total weight of the polymer.Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers. The term "copolymer," as used herein, means a polymer prepared from two or more different monomers. The term "monomer," as used herein, means a chemical compound that can be polymerized. The term "hydrocarbon," as used herein, refers to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, condensed (e.g., anthracene derivatives), or acyclic compounds, and combinations thereof. The term "alkyl," as used herein, means an alkyl group, which is a functional group, or a side chain, consisting of carbon and hydrogen atoms and containing only single bonds. An alkyl group may be straight or branched and may be unsubstituted or substituted.Non-limiting examples of suitable alkyl radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl (or 2-methylpropyl), and the like. Alkyls can contain from 1 to 20 carbon atoms. The term substituted alkyl as used herein refers to the alkyl discussed immediately above in which one or more (two, three, four, or more) hydrogen atoms attached to any carbon atom of the alkyl are replaced by another group such as a halogen atom, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, haloalkyl, hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, another heteroatom-containing group, and combinations thereof. Examples of suitable substituted alkyls include benzyl, trifluoromethyl, and the like. The term cycloalkyl as used herein refers to a saturated cyclic hydrocarbon group. A cycloalkyl group may be substituted or unsubstituted.Non-limiting examples of cycloalkyl radicals include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like. Cycloalkyls can contain from 3 to 20 carbon atoms. The term "aryl" as used herein refers to an aromatic substituent, which can be a single aromatic ring or multiple aromatic rings that are fused together, covalently linked, or linked by a common group such as a methylene or ethylene group. The aromatic ring(s) can, among other things, be phenyl, naphthyl, anthracenyl, and biphenyl. Aryls can contain from 6 to 20 carbon atoms. Aryls may contain heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur. The term substituted aryl as used herein refers to the aryl discussed immediately above in which one or more (two, three, four, or more) hydrogen atoms in the aromatic ring are replaced by another group.Thus, a substituted aryl group also encompasses alkaryl groups wherein one or more (two, three, four or more) hydrogen atoms in the aromatic ring are replaced by alkyl groups, as well as haloaryl groups in which one or more (two, three, four or more) hydrogen atoms in the aromatic ring are replaced by halogen atoms. The term carbocycle, as used herein, refers to a cyclic group consisting of carbon atoms. The carbocycle does not contain any atoms other than carbon and hydrogen atoms. The carbocycle may be saturated, unsaturated, or aromatic. The carbocycle may have from 3 to 20 carbon atoms. The term heterocycle, as used herein, refers to a cyclic group consisting of carbon atoms and at least one heteroatom. The heteroatoms may be F, Cl, Br, I, N, O, P, B, S, or Si. A heterocycle can have from 2 to 20 carbon atoms. The term halogens as used herein refers to F, Cl, Br, and I.The term "Ziegler Natta catalyst" as used herein means a transition metal-containing solid catalyst compound that comprises Ziegler Natta catalyst particles supported on a metallic or metalloid compound (e.g., a magnesium compound or a silicon compound). The term "Ziegler Natta catalyst particles" or "active catalyst particles" as used herein means transition metal-containing particles that comprise a transition metal halide selected from titanium halide, chromium halide, hafnium halide, zirconium halide, and vanadium halide.Unless otherwise stated, an indication that any group is independently selected from or independently represents means that, if several identical groups are present in the molecule, they may have the same or different meanings. For example, in the compound RM, where R is independently selected from ethyl or methyl, both R groups may be ethyl, both R groups may be methyl, or one R group may be ethyl and the other methyl. The present invention is described in more detail below. All embodiments of the present invention described with respect to one aspect of the invention are applicable to its other aspects, unless otherwise stated. The present invention is described more specifically with reference to the examples below.These examples merely illustrate the present invention and do not limit its scope. Carrying out the invention. Example 1. The polymerization was carried out in a 2-liter reactor equipped with an anchor stirrer, a thermocouple, a pressure sensor, and a thermostat for temperature control. The flow rate of ethylene and butene 1 was controlled using a Coriolis flowmeter; the mass ratio of ethylene to butene 1 was constant. An antistatic agent was fed to the reactor at the beginning of the reaction in the form of a hexane solution immediately after loading the catalyst. The pressure and temperature in the reactor were maintained at a constant level and did not change during the polymerization reaction. The yield of polyethylene (PE) was controlled using an ethylene flowmeter, and after the catalyst productivity reached 2 kg PE per gram of catalyst (kgPE / gcat), the pressure in the reactor was released to atmospheric pressure, which was accompanied by the termination of the polymerization reaction.Table 1 below presents the polymerization reactor data and test conditions.

[0002] Table 1 Reactor and polymerization conditions Reactor Reactor volume, l Stirrer speed, rpm Catalyst loading in the form of dry powder in a current of ethylene Comonomer butene Isobutane is used for more efficient heat transfer and to prevent the formation of polymer agglomerates Polymerization conditions Polymerization temperature, °C by weight Ethylene pressure, bar Total pressure, bar Catalyst weight, mg Productivity, kg ПЭ / G катIsobutane, g Amount of antistatic agent, ppm All antistatic agents were tested under the same conditions of gas-phase polymerization of ethylene using chromium oxide catalysts in a laboratory reactor. Table 2 below presents the types of antistatic agents used in accordance with Example 1. Test Methods The following approach was used to evaluate the effectiveness of the antistatic agent. Visual inspection of the reactor upon completion of the polymerization process. Measurement of the accumulated static charge in the reactor using a 715 device (manufactured by the company). Measuring the difference between the temperature of the coolant in the reactor jacket and a thermocouple. During normal reactor operation, the instantaneous flow rate of ethylene determines the amount of heat released during polymerization and, accordingly, a certain difference between the temperature inside the reactor ( ) and the temperature in the jacket ( ).When a static charge forms, growing PE particles adhere to the thermocouple, causing additional heating, resulting in an increased difference at the same ethylene flow rate. To compare the effectiveness of antistatic agents, the ratio of ∆ to the unit monomer flow rate at its maximum flow rate was used (see Fig. 1).Table 2 Used antistatic agentsAntistatic code Description of antistatic agentComparative Antistatic No. 1 Antistatic analogue based on a mixture of various liquid quaternary ammonium salts Antistatic No. 2 Antistatic analogue consisting of a mixture of various polysulfones Antistatic No. 3 Commercially available antistatic analogue Antistatic No. 4 Antistatic analogue based on a mixture of ethoxylated amines According to Component No. 1 Benzyldimethyl[3(myristoylamino)propyl]ammonium chloride Component No. 2 Dimethyl[3(myristoylamino)propyl]ammonium chloride Component No. 3 Dibenzylmethyl[3(myristoylamino)propyl]ammonium chloride Component No. 4 Cycloalkyldimethyl[3(myristoylamino)propyl]ammonium chloride Mixture No. 1 Antistatic mixture No. 3 with 10% by weight of component No. 1 Mixture No. 2 Mixture of antistatic agent No. 4 with 10% by weight of component No. 1 Below are the experimental data obtained as a result of the laboratory testing process of antistatic agents according to Example 1 described above.Table 3 provides links to graphic materials with photographs of the reactor immediately after the polymerization process is complete and presents the characteristics of the resulting polyethylene. The antistatic agent concentration in Table 3 corresponds to the minimum effective amount ensuring a stable polymerization process. The data presented in Table 3 show that components No. 4 exhibit high antistatic activity and outperform existing analogs even at lower concentrations. Component No. 1 exhibited higher antistatic activity compared to component No. 2, which is likely explained by the presence of an additional benzyl fragment in the molecule, which ensures greater affinity of antistatic molecules to the surface of growing PE particles. All antistatic agents presented in Table 3 have no negative effect on polymer characteristics or catalyst activity. Antistatic agents No. 3 and No. 4 are not effective in the dosage range up to 30 ppm.To increase their effectiveness, mixtures of these antistatic agents were prepared with 10% by weight of component No. 1. This resulted in an increase in the effectiveness of existing antistatic analogs (antistatic agents Nos. 3 and 4). It should be noted that when using mixture No. 2, the content of component No. 1 in the reactor was 1 ppm. This allows these substances to be used not only as a stand-alone antistatic agent but also as an additive to enhance the effectiveness of ineffective antistatic compounds. However, the use of the new antistatic agent in various variants, either as a single compound or in a mixture with other antistatic analogs, is aimed at achieving the same technical result: reducing static charge during polymerization. Figure 1 shows a histogram illustrating the effectiveness of antistatic agents in numerical terms.Some of the data presented in the histogram (Fig. 1) are consistent with those presented in Tables 3 and . Specifically, Fig. 1 shows the effectiveness of the antistatic agents in comparison with polymerization carried out without an antistatic agent and with the following types of antistatic agents: components Nos. 1 and 2 according to the invention, commercially available antistatic agents Nos. 1 through 4, and mixtures of the components according to the invention with similar antistatic agents. The histogram shows that the components proposed in the invention have the highest antistatic effectiveness. It should also be noted that components Nos. 1 and 2 can be used as additives to enhance antistatic properties.Moreover, all polymer characteristics, such as bulk and physical density, melting point, degree of crystallinity, median polymer particle size, activity and melt flow index are maintained when using the antistatic agents proposed in the invention, which indicates the absence of any influence on the active centers of the catalyst.

[0003] A 4 т № с And к т и Mr. N т и A ф A 3 т № с And к т g and н т и ф А A 2 т № с And к т g and т и н ф А A 1 т № с And к т g and и н т ф А 4 o № p м т он К е н в о 3 к O № и п т м т о н а К е т н с и 2 т O № н п а м т о н G и К е н и ф т с 1 о № н в т и н G т е и н ф к е о ф п ф м э о g K и ф е и н a z т е с а е к н . B и т и г вт а и н ф р а С , ь а A 0 1 м с m 3 и т т , / с / т с р G е р / е а а а н , а г т е а р , г о н м з м и е н В к c c g o k ya ь och ) я и и а в и n и т т г а , ь , ь ч и а р л о м / к о к е и , л б tt t l f a s a т к but the frost itself а а к 6 к , с т с я а т с л о и С л йп м с е н е е р A г о е ч т с / . р г т н в л г 1 е ч о н н п о н ° а т и н ц , ч ж е T / 2 i ) and I mr ф к с и л и т т с о т к а и т а ( т Э П Р and t y t s d t 0 t rn з о с о , li e s 5 a p и л пand e o n a o e k a g T i l a l r r a D t a oimSh h K a ch F r A k k P F p N p K S h ( С н pTable 4 Effect of component No. 1 on the efficiency of antistatic analogs Component code Mixture No. 1 Mixture No. 2 Amount of antistatic, ppm Photograph of reactor Fig. Catalyst activity, kg ПЭ / G кат / h PT Physical density, g / cm Bulk density, g / cm p л , °C Crystallinity, % Average polymer particle size (D50), µm Static voltage on the polymer, kV

Claims

CLAUSE OF THE INVENTION Use of a compound of formula (I): wherein R is selected from hydrogen and a group of aromatic radicals that contain at least 6 carbon atoms and may contain heteroatoms from nitrogen, oxygen and sulfur, and R is independently selected from hydrogen and a group comprising alkyl, cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen or sulfur, denotes alkyl, takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, as an antistatic agent. The use according to claim 1, wherein the compound of formula (I) is benzyldimethyl[3 (myristoylamino) propyl] ammonium chloride. Use according to claim wherein the compound of formula is dimethyl[3 (myristoylamino)propyl]ammonium chloride. Use according to claim wherein the compound of formula (I) is dibenzylmethyl[3 (myristoylamino)propyl]ammonium chloride. Use according to claimwherein the compound of formula (I) is cycloalkyldimethyl[3(myristoylamino)propyl]ammonium chloride. The use according to claim wherein the compound of formula exhibits antistatic activity at concentrations of 5 ppm during polymerization. The use of the compound of formula (I):. wherein R is selected from hydrogen and a group of aromatic radicals that contain at least 6 carbon atoms and may contain heteroatoms from nitrogen, oxygen and sulfur, and R is independently selected from hydrogen and a group comprising alkyl, cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen or sulfur, denotes alkyl, takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, in a mixture with other antistatic agents, in particular selected from the group comprising aliphatic and aromatic hydrocarbons, ethoxylated amines, polyethers and quaternary ammonium salts for increasing the antistatic activity of other antistatic agents in the polymerization of olefins. The use according to claim 1 wherein the compound of formula (I) is benzyldimethyl[3 (myristoylamino)propyl]ammonium chloride. The use according to claim 1 wherein the compound of formula is dimethyl[3 (myristoylamino)propyl]ammonium chloride. The use according to claim 1 wherein the compound of formula (I) is dibenzylmethyl[3 (myristoylamino)propyl]ammonium chloride. The use according to claim 1 wherein the compound of formula (I) is cycloalkyldimethyl[3 (myristoylamino)propyl]ammonium chloride. The use according to claim 1 wherein the compound of formula exhibits antistatic activity at concentrations of 5 ppm during the polymerization. Use of a compound of formula (I): Where selected from hydrogen and a group of aromatic radicals which contain at least 6 carbon atoms and may contain heteroatoms from nitrogen, oxygen and sulfur, and R are independently selected from hydrogen and a group comprising alkyl, cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents which are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen or sulfur, and alkyl takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, as an additive for increasing the antistatic activity of other antistatic agents, in particular selected from the group comprising aliphatic and aromatic hydrocarbons, ethoxylated amines, polyethers and quaternary ammonium salts. The use according to claim 1, wherein the compound of formula (I) is benzyldimethyl[3 (myristoylamino) propyl] ammonium chloride. The use according to claim 1.wherein the compound of formula is dimethyl[3(myristoylamino)propyl]ammonium chloride. Use according to claim wherein the compound of formula(I) is dibenzylmethyl[3(myristoylamino)propyl]ammonium chloride. Use according to claim wherein the compound of formula(I) is cycloalkyldimethyl[3(myristoylamino)propyl]ammonium chloride. Use according to claim wherein the compound of formula exhibits antistatic activity at a concentration of at least 5 ppm during polymerization. Use of a compound of formula (I). wherein is selected from hydrogen and a group of aromatic radicals that contain at least 6 carbon atoms and may contain heteroatoms from nitrogen, oxygen and sulfur, and R is independently selected from hydrogen and a group comprising alkyl, cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen or sulfur, denotes alkyl takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3 as an antistatic agent in the polymerization of two or more olefins in the presence of a catalytic system. The use according to claim wherein the compound of formula (I) is benzyldimethyl[3 (myristoylamino)propyl]ammonium chloride. The use according to claim wherein the compound of formula is dimethyl[3 (myristoylamino)propyl]ammonium chloride. The use according to claimwherein the compound of formula (I) is dibenzylmethyl[3 (myristoylamino) propyl] ammonium chloride. Use according to claim wherein the compound of formula (I) is cycloalkyl dimethyl[3 (myristoylamino) propyl] ammonium chloride. Use according to claim wherein the compound of formula exhibits antistatic activity at concentrations of 5 ppm during polymerization. Use of a compound of formula (I):. where R is selected from hydrogen and a group of aromatic radicals that contain at least 6 carbon atoms and may contain heteroatoms from nitrogen, oxygen and sulfur, and R is independently selected from hydrogen and a group that includes alkyl, cycloalkyl and aryl, which are optionally substituted by one or more identical or different substituents that are radicals of the aryl and alkyl series, with functional groups containing halogens, oxygen, nitrogen or sulfur. denotes alkyl takes values ​​from 1 to 20, preferably from 1 to 3, most preferably 3, in a mixture with other antistatic agents, in particular selected from the group consisting of aliphatic and aromatic hydrocarbons, ethoxylated amines, polyethers and quaternary ammonium salts, as an antistatic agent in the polymerization of two or more olefins in the presence of a catalytic system. Use according to claim wherein the compound of formula (I) is benzyldimethyl[3 (myristoylamino)propyl]ammonium chloride. Use according to claim wherein the compound of formula is dimethyl[3 (myristoylamino)propyl]ammonium chloride. Use according to claim wherein the compound of formula (I) is dibenzylmethyl[3 (myristoylamino)propyl]ammonium chloride. Use according to claim wherein the compound of formula (I) is cycloalkyldimethyl[3 (myristoylamino)propyl]ammonium chloride. Use according to claimwherein the compound of formula exhibits antistatic activity at concentrations of 5 ppm during polymerization. A method for polymerizing olefins using a compound of formula (presented in claims 1 to 3) which consists in that at least one olefin. are brought into contact with the catalyst system by adding the compound of formula (I) to the polymerization reactor.

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