Method for free-radical polymerisation or cross-linking in presence of selected organic peroxide obtained ex situ

FIELD: chemistry.

SUBSTANCE: described is a free-radical polymerisation method in which at least one polymerisable monomer reacts in the presence of at least one organic peroxide selected from a group, wherein the organic peroxide is obtained using a continuous method ex situ using closed plate heat exchanger. Described also is method for suspension polymerisation of vinyl chloride, as well as a method for suspension polymerisation of styrene in the presence of at least one organic peroxide selected from a group, wherein the organic peroxide is obtained using a continuous method ex situ using a closed plate heat exchanger. Described is a method for polymerisation of acrylic monomers in the presence of at least one organic peroxide selected from a group, wherein the peroxide is obtained using a continuous method ex situ using a closed plate heat exchanger. Described also is a free-radical polymerisation method in which a polymerisable monomer reacts in the presence of at least one organic peroxide selected from a group, wherein said method comprises steps (a)-(d) realised at the same place: a) obtaining a selected organic peroxide via a continuous method using a closed plate heat exchanger, b) feeding, if necessary, reaction mixture (a) into a purification apparatus, c) feeding the organic peroxide obtained at step (a) or step (b) into a polymerisation reactor, d) free-radical polymerisation of at least one polymerisable monomer in the presence of one or more organic peroxides fed at step (c). The invention also describes thermoplastic polymers and/or elastomers obtained using methods described above.

EFFECT: use, in free-radical polymerisation systems, of organic peroxides obtained directly where free-radical polymerisation takes place.

13 cl, 2 dwg, 3 ex

 

The present invention relates to free radical polymerization and free radical crosslinking and, more specifically, for use in free radical polymerization or crosslinking of free radical organic peroxide obtained by the method of ex situ using reactors with continuous action.

In reactors of free radical polymerization or crosslinking served free radical initiators, which can be a organic peroxides, azo compounds or the initiators of the formation of carbon-carbon bonds class hexosamine of Atanov (Encyclopaedia of Chemical Technology, Kirk-Othmer, Fourth Edition, Vol.14, 1996, pages 436-53). In most cases, free-radical initiators are organic peroxides, which are supplied by the manufacturers of organic peroxides and which typically require phase transport and storage.

Organic peroxides are unstable compounds that can undergo thermal decomposition at high or low temperatures, depending on their structure. Therefore, receipt, transport and storage require increased caution in order to prevent any accident in the course of their use.

To avoid problems concerning the regulation associated with transportation is Oh these dangerous products, and to limit their storage, it is sometimes recommended to get organic peroxide directly on the place of its use.

Organic peroxides are usually obtained in the usual open reactors periodic action (batch), because this type of action is most appropriate for safe production of small quantities of peroxides (Encyclopaedia of Chemical Technology, Kirk-Othmer, Fourth Edition, Vol.18, 1996, pages 292-293). However, not all organic peroxides can be obtained under normal conditions of periodic process because of their instability. Some can only be obtained in solution or should then be stabilized in the form of emulsion or by adding the stabilizer. In particular, in the case of highly reactive peroxides, in other words, peroxides, whose temperature corresponding to 10-hour half-life, is relatively low.

These drawbacks can be circumvented by obtaining peroxides in place, in other words, in a reactor in which the polymerization or crosslinking. You can refer to, for example, in U.S. patent 5700856, which describes how to obtain the ketone peroxides in the system that contains unsaturated polyester resin and accelerator linkage.

However, this type of manufacturing process of the organic peroxide to me is they don't allows you to automatically submit peroxide in the reactor-polymerizaton. The main drawback is the lack of precision in respect of the quantities of peroxide effectively used in the polymerization, and the need for a preliminary synthesis of the initiator in place before each polymerization cycle. As a result, the capacity of the plant is limited.

He had already made proposals related to obtaining organic peroxides close to the reactors of the polymerization or crosslinking (ex situ synthesis).

In the document FR 2253760 PEROXYDICARBONATE get from alkylhalogenide and inorganic peroxide in the presence of water and a volatile, water-immiscible solvent immediately prior to polymerization. Further, all of the thus obtained reaction mixture (organic phase and aqueous phase) is introduced into the reactor-polymerization, which is then loaded with the purpose of carrying out polymerization. This method does provide an automated feed of the organic peroxide in the reactor, but it requires precise amount of the initiator, which is sufficient, immediately before the polymerization. In addition, this method demonstrates the shortcomings related to the quality of polymerization and the resulting polymer.

International application WO 97/27229 describes a method of obtaining a solution dialkyldithiocarbamate, which is the most eligible is m for carrying out the process of the aqueous suspension polymerization of vinyl chloride. Solutions dialkyldithiocarbamate in liquid, insoluble in water dialkylaminoalkyl can be obtained in advance in sufficient quantity to supply in a number of reactors polymerization, but must be stored at low temperature in order to prevent any danger. They may be executed wholly or partly after the start of polymerization, which provides an automated feed to the reactor. However, the use of the organic peroxide in the form of solutions in complex air can adversely affect the polymerization kinetics and the General properties of the obtained polymers. In addition, to obtain solutions of dialkyldithiocarbamate includes the extraction of dialkyldithiocarbamate obtained in water using extraction using complex ether.

In the international application WO 03/074573 diazepamonline get in the aquatic environment by peroxidebased and served in the reactor-polymerization within the period of time between 2 hours and 168 hours after receiving them. The reactor, which are reaction peroxidative, can also be connected directly with reactor-polymerization. However, this way of working with highly reactive organic peroxides, for which the cooling requirement and explosion are simply impossible. In addition, using the selected authentication peroxide in aqueous solution in some polymerization processes, such as large-capacity processes for the production of foam or polyethylene or staple polyester resin or polyolefin, cannot be and speeches.

In the international application WO 05/075419 describes a multi-stage method for producing organic peroxides, such as PEROXYDICARBONATE, diazepamonline or paroxetine, in which the reagents, as well as the acid chlorides or chloroformiate take the place of phosgene, which also receive on the spot. Then thus obtained peroxides are used directly in the polymerization reaction.

The present invention consists in overcoming the above drawbacks and relates to a direct application in systems of free radical polymerization or crosslinking of organic peroxides obtained in microreactors or minireactor.

Direct application, in accordance with the present invention, means that organic peroxides selected from the group consisting of di(n-propyl)PEROXYDICARBONATE Reg. CAS no 16066-38-9, di(sec-butyl)PEROXYDICARBONATE Reg. CAS no 19910-65-7, di(2-ethylhexyl)PEROXYDICARBONATE Reg. CAS no 16111-62-9, 1,1-dimethyl-3-hydroxymethylphosphonate Reg. CAS no 95718-78-8, α-semiproletariat Reg. CAS no 26748-47-0, α-semiproletariat Reg. CAS no 104852-44-0, tert-anilinoquinazoline Reg. CAS no 68299-16-1, tert-b is temperaturepageant Reg. CAS no 26748-41-4, tert-Liliaceae Reg. CAS no 29240-17-3, tert-butylperoxybenzoate Reg. CAS no 927-07-1, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane Reg. CAS no 13052-09-0, tert-AMYLPEROXY-2-ethylhexanoate Reg. CAS no 686-31-7, tert-butyl peroxy-2-ethylhexanoate Reg. CAS no 3006-82-4, tert-AMYLPEROXY Reg. CAS no 690-83-5, tert-peroxyacetate Reg. CAS no 107-71-1, tert-amylbarbitone Reg. CAS no 4511-39-1, tert-butylperbenzoate Reg. CAS no 614-45-9, OO-tert-amyl-O(2-ethylhexyl)monoperoxyphthalate Reg. CAS no 70833-40-8, OO-tert-butyl-O-isopropylaminocarbonyl Reg. CAS no 2372-21-6, OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate Reg. CAS no 34443-12-4, poly(tert-butylperoxybenzoate)polyester Reg. CAS no 100-41-4, peroxide of decanoyl Reg. CAS no 762-12-9, peroxide of lauroyl Reg. CAS no 105-74-8, succinic acid peroxide Reg. CAS no 123-23-9, benzoyl peroxide Reg. CAS 94-36-0, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane Reg. CAS no 6731-36-8, 1,1-di(tert-BUTYLPEROXY)cyclohexane Reg. CAS no 3006-86-8, 1,1-di(tert-AMYLPEROXY)cyclohexane Reg. CAS no 15667-10-4, 4,4-di-n-butyl(tert-BUTYLPEROXY)valerate Reg. CAS no 995-33-5, ethyl-3,3-di(tert-AMYLPEROXY)butyrate Reg. CAS no 67567-23-1, tert-butylperoxide Reg. CAS no 3006-82-4, ethyl-3,3-di(tert-BUTYLPEROXY)butyrate Reg. CAS no 55794-20-2, gidroperekisi cumene Reg. CAS 80-15-9 and gidroperekisi tert-butyl Reg. CAS no 75-91-2 obtained at the site of free radical polymerization or stivan what I moreover, the process of synthesis is further defined as ex situ process. Therefore, under the ex situ process refers to the synthesis of organic peroxides on the venue for the polymerization, of at least one curable monomer or crosslinking at least one stitched connection. Organic peroxides are used immediately after they are received and therefore no longer requires any regulation of the conditions of storage or transport.

Technology microreactors or minireactor-based miniature reactors, agitators, heat exchangers, plate heat exchangers, and other items that have the details, the size of which can vary from micrometers to millimeters. The implementation of continuous processes in a closed reactor is one of the advantages of this technology. In addition, due to the reduced size of the channels, which have the function of the tubular reactor, the technical equipment is more efficient compared to conventional reactors periodic action. This technology is more suited for the safe synthesis of unstable chemical products, such as the above selected organic peroxides, which undergo thermal decomposition.

When the private plate exchanger is of Annika, working on technology micro-reactor or minireactor, made possible continuous receipt of the above selected organic peroxides directly on the place where the method of free radical polymerization or crosslinking; in particular, the above selected organic peroxides, even the most reactive, thus obtained, can safely be fed directly into the reactor polymerization or crosslinking in its pure form, without solvents or stabilizers. Thus, the quality of the obtained polymers is higher.

Thus, the present invention relates to a method of free radical polymerization or crosslinking, in which at least one curable monomer or at least one link connecting interact in the presence of at least one organic peroxide selected from the group consisting of di(n-propyl)PEROXYDICARBONATE, di(sec-butyl)PEROXYDICARBONATE, di(2-ethylhexyl)PEROXYDICARBONATE, 1,1-dimethyl-3-hydroxyethylphosphonate, α-semiproletariat, α-semiproletariat, tert-anilinoquinazoline, tert-butylperoxybenzoate, tert-Liliaceae, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-AMYLPEROXY-2-e is Elecsnet, tert-butyl peroxy-2-ethylhexanoate, tert-AMYLPEROXY, tert-peroxyacetate, tert-amylbarbitone, tert-butylperbenzoate, OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate, OO-tert-butyl-O-isopropylaminocarbonyl, OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate, poly(tert-butylperoxybenzoate)polyester, peroxide of decanoyl, peroxide of lauroyl, succinic acid peroxide, benzoyl peroxide, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane, 1,1-di(tert-BUTYLPEROXY)cyclohexane, 1,1-di(tert-AMYLPEROXY)cyclohexane, n-butyl-4,4-di(tert-BUTYLPEROXY)valerate, ethyl 3,3-di(tert-AMYLPEROXY)butyrate, tert-butylperoxide, ethyl-3,3-di(tert-BUTYLPEROXY)butyrate, gidroperekisi cumene and gidroperekisi tert-butyl, and mixtures thereof, characterized in that the organic peroxide receive continuously ex situ by means of a closed plate heat exchanger.

More specifically, the present invention relates to a method of free radical polymerization or crosslinking, in which at least one curable monomer or at least one link connecting interact in the presence of at least one organic peroxide selected from the group consisting of di(n-propyl)PEROXYDICARBONATE, di(sec-butyl)PEROXYDICARBONATE, di(2-ethylhexyl)PEROXYDICARBONATE is, 1,1-dimethyl-3-hydroxyethylphosphonate, α-semiproletariat, α-semiproletariat, tert-anilinoquinazoline, tert-butylperoxybenzoate, tert-Liliaceae, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-AMYLPEROXY-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-AMYLPEROXY, tert-peroxyacetate, tert-amylbarbitone, tert-butylperbenzoate, OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate, OO-tert-butyl-O-isopropylaminocarbonyl, OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate, poly(tert-butylperoxybenzoate)polyester, peroxide of decanoyl, peroxide of lauroyl, succinic acid peroxide, benzoyl peroxide, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane, 1,1-di(tert-BUTYLPEROXY)cyclohexane, 1,1-di(tert-AMYLPEROXY)cyclohexane, n-butyl-4,4-di(tert-BUTYLPEROXY)valerate, ethyl 3,3-di(tert-AMYLPEROXY)butyrate, tert-butylperoxide, ethyl-3,3-di(tert-BUTYLPEROXY)butyrate, gidroperekisi cumene and gidroperekisi tert-butyl, and mixtures thereof, with the specified method comprises steps (a)-(d)are performed at the same place:

(a) continuous receipt of selected organic peroxide with the private plate heat exchanger,

(b) supply, if necessary, the reaction mixture stud and (a) in an installation for cleaning,

(c) the filing of an organic peroxide, obtained in stage (a) or stage (b) into the reactor polymerization or crosslinking,

(d) reaction of free radical polymerization or crosslinking of at least one curable monomer or at least one stitched connection, in the presence of one or more organic peroxides, filed at the stage (c).

In the reactor a continuous portion of the liquid successively come one after another without any mixing. Conventional tubular reactor has a limited heat transfer coefficient. Therefore, the use of a plate heat exchanger will allow to solve this problem.

In order to obtain high productivity, measured in l/h in relation to the volume of the reactor, it is necessary, if the reactions are exothermic, so that the reactor had a high capacity for heat exchange, measured by the ratio of surface area to volume. In addition, if the above selected organic peroxides must limit the maximum attainable temperature, mainly in the field of reactor zone feed stream is injected reactive materials in many points, to regulate the specified maximum temperature. The use of plate heat exchangers provides good quality zones of the reaction, in the result that you can achieve good heat transfer. Consequently, it is possible to better control and manage the possible decomposition reactions of organic peroxides.

In the method according to the invention the reaction can be carried out within a few seconds, even in the case of two-phase mixtures in the case of reactions in microreactors or minireactor according to the method of the invention. Heat removal is facilitated by a high heat capacity, which is expressed by the ratio of surface area to volume.

Thus, on the basis of the benefits relative to the reaction medium, by comparison with data obtained from periodic processes in the usual open reactors, for which the relationship of the surface area/volume are of the order of a few m2/m3and especially for rapid and exothermic reactions, it is possible to get better performance, better turning, better selectivity, the best yield and best quality of organic peroxides, compared with organic peroxides obtained by the methods of the previous prior art. From a security perspective, it is possible to conduct the reaction without risk in higher temperature ranges than is typically used, while ensuring the effect of the acceleration of the reaction rate and, therefore, additional improvements production is titelliste processes.

Regarding the environmental aspect, the fact of the receipt of thermosensitive organic peroxides in the indoor heat exchangers to reduce the release of volatile organic compounds (VOCS).

These systems demonstrate other advantages in terms of flexibility, as the time can be adjusted by the number of plates constituting the heat exchanger; the heat exchanger may consist of a large number of mutually parallel plates.

Typically, plate heat exchangers, which can be used in accordance with the invention, include at least two inlet openings for the interaction of reagents capable of interacting with receiving the selected organic peroxides, preferably at least three inlet. The number of inlet holes is determined so that the temperature in the reaction zone does not exceed a certain value, which is typically a temperature above which the organic peroxide becomes unstable. Thus, it is possible to arrange the inlet for reagents capable of interacting with obtaining these organic peroxides in the multiplicity of holes, concurrently or sequentially, with one heat exchanger can take a variety of reagents and can be used to get you ukazannyh selected organic peroxides in accordance with a wide variety of reactions and different operational modes.

Plate heat exchangers that may be suitable for the method of the invention, are microreactors described in the previous prior art, for example, the system described in document EP 1313554 or in the application WO 02/085511, the contents of which are incorporated by reference.

These systems can further be improved by the installation of devices that allow you to divide the plate in the case of uncontrolled reactions, such as lifting pressure or temperature in the decomposition process. In the case of excess pressure in the heat exchanger, operating in closed mode, it becomes an open reactor that allows you to delete the product and solve the problem in a safe way. These devices for the separation of the plates may consist of a system that allows the plates to move apart, in particular, of:

systems nuts and bolts that are subjected to plastic deformation beyond a certain pressure,

systems nuts and bolts, which are equipped with springs which are compressed when the pressure in the reactor exceeds a certain value,

systems nuts and bolts, which are equipped with lock washers, such as Belleville washer, is designed so that the plates moved apart by a certain distance, if the pressure exceeds a certain value. In addition, the specified systems which has the advantage of returning to its original state, as soon as the pressure falls below a certain value.

Free radical initiators according to the invention are the above selected organic peroxides. The method according to the invention can also be made with organic peroxides selected from the group consisting of dialkylamides and ketone peroxides.

Reactions performed in order to obtain the above selected organic peroxides according to the invention, the reactions are usually liquid/liquid. They can occur in the presence of catalysts, in aqueous medium or in organic medium. You can get a mixture of the above selected organic peroxides according to the invention.

The sequence of reactions that lead to the formation of organic peroxides mentioned above, is described in the Encyclopaedia of Chemical Technology, Kirk-Othmer, Fourth Edition, Vol.18, 1996, pages 230-310.

In the method of the invention the speed of introduction of the reactants may vary within a wide range, possibly from 0.1 l/h 5000 l/h, preferably from 0.1 l/h to 2000 l/h, in particular from 1 l/h up to 2000 l/h

The reagents are injected by means of peristaltic pumps, dosing pumps, self-priming transfer pumps or centrifugal pumps; preferably, dosing pumps or pumps used in liquid chromatography (HPLC), used in the laboratory is tornam scale, and centrifugal pumps in industrial scale.

The heat exchanger can be equipped with thermocouples to measure temperature and pressure.

The temperature range for the reaction includes ranges from 0 to 100°C, preferably from 5 to 60°C.

The internal pressure of the heat exchanger may be in the range from 0 to 5 bar relative to atmospheric pressure, but depends on the number of plates and the volumetric flow rate at the entrance.

The residence time can range from several seconds to several minutes, preferably 1 second to 45 seconds, in particular up to 2-3 minutes.

The heat transfer fluid may consist of water, salt water or a mixture of water/alcohol. The temperature of the liquid coolant varies from -20°C to 90°C, and more specifically from 0 to 50°C.

An additional advantage provided by plate heat exchangers, compared with existing technologies, is the ability to obtain the above selected organic peroxides in solid form, using a higher temperature than its melting point. It is also possible to obtain compositions based on the above selected organic peroxides, such as microemulsions peroxides.

Thus, the above selected organic peroxide obtained ex situ, may be submitted directly the NGOs in the reactor, polymerization or crosslinking, in which the reaction mixture obtained from the plate heat exchanger may be subjected to the final stage of purification, such as the separation/washing, if necessary, and in this case to do the installation for continuous separation, such as, for example, described in Chemical Engineers' Handbook, R.H.Perry/C.H.Chilton, Vol.21, pp.11-12.

As mentioned above, various advantages are obtained through continuous ex situ receipt of the above selected organic peroxides in plate heat exchangers are used in polymerization processes svobodnoradikal of the polymerized monomers or processes of crosslinking compounds capable of free-radical crosslinking.

The reason for this is the fact that this provides a continuous flow reactor polymerization or crosslinking of a continuous and controlled way and, therefore, allows you to enter the above selected organic peroxide continuously during the polymerization reaction or crosslinking (also known as "continuous introduction").

Continuous introduction advantageous in order to improve the kinetics of polymerization or obtain resins at high temperatures, which show good thermal stability. Thus, it is possible to provide improved control of the heat of polymerization reaction in the course of time and Opti is to siroute the effectiveness of the above selected organic peroxide, that leads to increased outputs and reduce cycle of polymerization. The level of residual organic peroxide in the resin decreases, while the properties of the finished resin is improved.

Other advantages lie in the fact that the reactors of the polymerization or crosslinking can be entered directly and continuously, not only the above selected organic peroxides, but also and above selected organic peroxides in the presence of various additives, such as additives that can be included as components of the polymerization or decomposition accelerators.

Methods of free radical polymerization or crosslinking according to the invention are the methods that are typically undertaken in industry thermoplastic resins or polymers; their working conditions known to the skilled technician. We can mention, in particular, the polymerization or copolymerization of vinyl monomers, more specifically, the polymerization of vinyl chloride, ethylene, styrene or acrylic monomers, termootdelenii unsaturated polyester resins and elastomers, crosslinking of polyolefins, obtaining graft copolymers using vinyl monomers, and modified polypropylene. These processes represent a free-radical processes in mass, in solution, in emulsion or the suspension at temperatures in the range from 30°C to 250°C.

The effectiveness of the above selected organic peroxide depends on its rate of thermal decomposition and the effectiveness of radicals formed for the ongoing reaction. The above selected organic peroxide is selected in accordance with characteristics of polurethane that correspond to the temperature and duration of reaction.

Thus, in the case of suspension polymerization of vinyl chloride, the reaction proceeds at a temperature of 45-80°C for 3-10 hours. The above selected organic peroxides used in this polymerization, have a temperature of 10-hour period of polurethane, usually ranging from 20°C to 85°C, more specifically from 20°C to 50°C.

Thus, the invention additionally provides a method of suspension polymerization of vinyl chloride in the presence of at least one organic peroxide, characterized in that the organic peroxide receive a continuous method of ex situ with the private plate heat exchanger, and the organic peroxide is selected from the group consisting of di(n-propyl)peroxy-dicarbonate (Reg. CAS no 16066-38-9), di(sec-butyl)PEROXYDICARBONATE (Reg. CAS no 19910-65-7), di(2-ethylhexyl)PEROXYDICARBONATE (Reg. CAS no 16111-62-9), 1,1-dimethyl-3-hydroxyethylphosphonate (Reg. CAS no 95718-78-8), α-camelpox is neodecanoate Reg. CAS no 26748-47-0, α-semiproletariat (Reg. CAS no 104852-44-0), tert-anilinoquinazoline (Reg. CAS no 68299-16-1), tert-butylperoxybenzoate (Reg. CAS no 26748-41-4), tert-Liliaceae (Reg. CAS no 29240-17-3), tert-butylperoxybenzoate (Reg. CAS no 927-07-1).

In the method, the suspension polymerization of vinyl chloride according to the present invention, the organic peroxide, which is defined above, preferably served continuously during the reaction, which opens up additional application of highly reactive organic peroxides, as defined above, which decays very quickly with full security, and these organic peroxides would not be effective under normal conditions of initiation of free radical reactions.

The invention additionally provides a method of suspension polymerization of styrene in the presence of at least one organic peroxide selected from the group consisting of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (Reg. CAS no 13052-09-0), tert-butyl peroxy-2-ethylhexanoate (Reg. CAS no 3006-82-4), tert-amylbarbitone (Reg. CAS no 4511-39-1), tert-butylperbenzoate (Reg. CAS no 614-45-9), OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate (Reg. CAS no 70833-40-8), OO-tert-butyl-O-isopropylaminocarbonyl (Reg. CAS no 2372-21-6), OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate (Reg. CAS no 34443-2-4), poly(tert-butylperoxybenzoate)polyester (Reg. CAS 100-41-4), peroxide of decanol (Reg. CAS no 762-12-9), peroxide of lauroyl (Reg. CAS no 105-74-8), succinic acid peroxide (Reg. CAS no 123-23-9), 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane (Reg. CAS no 6731-36-8), characterized in that the organic peroxide receive a continuous method of ex situ with the private plate heat exchanger. This method leads predominantly to the foam.

The invention additionally provides a method of polymerization of acrylic monomers in the presence of at least one organic peroxide selected from the group consisting of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (Reg. CAS no 13052-09-0), tert-AMYLPEROXY-2-ethylhexanoate (Reg. CAS no 686-31-7), tert-butyl peroxy-2-ethylhexanoate (Reg. CAS no 3006-82-4), tert-AMYLPEROXY (Reg. CAS no 690-83-5), tert-peroxyacetate (Reg. CAS no 107-71-1), tert-amylbarbitone (Reg. CAS no 4511-39-1), characterized in that the organic peroxide receive a continuous method of ex situ with the private plate heat exchanger.

In the method of suspension polymerization of styrene or the method of polymerization of acrylic monomers according to the invention, the organic peroxide, which is defined above, may preferably be supplied continuously during the reaction.

Other ways Svobodnaya the Noah polymerization or crosslinking with the use of organic peroxides, selected from the group consisting of di(n-propyl)PEROXYDICARBONATE Reg. CAS no 16066-38-9, di(sec-butyl)PEROXYDICARBONATE Reg. CAS no 19910-65-7, di(2-ethylhexyl)PEROXYDICARBONATE Reg. CAS no 16111-62-9, 1,1-dimethyl-3-hydroxymethylphosphonate Reg. CAS no 95718-78-8, α-semiproletariat Reg. CAS no 26748-47-0, α-semiproletariat Reg. CAS no 104852-44-0, tert-anilinoquinazoline Reg. CAS no 68299-16-1, tert-butylperoxybenzoate Reg. CAS no 26748-41-4, tert-Liliaceae Reg. CAS no 29240-17-3, tert-butylperoxybenzoate Reg. CAS no 927-07-1, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane Reg. CAS no 13052-09-0, tert-AMYLPEROXY-2-ethylhexanoate Reg. CAS no 686-31-7, tert-butyl peroxy-2-ethylhexanoate Reg. CAS no 3006-82-4, tert-AMYLPEROXY Reg. CAS no 690-83-5, tert-peroxyacetate Reg. CAS no 107-71-1, tert-amylbarbitone Reg. CAS no 4511-39-1, tert-butylperbenzoate Reg. CAS no 614-45-9, OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate Reg. CAS no 70833-40-8, OO-tert-butyl-O-isopropylaminocarbonyl Reg. CAS no 2372-21-6, OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate Reg. CAS no 34443-12-4, poly(tert-butylperoxybenzoate)polyester Reg. CAS no 100-41-4, peroxide of decanoyl Reg. CAS no 762-12-9, peroxide of lauroyl Reg. CAS no 105-74-8, succinic acid peroxide Reg. CAS no 123-23-9, benzoyl peroxide Reg. CAS 94-36-0, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane Reg. CAS no 6731-36-8, 1,1-di(tert-BUTYLPEROXY)cyclohexane is it. CAS no 3006-86-8, 1,1-di(tert-AMYLPEROXY)cyclohexane Reg. CAS no 15667-10-4, n-butyl-4,4-di(tert-BUTYLPEROXY)valerate Reg. CAS no 995-33-5, ethyl-3,3-di(tert-AMYLPEROXY)butyrate Reg. CAS no 67567-23-1, tert-butylperoxide Reg. CAS no 3006-82-4, ethyl-3,3-di(tert-BUTYLPEROXY)butyrate Reg. CAS no 55794-20-2, gidroperekisi cumene Reg. CAS 80-15-9 and gidroperekisi tert-butyl Reg. CAS no 75-91-2 according to the invention, as should be understood, mean ways that lead to thermoplastic polymers and/or elastomers, which can be defined as a natural or synthetic polymers having thermoplastic and/or elastomeric in nature, and which can be crosslinked (solidified) under the action of a crosslinking agent. In Rubber World, "Elastomer Crosslinking with Diperoxyketals", October 1983, p.26-32 and Rubber and Plastic News, "Organic Peroxides for Rubber Cross-linking", September 29, 1980, p.46-50 describes the fusion process and crosslinked polymers.

Examples of polymers and/or elastomers include linear low-density polyethylene, low density polyethylene, high density polyethylene, chlorinated polyethylene, ethylene-propylene-diene terpolymer (EPDM), copolymers of ethylene and vinyl acetate, ethylene-propylene copolymers, siloxane rubber, natural rubber (NR), polyisoprene (IR), polybutadiene (BR), copolymers of Acrylonitrile and butadiene (NBR), copolymers of butadiene and styrene (SBR), chlorosulphurized polyethylene or floral tomary, ethylene-methyl(meth)acrylate copolymers and ethylene-glycidyl-methacrylate copolymers.

More specifically, we can mention the following.

- Reaction polymerization of ethylene at high pressure, are commonly used in organic peroxides selected from the group consisting of 1,1-dimethyl-3-hydroxybutyl-peroxyneodecanoate Reg. CAS no 95718-78-8, tert-anilinoquinazoline Reg. CAS no 68299-16-1, tert-butylperoxybenzoate Reg. CAS no 26748-41-4, tert-Liliaceae Reg. CAS no 29240-17-3, tert-butylperoxybenzoate Reg. CAS no 927-07-1, tert-AMYLPEROXY-2-ethylhexanoate Reg. CAS no 686-31-7, tert-butyl peroxy-2-ethylhexanoate Reg. CAS no 3006-82-4, tert-AMYLPEROXY Reg. CAS no 690-83-5, tert-peroxyacetate Reg. CAS no 107-71-1, tert-amylbarbitone Reg. CAS no 4511-39-1.

- Area of ABS (Acrylonitrile-butadiene-styrene) polymers, which are commonly used organic peroxides selected from the group consisting of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane Reg. CAS no 13052-09-0, tert-butyl peroxy-2-ethylhexanoate Reg. CAS no 3006-82-4, tert-amylbarbitone Reg. CAS no 4511-39-1, tert-butylperbenzoate Reg. CAS no 614-45-9, OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate Reg. CAS no 70833-40-8, OO-tert-butyl-O-isopropylaminocarbonyl Reg. CAS no 2372-21-6, OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate Reg. CAS no 34443-12-4, poly(tert-butylperoxybenzoate)polyester Reg. No. AS 100-41-4, peroxide of decanoyl Reg. CAS no 762-12-9, peroxide of lauroyl Reg. CAS no 105-74-8, succinic acid peroxide Reg. CAS no 123-23-9, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane Reg. CAS no 6731-36-8.

- Termootdelenii polyester resins, which are commonly used organic peroxides selected from the group consisting of tert-butyl peroxy-2-ethylhexanoate Reg. CAS no 3006-82-4, tert-butylperbenzoate Reg. CAS no 614-45-9, OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate Reg. CAS no 70833-40-8, OO-tert-butyl-O-isopropylaminocarbonyl Reg. CAS no 2372-21-6, OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate Reg. CAS no 34443-12-4, benzoyl peroxide Reg. CAS 94-36-0, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane Reg. CAS no 6731-36-8, 1,1-di(tert-BUTYLPEROXY)cyclohexane Reg. CAS no 3006-86-8, tert-butylperoxide Reg. CAS no 3006-82-4, gidroperekisi cumene Reg. CAS 80-15-9 and gidroperekisi tert-butyl Reg. CAS no 75-91-2.

- Termootdelenii elastomers such as ethylene-propylene copolymers (EPR), ethylene-propylene-diene terpolymer (EPDM), silicon rubber, natural rubber (NR), which can be used are peroxides include benzoyl peroxide Reg. CAS 94-36-0, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane Reg. CAS no 6731-36-8, 1,1-di(tert-BUTYLPEROXY)cyclohexane Reg. CAS no 3006-86-8, n-butyl-4,4-di(tert-BUTYLPEROXY)valerate Reg. CAS no 995-33-5.

The crosslinking of polyolefins, such as Lin is any low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), in the presence of benzoyl peroxide Reg. CAS 94-36-0, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane Reg. CAS no 6731-36-8, 1,1-di(tert-BUTYLPEROXY)cyclohexane Reg. CAS no 3006-86-8, n-butyl-4,4-di(tert-BUTYLPEROXY)valerate Reg. CAS no 995-33-5.

The present invention additionally provides thermoplastic polymers and/or elastomers thus obtained.

The following examples illustrate the invention, but without limiting its scope.

Example 1

An example of a plate heat exchanger used in the method according to the invention shown in figures 1 and 2

The specified heat exchanger 1 includes 3 parallel plates 3, 4, 5, touching each other forming chambers connected in series, designed for the synthesis of, for example, compounds of the above type selected organic peroxides and set in contact with each other during the synthesis by means of nuts and bolts 9. This system 9, the details of which are shown in figure 2, can be opened in case of an increase of pressure or temperature for unclamping 2 plates and removal of reagents in complete safety. In the event of a leak or unsatisfactory work, the use of microreactors provides a small loss products, limiting thus, faith is the likely accident or explosion. The specified heat exchanger contains a number of inlet holes 11 for the reagents required to obtain the above defined organic peroxides. Cooling system (not shown in the figure), which are known to a skilled specialist, provides cooling of the system by circulating the liquid coolant.

Example 2

One of the variants of the method according to the invention, in which the organic peroxide is fed continuously during the polymerization of the polyvinyl chloride

Example 3

The suspension polymerization of vinyl chloride

- Obtain di(2-ethylhexyl)PEROXYDICARBONATE (known under the trade name Luperox©223)

Used the indoor heat exchanger such as shown in figure 1, but including 6 additional plates.

8%Solution of sodium hydroxide NaOH was continuously applied with speed 2,62 l/h in the plate heat exchanger through the hole 11a, and the 70%solution of hydrogen peroxide (H2O2served through hole 11b speeds 0,19 l/H. Then, after the reaction at 22°C in the first plate through hole 11c in the second plate at the rate of 0.99 l/h continuously introduced 2-ethylhexylcarbonate. In the following 8 plates the reaction was carried out at 25°C. Di(2-ethylhexyl)PEROXYDICARBONATE recip is whether with the release of 26% compared to chloroformiate.

Full stream is received in the heat exchanger, filed in the reactor-polymerization within 85, which corresponds to 96.9 g of the solution containing the 5.45 g of di(2-ethylhexyl)PEROXYDICARBONATE.

- Obtain PVC resin in the presence of Luperox©223, obtained earlier in a plate heat exchanger

14 kg Demineralizing water, 2,52 g of citric acid, of 3.73 g of polyvinyl alcohol having a degree of hydrolysis of 78 mol.%, of 3.73 g of polyvinyl alcohol having a degree of hydrolysis of 72 mol.%, 8,08 g of an aqueous solution (comprising 39% of active material) of polyvinyl alcohol having a degree of hydrolysis of 55 mol.%, and 96.9 g of the solution obtained in the heat exchanger, including the 5.45 g of di(2-ethylhexyl)PEROXYDICARBONATE, was introduced at ambient temperature under stirring (250 rpm) in a reactor with a capacity of 30 liters, equipped with a stirrer vane type comprising three blades, and shirt. The content of active oxygen was set at 28 ppm relative to the weight of vinyl chloride monomer (VCM), which is then loaded.

After sealing the reactor, it created a partial vacuum (absolute value of 6.66 kPa), and the vacuum was maintained for 15 minutes. Then the stirring was set at a speed of 330 rpm, after which he introduced 9 kg VCM. The heating is regulated by circulation of cold water in the jacket, resulting in 30 minutes the temperature is round polymerization was 56°C. When the environment of polymerization reached 56°C, regarded as the beginning of the polymerization (time = t0), and the pressure at a given point (P0) was taken as control.

After polymerization for 30 minutes (i.e. at time t0+ 30 min) 4 kg of water is continuously fed into the reactor at a constant flow rate of 1.2 kg/h to improve heat transfer by maintaining a constant surface area of heat transfer shirts and reduce the viscosity of the aqueous suspension after 60% conversion of VCM in PVC, with a specified degree of conversion was calculated from the heat balance, a particular inside the reactor.

The depletion of the gas phase VCM in the reactor was reflected pressure drop between 65 and 70% conversion. As soon as the pressure dropped to 1 bar relative to P0the polymerization was stopped by rapid cooling of the environment through the introduction of the shirt in cold water.

The residual content of di(2-ethylhexyl)PEROXYDICARBONATE was approximately 90 ppm by weight relative to the original weight of the monomer.

Then the residual VCM is removed from the reaction medium by conventional means by returning to atmospheric pressure (degassing), and then traces VCM was removed by degassing in a vacuum 13,33 kPa at 50°C (distillation).

The total amount of PVC resin was 7.6 kg

1. The method of free radical polymerization, in which, p is at least one curable monomer interacts in the presence of at least one organic peroxide selected from the group consisting of di(n-propyl)PEROXYDICARBONATE, di(sec-butyl)PEROXYDICARBONATE, di(2-ethylhexyl)PEROXYDICARBONATE, 1,1-dimethyl-3-hydroxyethylphosphonate, α-semiproletariat, α-semiproletariat, tert-anilinoquinazoline, tert-butylperoxybenzoate, tert-Liliaceae, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-AMYLPEROXY-2-ethylhexanoate, tert-BUTYLPEROXY-2-ethylhexanoate, tert-AMYLPEROXY, tert-peroxyacetate, tert-amylbarbitone, tert-butylperbenzoate, OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate, OO-tert-butyl-O-isopropylaminocarbonyl, OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate, poly(tert-butylperoxybenzoate)polyester, peroxide of decanoyl, peroxide of lauroyl, succinic acid peroxide, benzoyl peroxide, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane, 1,1-di(tert-BUTYLPEROXY)cyclohexane, 1,1-di(tert-AMYLPEROXY)cyclohexane, n-butyl-4,4-di(tert-BUTYLPEROXY)valerate, ethyl 3,3-di(tert-AMYLPEROXY)butyrate, tert-butylperoxide, ethyl-3,3-di(tert-BUTYLPEROXY)butyrate, gidroperekisi cumene and gidroperekisi tert-butyl, and mixtures thereof, characterized those who, what organic peroxide continuously receive the ex situ method using the private plate heat exchanger.

2. The method according to claim 1, characterized in that the organic peroxide get at a temperature within the temperature range from approximately 0 to approximately 100°C., preferably from approximately 5 to approximately 60°C.

3. The method according to claim 1 or 2, characterized in that the heat exchanger includes at least two inlets for the reactants, preferably at least three inlet.

4. The method according to claim 1, wherein the heat exchanger further includes a device for separating the plates, which allows to decompress the plate.

5. The method according to claim 4, characterized in that said device consists of systems of nuts and bolts that are subjected to plastic deformation beyond a certain pressure systems nuts and bolts that are supplied with springs, which are compressed when the pressure in the reactor exceeds a certain value systems nuts and bolts, which are provided with lock washers of the Belleville type, which are designed so that the plates moved apart by a certain distance, if the pressure exceeds a certain value.

6. The method according to claim 1, characterized in that the organic peroxide is served continuously is the reaction of free radical polymerization.

7. The method according to claim 1, wherein the free radical polymerization is the polymerization or copolymerization of vinyl monomers, thermotherapies unsaturated polyester resins and elastomers, obtaining graft copolymer with the help of vinyl monomers.

8. The method of suspension polymerization of vinyl chloride in the presence of at least one organic peroxide selected from the group consisting of di(n-propyl)PEROXYDICARBONATE, di(sec-butyl)PEROXYDICARBONATE, di(2-ethylhexyl)PEROXYDICARBONATE, 1,1-dimethyl-3-hydroxyethylphosphonate, α-semiproletariat, α-semiproletariat, tert-anilinoquinazoline, tert-butylperoxybenzoate, tert-Liliaceae, tert-butylperoxybenzoate, characterized in that the organic peroxide receive a continuous method of ex situ with the private plate heat exchanger.

9. The method of suspension polymerization of styrene in the presence of at least one organic peroxide selected from the group consisting of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-BUTYLPEROXY-2-ethylhexanoate, tert-amylbarbitone, tert-butylperbenzoate, OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate, OO-tert-butyl-O-isopropylaminocarbonyl, OO-tert-butyl-1-(2-ethylhexyl)sonoperoxone is a, poly(tert-butylperoxybenzoate)polyester, peroxide of decanoyl, peroxide of lauroyl, succinic acid peroxide, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane, characterized in that the peroxide receive a continuous method of ex situ with the private plate heat exchanger.

10. The method of polymerization of acrylic monomers in the presence of at least one organic peroxide selected from the group consisting of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-AMYLPEROXY-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-AMYLPEROXY, tert-peroxyacetate, tert-amylbarbitone, characterized in that the peroxide receive a continuous method of ex situ with the private plate heat exchanger.

11. The method according to any of PP-10, characterized in that the organic peroxide is served continuously during the polymerization reaction.

12. The method of free radical polymerization, in which the polymerized monomer interacts in the presence of at least one organic peroxide selected from the group consisting of di(n-propyl)PEROXYDICARBONATE, di(sec-butyl)PEROXYDICARBONATE, di(2-ethylhexyl)PEROXYDICARBONATE, 1,1-dimethyl-3-hydroxyethylphosphonate, α-semiproletariat, α-semiproletariat, tert-anilinoquinazoline, tert-is utilizationof, tert-Liliaceae, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-AMYLPEROXY-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-AMYLPEROXY, tert-peroxyacetate, tert-amylbarbitone, tert-butylperbenzoate, OO-tert-amyl-O-(2-ethylhexyl)monoperoxyphthalate, OO-tert-butyl-O-isopropylaminocarbonyl, OO-tert-butyl-1-(2-ethylhexyl)monoperoxyphthalate, poly(tert-butylperoxybenzoate)polyester, peroxide of decanoyl, peroxide of lauroyl, succinic acid peroxide, benzoyl peroxide, 1,1-di(tert-BUTYLPEROXY)-3,3,5-trimethylcyclohexane, 1,1-di(tert-BUTYLPEROXY)cyclohexane, 1,1-di(tert-AMYLPEROXY)cyclohexane, n-butyl-4,4-di(tert-BUTYLPEROXY)valerate, ethyl 3,3-di(tert-AMYLPEROXY)butyrate, tert-butylperoxide, ethyl-3,3-di(tert-BUTYLPEROXY)butyrate, gidroperekisi cumene and gidroperekisi tert-butyl, as well as their mixtures, however this method involves the following stages (a)to(d), carried out in the same place:
A. getting selected organic peroxide in a continuous way with the private plate heat exchanger,
b. filing, if necessary, the reaction mixture (a) in the cleaning device,
C. filing of an organic peroxide, obtained in stage (a) or stage (b)in the polymerization reactor,
d. reaction of free radical is olymerization, at least one polymerized monomer in the presence of one or more organic peroxides, filed at the stage (s).

13. Thermoplastic polymers and/or elastomers obtained by the method according to one of claims 1 to 12.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: method involves installation and mounting of said equipment, e.g., a pressure release device, onto process apparatus, e.g., a fractionation column, near the wetted region in the process apparatus, containing a flowing liquid-phase medium such that the mobile flowing liquid-phase medium at least periodically gets into contact with the equipment and washes off it at least one group comprising deposits of polymerisable material, a condensate containing said material and a polymer. The disclosed apparatus has a reservoir having at least one wall which forms an inner space which, when carrying out the process in the process apparatus, includes at least one wetted region with a flowing liquid-phase medium; and equipment attached to said wall near the wetted region.

EFFECT: providing safe prolonged use of processing apparatus for fractionation.

20 cl, 9 dwg, 2 ex

FIELD: rubber industry.

SUBSTANCE: invention refers to production of modified cis-1,4-polybutadiene with the presence of the Ziegler-Natta catalyst systems; the obtained polymer is used in manufacturing of general mechanical rubber goods, tyres with good operational characteristics. The way of production is performed by means of butadiene polymerization in the hydrocarbon solvent with the presence of the neodymium-containing catalyst with further addition of a modifier and antioxidant, extraction and drying of the polymer; as a modifier, low molecular non-saturated polyketones are used that contain from 0.1 to 16 weight % of oxygen in the form of carbonyl group and double carbon-carbon bonds; the number average molecular weight of the polyketones is from 5,500 to 15,000; the polyketones are introduced into the polymerizate in the course of monomer conversion that equal or exceed 95 % in the amount from 1 to 40 mmol/kg of butadiene (0.2-12.0 g/kg of butadiene) that goes to polymerization at continuous mixing within 15-60 min. at the temperature of 55-85°C; as a neodymium catalyst, neodymium ethylhexylphosphate or neodymium versatat is used; after the modification process has been completed, the antioxidant in the amount of 4-5g/kg of the ploymer is used.

EFFECT: production of cis-1,4-polybutadiene with the Mooney viscosity of 40-50 n. units, with narrow MMD (<2.5), low cold flow (<25 mm/hour) and improved characteristics of vulcanizing agents.

4 cl, 2 tbl, 16 ex

FIELD: technologies.

SUBSTANCE: nozzle for catalyst injection is provided. The nozzle nozzle for catalyst injection for olefin polymerization includes a first conduit including a body, a tapered section, and an injection tip. The nozzle also includes a second conduit having an inner surface and an outer surface. The first conduit is disposed about the second conduit defining a first annulus there between. The second conduit comprises a first line of axially spaced orifices and a second line of axially spaced orifices, wherein each line is helically disposed about the second conduit such that corresponding axial orifices in the first and second lines are radially spaced. The nozzle further includes a support member at least partially disposed about the outer surface of the first conduit defining a second annulus there between. The support member has a converging outer surface at a first end thereof. The invention comprises also a method for uniform and reproducible method for catalyst injection into a gas phase polyolefine polymerization reactor that provides for polymer dimensions and particle part control.

EFFECT: effervescent nozzle allows for the uniform and reproducible injection of the catalyst into a gas phase polyolefine polymerization reactor to promote uniform, consistent production of polymer product.

26 cl, 6 dwg

FIELD: technologies.

SUBSTANCE: nozzle for catalyst injection is provided. The nozzle nozzle for catalyst injection for olefin polymerization includes a first conduit including a body, a tapered section, and an injection tip. The nozzle also includes a second conduit having an inner surface and an outer surface. The first conduit is disposed about the second conduit defining a first annulus there between. The second conduit comprises a first line of axially spaced orifices and a second line of axially spaced orifices, wherein each line is helically disposed about the second conduit such that corresponding axial orifices in the first and second lines are radially spaced. The nozzle further includes a support member at least partially disposed about the outer surface of the first conduit defining a second annulus there between. The support member has a converging outer surface at a first end thereof. The invention comprises also a method for uniform and reproducible method for catalyst injection into a gas phase polyolefine polymerization reactor that provides for polymer dimensions and particle part control.

EFFECT: effervescent nozzle allows for the uniform and reproducible injection of the catalyst into a gas phase polyolefine polymerization reactor to promote uniform, consistent production of polymer product.

26 cl, 6 dwg

Propylene polymers // 2441028

FIELD: chemistry.

SUBSTANCE: invention relates to propylene polymers, having specific values of total comonomer content and melting point. Described is a propylene polymer having total content of links obtained from ethylene of 4.5-6.0 wt %. The polymer has melting point of 148°-160°C. The invention also describes a gas-phase polymerisation method for obtaining a propylene polymer, a method of producing moulded articles and a moulded article obtained using blow extrusion.

EFFECT: obtaining a propylene polymer having good balance of physical and mechanical properties which can improve efficiency of extrusion methods.

6 cl, 2 tbl, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates controlling the beddings in gas phase reactor with fluidised bed. Proposed comprises producing polyolefin using metallocene catalyst and static charge regulator in gas phase reactor; measuring static charge level in gas phase reactor using first static charge pickup; measuring the loss static charge level in has phase reactor using second pickup of static charge; and feeding static charge regulator into gas phase reactor in amount sufficient for maintaining measured level of static charge loss and measured static charge level in layer at positive magnitude. Note here that amount of static charge regular fed into gas phase reactor is based on measure static charge loss level and layer static charge level.

EFFECT: regulation and minimisation of bedding on walls and dome of gas phase reactor.

16 cl, 1 ex, 4 dwg

FIELD: process engineering.

SUBSTANCE: invention may be used in chemical industry. Proposed method comprises polymerisation of olefin polymer (not obligatorily, together with olefin commoner) in at least one tubular continuous-operation circulation reactor incorporated with multi-reactor system, in the presence of polymerisation catalyst in diluting agent. Suspension including solid particles of olefin polymer and diluting agent are produced. Mean ID of tubular reactor, on at least 50% of its length, makes at least 700 mm. Total pressure drop in reactor circuit makes less than 1.3 bar. High-molecular weight polymer is produced in first reactor while low-molecular weight polymer is obtained in second reactor. First reactor features cubic capacity exceeding 100 kg/m3/h polymer. Ratio of first reactor cubic capacity to that of second reactor exceeds 1. Polymer output exceeds 25 t/h.

EFFECT: reduced specific consumption of electric power.

17 cl, 3 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: ethylene/tetrafluoroethylene copolymer has content of chlorine atoms of not more than 70 parts per million(ppm) and copolymerisation ratio (molar ratio) of polymerised structural units based on tetrafluoroethylene/polymerised structural units based on ethylene ranging from 40/60 to 70/30. Said copolymer contains polymerised structural units based on one more copolymerisable monomer as an optional component in amount of 0.1-10 mol %, in terms of all polymerisable structural units on the whole, and has volume flow rate ranging from 0.01 to 1000 mm3/s.

EFFECT: obtaining thermally stable ethylene/tetrafluoroethylene copolymer having low content of chlorine atoms.

9 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: ethylene/tetrafluoroethylene copolymer has content of chlorine atoms of not more than 70 parts per million(ppm) and copolymerisation ratio (molar ratio) of polymerised structural units based on tetrafluoroethylene/polymerised structural units based on ethylene ranging from 40/60 to 70/30. Said copolymer contains polymerised structural units based on one more copolymerisable monomer as an optional component in amount of 0.1-10 mol %, in terms of all polymerisable structural units on the whole, and has volume flow rate ranging from 0.01 to 1000 mm3/s.

EFFECT: obtaining thermally stable ethylene/tetrafluoroethylene copolymer having low content of chlorine atoms.

9 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: polybutadiene is obtained through polymerisation of butadiene in toluene at 25±1°C in the presence of a catalyst. After adding the catalyst, the reaction mixture is exposed to ultrasound for 1 minute.

EFFECT: low cost of the product.

3 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention discloses a polymerisation method involving the following steps: (a) reacting aqueous suspension containing an initiator, vinyl chloride and optionally one or more copolymers in a continuous action mixing reactor; and (b) further reaction of the obtained suspension in at least one second reactor; where the degree of conversion of vinyl chloride in the continuous action mixing reactor at step (a) ranges from 10 to 40 wt %.

EFFECT: invention can be used to produce copolymers with excellent heat resistance and constant particle size distribution of the obtained polyvinyl chloride(D50=150 mcm).

14 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: method for suspension polymerisation of vinyl chloride is realised in the presence of an initiator, a complex dispersing system and additive agents to obtain polymer particles with relatively high packed density and porosity, improved thermal stability and processability. The polymerisation process takes place in the presence of a complex dispersing system consisting of a protective colloid - a combination of polyvinyl alcohols - partially hydrolysed polyvinyl acetate derivatives having degree of hydrolysis of 69.0-73.5% and 78-82%, in ratio of (1-3):(5-1) and a modifying additive - calcium salt of stearic acid, while adding the complex dispersing system to the polymerisation mixture before adding vinyl chloride.

EFFECT: obtaining vinyl chloride particles with relatively high packed density, good porosity, improved thermal stability and processability into articles using existing methods without using liquid plasticisers.

3 cl, 9 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: method of producing polyvinyl chloride involves the following steps: i) feeding water, a polymerisation initiator, an additive in form of a protective colloid, pH regulator and a vinyl chloride monomer into a reactor; ii) first polymerisation by keeping temperature inside the reactor at 30-80°C; and iii) second polymerisation by raising temperature by 5-20°C from first polymerisation temperature when degree of polymerisation conversion reaches 60% or higher, and addition of an anti-oxidant in amount of 0.001-0.03 pts. wt per 100 pts. wt of all the monomer with completion of polymerisation.

EFFECT: polyvinyl chloride has excellent processibility.

12 cl, 21 ex

FIELD: chemistry.

SUBSTANCE: proposed is a polymerisation method for producing (co)polymer of one or more monomers from which at least 50 wt % is vinyl chloride, an in which one or several organic peroxides, chosen from a group consisting of diacyl peroxides, peroxy esters, peroxydicarbonates and their mixtures, are used together with control agents, chosen from a group consisting of organic hydroperoxides, organic compounds with ethylene saturation, which cannot be homo-polymerised, compounds with unstable carbon-hydrogen bonds, oximes and their mixture, under the condition that, solubility of peroxydicarbonate (peroxydicarbonates) in water at 0°C is not less than 5 pts/mln. The method is a standard polymerisation method in an aqueous dispersion or a polymerisation method in an aqueous dispersion in which at least part of one or several organic peroxides, used as the initiator, is added to the reaction mixture at polymerisation temperature. The invention also relates to formulations, containing organic peroxide and sufficient amount of additive, stabilising the organic peroxide, suitable for use in the given polymerisation method and (co)polymers, obtained using method of polymerisation in an aqueous dispersion.

EFFECT: wider field of using the compounds.

14 cl, 1 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to polymerisation process wherein, at least, one peroxide of half-period 1 to 0.001 h at polymerisation temperature the moment being added, is dosed to the reaction mixture at polymerisation temperature and wherein, at least, during a part of peroxide dosage period i) a coolant unit of a reactor is exposed essentially to maximum cooling ability and ii) mount or initiator added is actively regulated by a temperature controller, thus ensuring polymerisation temperature to be maintained within 0.3°C or lower than specified desirable polymerisation temperature.

EFFECT: improved reproducibility of polymers.

9 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: method of obtaining polyvinyl chloride is realised by means of suspension polymerisation of vinyl chloride in presence of protecting colloid, poorly dissolving initiator, 2,6-di-tret-butyl-2-methylphenol, before charging VC, Zn-containing glycerin mono-oleate or Zn-Mg-containing glycerin mono-oleate in amount 0.03-0.06% of VC weight is introduced into polymerisation recipe composition. In order to enhance thermostabilisation effect, before monomer feeding, Ca stearate or Ca-Zn stearate is introduced into reaction mixture in amount, % of VC weight: -0.03-0.06.

EFFECT: obtaining polymer with higher thermostability, with high ability to absorb plastificator and improved morphologic homogeneity.

1 tbl

FIELD: chemistry.

SUBSTANCE: proposed here is a polymerisation method of one or more monomers using at most, 90 wt % safe amount of a first initiator. The safe amount of initiator used is the maximum amount of the given initiator, which can be used in an identical method, realised at maximum cooling power, and temperature of which does not exceed a set temperature value. A second initiator is used, with half-life from 0.0001 to 1.0 hours at polymerisation temperature. The second initiator has less thermal stability than the first initiator. 10% monomer(s) are at least partially added before polymerisation, in such a quantity and preferably at a different rate such that, not less than 92% of the maximum cooling power is used, at least, in the period of time, in which not less than 10 wt % monomer is polymerised. The initiators are chosen from organic peroxides and standard azo-initiators.

EFFECT: cheap method of producing polymers, particularly polymers containing polymerised vinylchloride.

9 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: in the method of obtaining polyvinylchloride through suspension polymerisation of vinylchloride in the presence of a protective colloid, oil-soluble initiator, 2,6-di-tret-butyl-4-methylphenol, Zn-containing or Zn-Mg-containing glycerine monoester based on alpha-branched saturated monocarboxylic acids of the C10-C28 fraction in quantity of 0.03-0.06 wt % of vinylchloride, is added to the reaction mixture before adding vinylchloride. When necessary, with the aim of boosting the thermostabilisation effect, a Ca stearate or Ca-Zn stearate in quantity of 0.03-0.06 wt % of vinylchloride, is added to the reaction mixture before adding the monomer.

EFFECT: obtaining polyvinylchloride with high thermal stability and good melt fluidity, with improved morphological uniformity and, consequently, improved processing properties.

1 tbl

FIELD: polymer materials.

SUBSTANCE: suspension polyvinylchloride according to invention represents suspension polyvinylchloride with Fickentcher constant = 35-42, which is white powder of nonporous glass-like particles characterized by ratio of Fickentcher constant to "plasticizer absorption time" ranging from 0.3 to 3.0. The powder is prepared via water-suspension polymerization of reaction mixture containing vinyl chloride, peroxide initiator, water, stabilizer, and molecular mass regulator (chlorinated hydrocarbon), which polymerization proceeds on heating and vigorous stirring of reaction mixture (0.5-3.5 s-1) at 60-80°C. Thus obtained polyvinylchloride shows elevated solubility in organic vanish solvents (at least 99%) and finds use in preparation of compositions with elevated aggregative stability in organic vanish solvents useful in production of stable high-concentration varnishes and enamels and containing volatile compounds up to 50%. Polyvinylchloride with indicated characteristics is employed as binder in production of lacquer materials capable of forming coatings with good physicochemical and protective properties. Polyvinylchloride solution itself is characterized by high stability on storage, also at negative temperatures.

EFFECT: extended application area of polyvinylchloride.

5 cl, 2 tbl

FIELD: chemistry and technology of polymers.

SUBSTANCE: invention relates to a method for suspension polymerization of vinyl chloride. The polymerization reaction of vinyl chloride in an aqueous suspension is carried out in the presence of a protective colloid and peroxide initiating agent used in the amount 0.03-0.1% of monomer mass. As a initiating agent method involves using multi-component system comprising the following components, wt.-%: mixture of symmetric and non-symmetric dialkyl peroxydicarbonates, 75-82; synthetic saturated (C5-C22)-alcohols, 1-2.5; alkyl chlorides, 7.5-10; dialkylcarbonates and diethylene glycol esters, 8-14. This composition of mixture provides the constant rate of polymerization of vinyl chloride, uniform heat evolving during all process and creates the possibility for the improved rational using equipment exploited in the polymerization process, significant decreasing auto-acceleration of polymerization in the field of deep conversions, to reduce the process time, to enhance the yield and quality of polymer. All said above results to improvement of thermal stability, granulometric composition, increasing porosity of polyvinyl chloride, its improved capacity for processing and physicochemical properties of synthesized polymeric materials.

EFFECT: improved method for polymerization.

2 cl, 5 tbl, 1 dwg, 21 ex

FIELD: polymer production.

SUBSTANCE: object of invention are particle of foaming polystyrene showing improved foaming ability and strength. Process of invention comprises: (i) polymerization of mixture containing polystyrene granules, styrene monomer, cross-linking agent, foaming substance, poly(oxyethylenesorbitol monolaurate) added when degree of polymerization reaches 70-90% in amount 0.05 to 0.15 wt parts per 100 wt parts monomers, and polyethylene wax synthesized from formaldehyde in amount 0.05 to 0.2 wt parts per 100 wt parts monomers; and (ii) coating the mixture with containing substance. Described is also foaming polystyrene resin composition containing wax Sasol.

EFFECT: improved foaming ability and moldability, and increased strength.

8 cl, 1 tbl, 8 ex

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