CS200486B2 - Process for continuous polymerization and device for making this process - Google Patents

Description

The invention relates to a process for the continuous polymerization of at least one polymerizable monomer in the vapor phase.

The invention further relates to a novel vapor phase polymerization apparatus, and more particularly to a vapor phase monomer polymerization apparatus in a substantially isobaric process using a high yield catalyst and, if necessary, a cocatalyst. The apparatus comprises a horizontal, liquid-cooled stirred bed reactor in which substantially all of the gases leaving the reactor are utilized.

Process according to the invention for the continuous vapor phase polymerization of at least one polymerizable monomer selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentane, butadiene, styrene and vinyl chloride, comprising introducing steam monomer in at least one horizontal a temperature controllable polymerization zone containing agitated polymer particles, wherein the polymerization of the monomer is carried out in the presence of a catalyst in the zone and preferably in at least two zones in series, wherein the polymer particles are optionally fed to at least one additional zone and preferably from all zones and the removal of polymer product particles from the zone or the last of the zones connected in series, characterized in that monomer vapors optionally together with hydrogen are introduced below the surface of the particles in the polymerization zone and preferably all zones under control. temperature by spraying and rapidly evaporating the coolant from the surface in the polymerization zone and preferably most of the zones, wherein from the zones and preferably from all zones a gas stream containing monomer and coolant vapors is removed, the gas stream removed is condensed to form a recirculated coolant stream; the gaseous recirculated stream containing the monomer vapors and the recirculated coolant stream, optionally with coolant replenished, are recirculated to this zone and preferably to each zone where the recirculated gas stream with the monomer in the vapor phase is also recirculated.

The apparatus of the invention comprises a horizontal valence reactor for carrying out continuous polymerization of at least one polymerizable monomer in the vapor phase, comprising, at least one polymerization zone, a centrally longitudinally located drive shaft to which are attached internally groups of adjacent blades extending transversely to the internal surface of the reactor; inlets for introducing a gas stream consisting of monomer feathers into the polymerization zone of the reactor, outlets for an outgoing gas stream consisting of monomer and coolant vapors from the polymerization zone of the reactor, outlet of removed polymer particles from the reactor and at least one inlet for introducing coolant into the polymerization zone. The apparatus is characterized in that the mixing device comprises flat rectangular blades, at least one inlet for introducing a gas stream into the polymerization zone is located in the space at the bottom of the reactor, at least one inlet for introducing the catalyst into the reactor is introduced into the polymerization zone, The polymerization zone is at least one inlet connected at the top of the reactor and at least one outlet is located at the top of the reactor to remove the gas stream from the polymerization zone.

According to the present invention, a reactor can be constructed in which the polymerizable monomer or mixture thereof can be converted economically and efficiently into a polymeric substance in the vapor phase by a substantially isobaric polymerization process. In this case, a horizontal stirred bed reactor is used as the reactor, which is cooled by a coolant and where substantially all the gases leaving the reactor can be recirculated during processing at several different temperatures. In the apparatus, the slightly fluid content of the polymer bed is mixed with transversely oriented stirrers attached to a longitudinally oriented shaft, which is conventionally centrally located in the reactor and the reactor is usually divided into several polymerization sections. The sections are separated from each other by suitable bulkheads, such as overflows. These sections can be individually controlled taking into account the rate of production of the polymer and the polymerization temperature, and in some cases also the partial pressure of the gases in the reactor.

The invention relates to a new split reactor and to a process for the polymerization of a polymerizable monomer or a mixture thereof in a vapor phase, wherein at least two chambers are arranged in the reactor which can be maintained at different hydrogen partial pressures and also at different polymerization temperatures. In particular, the invention relates to a split, horizontal, liquid-cooled stirred bed reactor in which substantially all of the gases leaving the reactor are recirculated in the form of vapors, essentially in the isobaric polymerization of the monomer or mixtures thereof using a catalyst or optionally a cocatalyst. high yields where each of the at least two chambers in the reactor can be maintained at different hydrogen partial pressures and, if desired, at different polymerization temperatures and polymer production rates, controlling the molecular weight, molecular weight distribution and particle size distribution of the lean polymer is produced in the reactor.

The invention relates to a new split reactor and to a process for the polymerization of polymerizable monomer or mixtures thereof in vapor phase, wherein both the polymerization sections and the chambers are arranged in the reactor. Such a reactor makes it possible to combine the advantages obtained by incorporating both sections and chambers.

One of the problems in the polymerization of monomers in solution or suspension is the cost of manufacturing. The monomer polymerization using the vapor phase process can be considerably more economical if the problems associated with it are solved. These problems include thermally controlled mode polymerization, avoiding hot spots and maintaining appropriate particle size distributions, and when using catalysts that provide extremely high yields but are extremely sensitive to poisons, the amount of catalyst, based on the amount of product formed, should be kept to a minimum. Another problem relating to some catalyst combinations is the narrow molecular weight distribution of the products resulting from the use of these catalysts.

The present inventors have focused on solving these problems and in particular on saving energy, raw materials and manufacturing costs. Therefore, they have developed a novel process for the continuous polymerization of at least one polymerizable vapor phase monomer using a horizontal cylindrical reactor.

The inventors were aware that attempts had been made previously to overcome the above problems and that these problems were only partially solved, as is evident from the review of the prior art below.

U.S. Pat. No. 2,502,953 (Jahnig) discloses an overflow device directed downwardly for contacting fluidized solid particles with a gaseous liquid, for purifying or stripping volatiles from solids containing them.

U.S. Patent No. 2,936,303 to Goins discloses conducting a gas-phase polymerization of ethylene, propylene or a mixture thereof in a countercurrent fluidized bed in the presence of an inert diluent gas. In the process described, the solid phase catalyst is passed down the reactor and, for example, the ethylene mixed with the diluent gas is passed upstream through a series of vertical fluidized beds through the reaction zones. In this process, the reaction in the different reaction zones can be independently controlled by evacuating the gas from the last reaction zone, cooling it, and recirculating a portion of the gas to each reaction zone. However, since dilution gas and fluidized bed are used, they must be passed through the reactor. a large amount of gas per unit of polymer produced.

U.S. Patent No. 3,023,203 (Dye) discloses gas-phase suspension polymerization of olefins using a reactor having three concentrically stacked vertical sections, wherein the comminuted catalyst is added suspended in the incoming gas and the temperature is controlled by cooling the gas. In the process, the polymer is removed without pressure drop.

U.S. Pat. No. 3,254,070 (Roelen) discloses a method for gas-phase polymerization of ethylene using conventional cooling, wherein the mixture of reaction products and solid or liquid catalysts is constantly mechanically separated. This patent additionally provides guidance on how to react by agitating the reactants through a series of stages, each having different polymerization conditions. The additional method described herein provides guidance on how liquid phase polymerization can be carried out in the first few steps and vapor phase polymerization terminations. Different polymerization temperatures can be used in separate reactors.

U.S. Patent No. 3,256,263 to Wisseroth et al. Discloses a method for removing heat and making polymer under intense motion, in gas phase olefin polymerization, in a stirred, vertical, fluidized bed reactor with mechanical agitation, and introducing a polymerizable monomer immediately after expansion cooling in the form of a moving gas or liquid stream.

U.S. Pat. No. 3,300,457 (Schmid et al.) Discloses a fluidized bed polymerization of monoolefins, especially ethylene or propylene, using a stirred, vertical reactor. The catalysts and polymer in the reactor are moved downstream of the monoolefins while stirring, and heat is removed by cooling the vessel walls. In operation, a gas stream or a liquefied monoolefin is introduced.

U.S. Pat. No. 3,469,948 to Anderson et al. Discloses a horizontal vane type polymerization reactor that utilizes pulsating purge gases that contain poles of measurable olefin. In the process of this patent, elongate blades that are suitably adapted to allow the movement of the solid polymer resulting from vapor phase polymerization can be used directly.

U.S. Patent No. 3,652,527 to Trieschmann et al. Discloses a gas phase polymerization process of propylene in a stirred bed vertical reactor where the reactor is cooled by evaporation.

It is stated in this patent that it is essential that one component of the catalyst mixture is directly introduced into the bed of solid polymer produced in the polymerization and the other component of the catalyst is supplied above the bed in the gas phase.

Finally, British Patent No. 1 354 020 (Badische) describes a process for the vapor phase olefin polymerization in which the heat produced by the polymerization process is removed by introducing a monomer and a heat transfer agent in a gaseous or liquid state into the polymerization zone.

However, the use of multiple polymerization temperatures in a vertical stirred tank reactor and a fluidized bed is not mentioned, and it is difficult to predict how such an individual device could be achieved in the context of the described device.

The attached drawings show the following:

Fig. 1 is a longitudinal view of the reactor body of the invention described below.

Giant. 2 shows a cross-sectional view of the reactor in section 2-2 of FIG. 1. β

Giant. 3 is another cross-sectional view of the reactor of FIG. 1, taken along section 3-3 of FIG. 1.

FIG. 4 illustrates an embodiment of a substantially isobaric process using the reactor described in FIG. 1 and substantially re-circulating substantially all of the gases leaving the reactor.

Fig. 5 is a longitudinal view of the reactor body according to the invention, which is different from the reactor body shown in Fig. 1.

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Giant. 6 is a schematic of the isobaric process utilizing the reactor shown in FIG. 5 and substantially recirculating all gases leaving the reactor.

As already mentioned, the horizontal reactor and the substantially vapor phase isobaric polymerization process of the polymerizable monomer in which substantially all of the gases leaving the reactor are recirculated employ coolant and stirred bed techniques. The reactor is particularly adapted to use polymerization catalysts which provide a fairly high polymerization yield. Therefore, the remaining catalyst need not be removed from the polymer product during the final stage of polymerization. Generally, the reactor utilizes the controlled introduction of catalyst and coolant components into its at least two polymerization sections directly upwards and into a stirred, slightly liquid bed of the resulting polymer, monomer polymerization being carried out from the vapor phase in the bed. The solid polymer is continuously removed by conduction through an outlet baffle generally at one end into the outlet zone. The monomer or mixture thereof is introduced into the reactor and, if necessary, hydrogen is substantially or completely below the surface of the polymerization bed, and the coolant is introduced onto the bed surface. The reactor generally has at least two polymerization sections, and the individual sections are separated from one another by overflows or other suitably shaped bulkheads to prevent large back-mixing between sections. In each section, the polymerization temperature and polymer production rate can be individually controlled over time so that a product having a controlled molecular weight and particle size distribution can be more easily produced.

The gas leaving the reactor is removed from the top of the reactor after removing entrained fine polymer particles that are removed as much as possible from the gas.

The gas leaving the reactor is then fed to the separation zone, whereby at least some of the fine polymer particles and some of the catalyst components are removed by rapid liquefaction.

if used. The monomer and hydrogen are then recirculated to the feed space in the various polymerization sections of the reactor and introduced to a large extent or completely below the surface of the polymer bed.

to

Some of the coolant, including other fine polymer particles, is discharged from the separation zone and a larger portion is returned to the feed head to the reactor head. A minor part of this coolant, cleaned of fine polymer particles and catalyst components, is fed to the catalyst preparation zone for slicing, so there is no need to supply fresh coolant for this purpose. Provision must be made in the individual reactor sections for introducing different catalyst components and coolant into the different reactor sections.

speed to help individually control the polymerization temperature and polymer production rate in the various sections. The catalyst components may be added to or on a stirred bed.

In another aspect, the present invention describes a horizontal reactor divided into sections and chambers and a method suitable for substantially isobaric vapor phase polymerization of polymerizable monomer while substantially completely recirculating the gases leaving the reactor and cooling with the cooling fluid using a stirred bed technique. wherein the at least one section has a different steam composition than the other sections, and wherein at least one section can be operated at a different polymerization temperature and / or different polymer production rate than the other sections.

The reactor is particularly adapted to use polymerization catalysts which provide a relatively high polymer yield so that catalyst residues need not be removed from the polymer product during the last part of the polymerization process. Generally speaking, the reactor is used for the controlled introduction of catalysts and coolant into at least one section in each chamber directly into or onto a stirred, slightly liquid bed of the resulting solid polymer, and the polymerization of the monomer in the vapor phase is performed above and in the bed. The solid polymer is continuously removed by conduction through an outlet baffle, usually located at one end of the reactor, into the outlet vessel,

The monomer or mixture thereof, and preferably hydrogen to a large extent or completely below the polymer bed and coolant to the bed surface are introduced into the reactor. Each chamber has a separate conduit for the gases removed from the reactor, a coolant separation zone, and a separate recirculation of the vapors returning. Each reactor chamber may have at least one polymerization section separated by baffles, and in a preferred method at least two sections in each chamber are separated from one another by overflows or other suitably formed barriers to prevent large back-mixing between sections. In each section, the polymerization temperature and polymer production rate can be individually controlled.

The at least two chambers are separated by a separating structure which is adapted to prevent mutual mixing of the steam between the chambers but allows free movement of polymer particles from one chamber to the other substantially towards the exit. The polymer product produced in the reactor described above is easier to control the molecular weight, molecular weight distribution, and particle size distribution.

The gas leaving the reactor from each chamber is removed from the reactor head after the fine polymer particles are removed from the effluent stream as completely as possible. This gas is fed to a separation zone, whereby the cooling liquid is at least partially separated with other fine polymer particles and some of the catalyst components from the polymerizable monomer and hydrogen, if used, wherein the monomer and hydrogen are then re-enriched into the feed space of the different polymerization sections of the chambers. usually under the surface of the polymer bed. some of the coolant, including other fine polymer particles, is discharged from the separation zone, and a larger portion is returned to the feed space along the head of the reaction chambers. A second small portion of the separated coolant cleaned of fine polymer particles and catalyst components is fed to the catalyst preparation zone to make it so that there is no need to supply fresh coolant _t for this purpose. In the individual sections of the reactor, provision should be made for the catalyst components and the coolant to be introduced into the different sections of the reactor at different rates to aid in the individual control of the polymerization temperature and polymer production rate. The catalyst components may be added to or below the bed surface.

•

By vapor phase reactor or vapor phase process is meant a reactor or process wherein the monomer or monomers are present as feathers or gases under conditions prevailing in the reactor.

The recirculation system and the reactor are thus referred to because essentially isobaric agents are used. This means that there are no changes other than those normally occurring during processing. Suitably, in the reactor and in the recirculation system, the pressure changes are not greater than - 180 kPs and preferably + are not greater than - 70 kPa.

An embodiment of the process utilizing the reactor of the present invention is illustrated in detail in FIG. 4, which can be divided into approximately two spaces, a reaction space, and a space for processing (separating) gases discharged from the reactor and a space for catalyst production. . '

As seen in FIG. 4, the reaction volume of the horizontal polymerization reactor 401 is divided into several vigorously stirred sections 467, 469, 471 and 473, allowing processing in different reactor sections at different temperatures and / or different product production rates. The polymerization is carried out in each of the above sections to form a polymer bed distributed in the reactor. The polymerization temperature in each section can be individually controlled by a combination of methods including vigorous mixing, controlled differential introduction of recirculated steam into each section via line 475, 477, 479, and 481 located in the bottom of the reactor, and introduction of inert coolant and catalyst components into each section differently. at a feed rate of 453, 455, 457, and 459, and catalyst feed 423, 425, 427, and 429 into the space along the reactor head.

The gases leaving the reactor are removed via the exhaust ducts 483, 485, 487, and 489. Since some defective amounts of fine polymer particles can be produced in the reactor, they are preferably substantially removed prior to evacuating the gases leaving the reactor in the treatment area of these gases and catalysts. in the treatment area using traps, filters, settlers, cyclones or washing machines, or a combination thereof.

The solid polymer is produced in each of the agitated sections 467 to 473 for continuous polymer production. The product in a constant amount passes through the outlet baffle and is fed from the reactor to the polymer vessel 403.

The catalyst, which is dissolved or suspended in the recirculated coolant, is preferably introduced onto the bed surface in at least one of the polymerization reactions section through the catalyst inlet 423 425. 427 and 429. Similarly located feed lines 453, 455, 457 and 459 are used for introducing recirculated coolant, which may contain catalyst, on the bed in the individual reaction sections. However, depending on the nature of the catalyst, cocatalyst and monomer to be polymerized, the catalyst and / or cocatalyst may be injected or otherwise introduced into the reactor as such or in another non-polymerizable additive. For some monomers, the catalyst and cocatalyst may optionally be mixed in the process zone 445 and added together to the polymerization reactor 401.

In one embodiment of the process, it has been found to be advantageous to feed the catalyst and the coolant simultaneously so that the catalyst and the coolant are sprayed onto the surface of the polymer bed in the reactor to distribute the catalysts uniformly over the surface of the polymer bed. However, the catalyst and the coolant may be separated and introduced separately on the bed.

The gas leaving the reactor is passed through line 431 to the scrubbing tower 433, where at least a portion of the coolant, other fine polymer particles, and some catalyst components from the polymerizable monomer and hydrogen, if used, are removed from the gases. The polymerizable monomer and hydrogen, along with some of the coolant vapor, are returned to the polymerization reactor 401 from the scrub head 433, preferably after passing through the heat exchanger 460 and separator 461 to condense additional coolant through blower 444 and recirculated steam line 456 with additional hydrogen and monomer, which are added via lines 463 and 465. The monomer and hydrogen can optionally be returned from the scrubbing tower 433 to the polymerization reactor 401 by bypassing the heat exchanger 460 and separators 461. The amount of steam recirculated to each section of the reactor via 475 477. 479 and 481 can be individually controlled by valves 491. 493.

495 and 497 so that the bed can be kept in a slightly fluid state. The coolant from the separators 461 is substantially free of fine polymer particles and catalyst components and is suitable for use in the production zone 445 for catalyst processing. The coolant separated from the gases that left the reactor is cooled in the heat exchanger 454 and most of it is returned to the scrub head 433 via line 438.

A minor portion of the coolant is returned via line 437 through heat exchanger 443, pump 439, and recirculated coolant line 451 to supply line 453 455, 457, and 459, carrying some of the monomer, hydrogen, cocatalyst and fine polymer particles that have with the gases that have left the reactor, to the scrubbing tower 433. The prepared coolant can be added via line 440. In an important embodiment where a cocatalyst is used, the cocatalyst can be added to the catalyst in the production zone 445 by injection directly into the recirculated coolant stream through line 447 or. can be added directly in the non-polymerizable additive to the polymerization reactor 401. To prepare the catalyst, a small amount of coolant substantially free of fine polymer particles and catalyst components is removed from separator 461 and passed through line 434 and pump 436 to production zone 445. production of a catalyst.

Polymerization in the catalyst production zone 445 or connected line 449 and catalyst feed 423 to 429 can cause a number of clogging problems and can be controlled by keeping the cocatalyst concentration in the catalyst below a certain value, in the production zone 445. This value depends on the type the catalyst and cocatalyst used and the monomer to be polymerized. When the prepared cocatalyst is added to the catalyst in the process zone 445, polymerization can be prevented by possibly connecting a cooling line to the production zone, thereby extending the time required to settle catalyst components, etc. Alternatively, coolant from line 440 may also be used instead of recirculated coolant in a catalyst production zone 445, thereby preventing monomer polymerization in the zone.

Valve 499 may be provided with a bypass line in the catalyst production zone to more easily vary the catalyst concentration in the catalyst ready for introduction into the reactor. It has been found that the particle size of the polymer produced in the polymerization reactor 401 can be advantageously varied by varying the concentration of the catalyst that is introduced by the catalyst inlet 423.

425. 427 and 429. It has further been discovered that a change in catalyst concentration can advantageously be achieved either by varying its concentration in the production zone 445 or additionally or by varying its concentration due to the coolant introduced via line 449 through valve 499 just before the catalyst entry point. 423. 425. 427 and 429. The catalyst is added via line 442.

The solid polymer formed in the stirred polymerization reactor 401 is conducted across the reactor, mainly because the polymer is formed in the reactor bed and not under vigorous stirring. The conditions are provided by blades of a design type that allows mixing but not the forward or backward movement of the bed. The polymer particles in the bed adjacent to the exit baffle are removed by stirring through the open exit baffle, where the orifice size may vary according to the size and position of a number of different devices to maintain the solid polymer level in the reactor.

If an overflow is used, it can be attached to a driven shaft 404 which moves the ring or is attached to the reactor walls and can thereby be conveniently positioned such that the top of the overflow is approximately at bed level during mixing. Thus, emptying can be carried out along the entire length of the top of the partition. However, weirs can be placed horizontally if necessary. Other types of baffles may be used instead of weirs to prevent large back-mixing between two or more reactor sections. For example, the thin wall baffles allow the shaft 404 to be driven. At least one opening can be cut in these thin wall baffles as will be appreciated by those skilled in the art.

The polymer particles guided through the open exit baffles fall into the polymer container 403. The solid polymer collected can be processed with additives and melt extruded into articles in a conventional manner, or can be withdrawn without significant pressure drop from the polymer container 403 as a solid melt and the resulting molten polymer. It is treated with a catalyst decomposing substance and degassed with the additives while still in the molten state and then finally converted to a commercial product size by conventional techniques.

Giant. 1 shows a detail of the polymerization reactor 401 of FIG. 4. As can be seen, the interior of the reactor 101 is formed by four individually controllable polymerization sections 167-173 separated by cases 110-114 which somewhat extend over the center of the reactor and are positioned such that their upper edge is approximately flush with the surface of the polymer bed during mixing. In a preferred embodiment, weirs 110, 112 and 114 are so high that the polymer bed. it fills approximately half the reactor volume. When the solid polymer exceeds the height of the overflow, it falls into the adjacent section while moving towards the outlet.

In an embodiment in which it is desirable to operate at least two gas mixtures (different concentrations of hydrogen) as well as different temperatures in the sections, all these overflows are constructed as above, except for at least one manifold structure that divides the reactor into chambers with different gas mixtures. The manifolds are thin wall baffles extended upwards and fill the cross-sectional area of the reactor with the opening below the polymer bed of the moving solid polymer. Thus, with different gas mixtures, the individual chambers may have separate treatment and recirculation of the gases leaving the reactor and may have separate hydrogen and monomer feeds.

Conventionally split constructions are intended to prevent considerable vapor mixing between the individual chambers, but in one embodiment where hydrogen is treated several times, the vapor is intentionally mixed. In dosing, the vapors from the low hydrogen chambers are introduced into the chambers with sufficient hydrogen, and the monomer is preferably added to the low hydrogen chambers, while hydrogen is preferably fed to the chambers with sufficient hydrogen.

The inside of the reactor is equipped with circulating blades driven by a shaft 104 disposed longitudinally in the reactor 101. The blade is mounted transversely to the shaft and forms a gap gap with the internal wall of the reactor 101, thereby allowing adequate mixing of the bed at the reactor wall. The vanes are preferably flat for maximum mixing of the bed at a given rotational speed. Preferably two impellers are used. The width of the blades is such that between approximately 4 to 12 impellers (8 to 24 blades) the reaction sections are about 910 mm long. The location of the blades relative to the adjacent impellers is approximately 90 °. The vanes are driven by a speed motor 102 that allows the entire polymer bed that is in the reactor to be slowly and regularly inverted. The velocity at which the orbiting colloid should be sufficient for the desired transfer of heat and mass between the liquid, the solid and the gas, but should not be so high that the fine polymer particles get in larger quantities from the polymer bed into the space above him. Typically, the blades rotate 5 to 30 times per minute, allowing the integrity of the bed to be maintained.

Similarly, the space behind the exit baffle and above the exit vessel is provided with at least one similar impeller 120. The number thereof depends on the size of the exit. However, it is also possible to use an outlet assembly or termination or a side outlet device which is mounted in place of the outlet baffle, as will be apparent to those skilled in the art.

A plurality of catalyst and coolant feeds may be used in reactor 101. At least one pair may be used for each polymerization section 167-173.

Catalyst and coolant feeds are of conventional design type. The catalyst and the coolant are introduced into the above stirred bed at approximately the same location. It has been found that the introduction of catalyst and coolant, coupled with slow agitation, provides more uniform polymerization and prevents local melting in the polymer bed, thus reducing the number of molten pieces of polymer formed and reducing reactor performance defects. In one preferred embodiment of the polymerization, the addition of catalyst components and coolant components to different sections, for example by means of valves, is separately controlled in the reactor. Separate addition to the polymerization sections 167-173 of the reactor allows separate control of the polymerization temperature and polymer production rate in the sections and can be used to alter and control the molecular weight and particle size distribution of the polymer.

When recirculated vapors containing polymerizable monomer (s) and hydrogen are used, they are fed via the steam recirculation line 136 to the steam recirculation lines 175 to 181 at a predetermined rate that prevents bed fluidization. The rate at which the recirculated vapors are fed to the individual polymerization sections 1.67 to 173. may be controlled by valves ISi to 197 and may optionally be used to allow the polymerization temperatures and polymer production rate to be varied as desired.

A variant of the process utilizing the reactor according to the present invention is shown in Fig. 6, which can be divided into approximately two spaces, the reaction space itself, and a space for processing (separating) gases withdrawn from the reactor and a space for catalyst production. .

As seen in FIG. 6, the reaction volume of the horizontal polymerization reactor 401 is divided into several agitated sections 467, 469, 471, and 473. allowing processing in different reactor sections at different temperatures and / or different product production rates. The reactor is also divided into two chambers by baffle 428. The polymerization is carried out in each of the above sections to form a polymer bed distributed in the reactor.

The degassing temperature in each section may be individually controlled by a combination of methods including vigorous mixing, controlled differential introduction of recirculated steam into each section via line 475, 477, 479, and 481 located in the bottom of the reactor, and introducing different coolant and catalyst components into each section. at a feed rate of 453, 455, 457, and 459, and catalyst feed 423, 425, 427, and 429 into the space along the reactor head.

The gases leaving the reactor are removed via the exhaust ducts 483, 485, 487, and 489. Since some fine polymer particles may be produced in the reactor, the particles are preferably substantially removed prior to venting the gases leaving the reactor in the gas and catalyst treatment space. space to be treated using traps, filters, indexes, cyclones or washing machines, or a combination thereof.

The solid polymer is produced in each of the agitated sections 467 and 473 which serve for continuous polymer production. The product in a constant amount passes through the outlet baffle and is fed from the reactor to the polymer vessel 403.

The catalyst, which is dissolved or suspended in the recirculated coolant, is preferably introduced onto the bed surface in at least one of the polymerization reaction sections through a catalyst feed 423, 425. 427 and 429. Similarly located feed lines 453, 455, 457 and 459 are used for introducing the recirculated coolant, which may contain the catalyst, in the individual sections. However, depending on the nature of the catalyst, cocatalyst and monomer to be polymerized, the catalyst and / or cocatalyst may be injected or otherwise introduced into the reactor as such or in another non-polymerizable additive. For some monomers, the cocatalyst catalyst is alternatively mixed in process zones 445 and 445a and added together to the polymerization reactor.

As can be seen from FIG. 6, each chamber has its own conduits 551 and 451 and recirculated coolant, and catalyst supply conduits 449 and 449a. However, the catalyst production zones 445 and 445a may be interconnected and, if necessary, only one may be used. Also, a reactor with a plurality of chambers may only use a single coolant separation zone, as long as a different amount of hydrogen can be maintained in the separated steam recirculation lines and hence in the reactor chambers.

In an important embodiment, more than one monomer may be used in the chamber and such monomers may be used in each of the two or more chambers at the same or different partial pressure.

In carrying out the process, it is preferable to feed the catalyst and the coolant simultaneously so that the catalyst and the coolant are sprayed onto the surface of the polymer bed in the reactor. to distribute the catalysts evenly over the surface of the polymer bed. However, the catalyst and the coolant may be separated and introduced separately on the bed.

Catalyst components are typically added to at least one zone in a higher hydrogen concentration chamber, but catalyst components may be added to at least one zone in each chamber.

The gas leaving the reactor is passed through lines 431 and 431a to scrubbers 443 and 443a. wherein at least a portion of the coolant, other fine particles of polymer and optionally used cocatalyst are removed from the polymerizable monomer and hydrogen, if any, from these gases. The polymerizable monomer and hydrogen, together with some of the coolant vapor, are returned to the polymerization reactor 401 from wash heads 433 and 433a, and preferably after passing through heat exchangers 460 and 460a and separators 461 and 461a to condense additional coolant through blowers 444 and 444a. and guiding recirculated feathers 456 and 456a with additional hydrogen and monomer, which are added via line 463, 463a. 465 and 465a. The amount of recirculated steam introduced into the individual sections of the feed reactor 475. '477. 479 and 481 can be individually controlled by valves 491. 493. 495 and 497. The coolant from separators 461 and 461 and is substantially free of fine polymer particles and catalyst components and is suitable for use in production zones 445 and 445a for catalyst processing.

The coolant separated from the gases that left the reactor is cooled in heat exchangers 454 and 454a and most of it is returned to the scrub head 433 and 433a via conduits 438 and 438a. A minor portion of the coolant is returned via conduits 437 and 437a through heat exchangers 443 and 4436, pumps 439 and 439a, and recirculated coolant conduits 451 and 451 and into supply lines 453, 455, 452, and 459, carrying certain amounts of monomer, hydrogen , cocatalyst, and fine polymer particles that were fed with the reactor gases to the scrubbers 433 and 433a.

In an important embodiment using a cocatalyst, the cocatalyst may be added to the catalyst in process zones 445 and 445a by injection directly into the recirculated coolant stream through lines 447 and 447a, or may be added directly in the non-polymerizable additive to the polymerization reactor 401. coolant from separators 461 and 461a and leads with lines 434 and 434a and pumps 436 and 436a to the catalyst production zones 445 and 445a. and

Polymerization in the catalyst production zones 445 and 445a or in the attached lines 449 and 449a and in the catalyst feeds 423 to 429 can cause a number of clogging problems and can be controlled by keeping the catalyst cocatalyst concentration below a certain level in the production zones 445 and 445a. this value depends on the type of catalyst and cocatalyst used and on the monomer or monomers to be polymerized. When prepared cocatalyst. adds to the catalyst in the production zones 445 and 445a. Polymerization can be prevented by possible connection, for example, cooling to the inlet and outlet of the production zone, or by reducing the residence time. Optionally, coolants from lines 440 and 440a may also be used instead of recirculated coolant in the catalyst production zones 445 and 445a, thereby preventing monomer polymerization in this zone.

Valves 499 and 499a may be provided with a bypass line in the catalyst production zone to more readily vary the catalyst concentration in the catalyst ready for introduction into the reactor. It has been found that the particle size of the polymer produced in the polymerization reactor 401 can be varied advantageously by varying the concentration of the catalyst introduced by the catalyst inlet of 2, 422, 422, and 422. It has further been found that or additionally, optionally by changing its concentration due to the coolant introduced through lines 449 and 449a through.

valves 4.9-9 θ 499a, just in front of where the catalyst enters the inlet 421) 425. 427 and 429. The produced catalyst is added via lines 442 and 442a.

The solid polymer formed in the stirred polymerization reactor 401 is conducted across the reactor, mainly because the polymer is formed in the reactor bed and not under vigorous stirring. The conditions are provided by blades that allow mixing but not the forward or backward movement of the bed. The polymer particles in the bed adjacent the exit baffle are removed by stirring the open exit baffle, where the orifice size may vary according to the size and position of a number of different devices to maintain the solid polymer level in the reactor bed.

If an overflow is used, it can be attached to the driven shaft 404 or is attached to the walls of the reactor 401, and thus can conveniently be positioned such that the top of the overflow is approximately at bed level during mixing. Thus, emptying can be carried out along the entire length of the top of the partition. However, weirs can be placed horizontally if necessary. Other types of baffles may be used instead of weirs to avoid large back-mixing in several polymerization sections. For example, thin baffles in the form of a wall attached to shaft 404 may be used which fill the reactor cross section and have at least one opening in these thin baffles.

The baffle 428 is designed to fill the entire cross section of the reactor 401 to prevent intermixing of the vapors in the two chambers. The baffle 428 has at least one opening that is positioned completely below the bed surface to allow free movement of the solid polymer from one chamber to the adjacent chamber in the direction of the polymer container 403.

The purpose of the baffles is to prevent extensive mixing of the vapors in the individual chambers, but in one embodiment of the invention the vapors are mixed by introducing the vapors from the low hydrogen chamber to the high hydrogen chamber and adding monomer to the low hydrogen and hydrogen chamber. into a high-volume chamber.

The polymer particles guided through the open exit baffle fall into the polymer container 403. The solid polymer collected can be processed with additives and melt extruded into articles in a conventional manner, or can be withdrawn without significant pressure drop from the polymer container 403 as a solid melt and the resulting molten polymer. It can be treated with the catalyst decomposer and the additives while still in the molten state to be degassed and then finally converted to a commercial product size by conventional techniques.

Giant. 5 shows a detail of the polymerization reactor 405 of FIG. 6. As can be seen, the interior of the reactor consists of four individually controllable polymerization sections 167 to 173 separated by overflows 110 to 114 which extend somewhat over the center of the reactor and are positioned such that their upper edge it is approximately flush with the surface of the polymer bed during mixing. The reactor shown is provided with one partition 128 which divides the reactor 101 into two chambers having a different steam composition.

The baffle 128 includes an aperture 130 located at the bottom of the polymer bed to allow the solid polymer to move freely from one chamber to the other towards the outlet 103. All baffles are constructed so high that the polymer bed fills approximately half the reactor volume. When the solid polymer exceeds the height of the overflow, it falls over the adjacent section while moving towards the outlet. The baffle comprises a thin wall filling the reactor cross section, which is located at the top of the reactor 101 and has a variable size aperture 130 positioned at the bottom of the polymer bed to allow the polymer to move to exit 103.

In embodiments having different gas composition, the individual chambers may have separate treatment and recirculation of the gases leaving the reactor and may have separate hydrogen and monomer feeds to separate re-circulated vapor lines. The reactor 101 is generally provided with false ends formed by plates 124 and 126 to facilitate mechanical construction.

The inside of the reactor is equipped with circulating blades driven by a shaft 104 disposed longitudinally in the reactor 101. The blade is mounted transversely to the shaft and forms a gap gap with the inner wall of the reactor 101, thereby allowing adequate mixing of the bed at the reactor wall.

The vanes are preferably flat for maximum mixing of the bed at a given rotational speed. Preferably ae uses two impeller blades. The width of the blades is such that between approximately 4 to 12 impellers (8 to 24 blades) the reaction sections are about 91 cm long. The location of the blades relative to the adjacent impellers is approximately 90 °.

The blades are designed to ab. ”Minimize the forward and backward movement of the bed during mixing. They are driven by a motor 102 at a rate that allows the entire polymer bed that is in the reactor to be reversed slowly and regularly. The speed at which the impeller rotates should be sufficient for the desired transfer of heat and mass between the liquid, the solid and the gas, but should not be so high that the fine polymer particles get in larger quantities from the polymer bed into the polymer bed. the space that is above it. The blades typically rotate about 5 to 30 times per minute, allowing the integrity of the bed to be maintained.

4 ·

Similarly, the space behind the exit baffle and above the exit vessel is provided with at least one similar impeller 120. The number thereof depends on the size of the exit. However, it is also possible to use an outlet assembly or termination or a side outlet device which is mounted in place of the outlet baffle, as will be apparent to those skilled in the art.

A plurality of catalyst and coolant feeds may be used in the reactor 101 and one or more such pairs may be used for each section 167 to m.

Catalyst and coolant feeds are of conventional design type. The catalyst and the coolant are introduced to the surface of the stirred bed at approximately the same location. It has been found that the introduction of catalyst and coolant, coupled with slow agitation, provides more uniform polymerization and prevents local melting in the polymer bed, and therefore, the number of molten pieces of polymer formed is reduced and reactor performance is reduced. In a preferred embodiment of the polymerization, the reactor provides separately controllable addition of catalyst components and coolant to the different sections, for example by means of valves. Separate addition to polymerization sections 167-173 of the reactor allows separate control of polymerization temperature and polymer production rate in the sections and can be used to alter and control the molecular weight and particle size distribution of the polymer.

When recirculated vapors containing polymerizable monomer (s) and hydrogen are used, they are fed to both chambers via steam recirculation line 156 (a) 56a to the steam recirculation lines 175 to 181 at a determined rate that prevents bed fluidization. The rate at which recirculated vapors are fed to the individual polymerization sections 167-173 can be controlled by valves 191-197, and this control can optionally be used to allow the polymerization temperatures and polymer production rate to be varied as desired.

In a significant embodiment of the process of the invention, the reactors described above are used in which the polymerization temperature in at least one section is maintained at a different value than in the other section or sections (dual temperature or different processing temperatures) and changes the concentration of some or all of the catalyst component. that are bootable into different sections.

The particle size distribution and the molecular weight distribution are preferably applied.

This can be achieved by individually introducing the catalyst into different sections. Also, at one processing temperature, it may be advantageous to introduce catalyst components at a different concentration than the catalyst components introduced into the other section or sections into at least one section.

E

The reaction temperature range for the polymerization depends on the individual monomer to be polymerized and the desired commercial product to be formed, as is well known to those skilled in the art. The generally used temperature range varies from about 40 ° C to the bed softening temperature. The total polymerization pressure consists of the polymerizable monomer pressure, the vapor pressure of the coolant and the hydrogen pressure, if used, and this total pressure usually varies from about atmospheric pressure to about 43 MPa. The individual partial pressures of the components that make up the total pressure depend on the ratios at which the polymerization occurs, the molecular weight, and the molecular weight distribution of the polymer being produced. The polymerization temperature is monitored in a manner known to those skilled in the art.

The ends of the dummy screens built into the reactor 101 for mechanical design purposes are designated 124 and 1226.

Giant. 2 is a cross-sectional view of the reactor 101 shown in FIG. The figure shows a blade connected at 90 ° to the impeller, an adapted outlet opening in the baffle 218 and a discharge opening 216. Furthermore, the location of the overflow 214 of the polymer bed in the reactor 201 and the direction of movement of the blade with respect to the bed position are obvious.

FIG. 3 is a cross-sectional view taken along line 3-3 of the reactor 101 of FIG. 1. Also shown is the discharge port 316. the outlet port in the baffle 318 and the direction of vane movement with respect to the outlet port in the baffle 318 and the location of the polymer bed.

The apparatus and method described herein can be used to polymerize polymerizable monomers that can be polymerized below the softening point of polymers made therefrom. Such monomers include ethylene, propylene, 4-methylpentene-1, butene-1, vinyl chloride, butsdienes, styrene, and mixtures thereof. Particularly suitable is the polymerization of ethylene and propylene.

The coolant used to control the temperature is readily volatile and can be sprayed onto the surface of the polymer bed to remove heat from the polymer bed by evaporation. It must be inert to the monomer to be polymerized and not contain the catalyst components used in the polymerization. The coolant has a high evaporation heat consumption and is readily volatile in the reactor at the polymerization temperature. Generally, alkanes such as propane, butane, pentane or hexane or closed boiling mixtures thereof may be used. A preferred coolant is ethylene is isobutane or isopentane. It is to be understood that when the monomer for polymerization is readily condensable, such as propylene, a liquefied monomer or a mixture of a liquefied monomer and another coolant may be used as the coolant.

The rate of addition of the c-smoothing fluid should be sufficiently low to keep the polymerization bed dry, i.e., to maintain the partial vapor pressure of the coolant below the dew point, low enough to maximize the cooling effect of the coolant. Generally, the coolant should dissipate at least 50% _{of the} heat of polymerization. It is desirable for propylene to remove more than 90% of the polymerization heat by means of a coolant.

At a polymerization temperature of 93 ° C for ethylene polymerization, it is desirable to remove more than 70% of the heat of polymerization using isobutane and to remove more than 50% of the heat using isopentane.

In general, the catalysts most suitable for the process described herein are those that are very efficient and provide high yield. Also included in this group are cocatalysts consisting of organometallic compounds of Groups Ia, IIa and IIIa of the Periodic System p. Catalysts based on compounds containing transition metal elements. Particularly preferred are cocatalysts comprising an aluminum compound with an alkyl such as a trialkylaluminum or an alkylaluminium halide such as a dialkylaluminum chloride. The transition elements contained in the catalysts may be metals of the IV. or a group V of the periodic system, such as a titanium or vanadium compound, a compound of the VI, a group of the periodic system, such as chromium or molybdenum oxides, or they may be one of the above-mentioned catalysts supported on magnesium or supported on alumina, silica or mixtures thereof .

Preferred catalysts and cocatalysts provide, as mentioned above, high yields.

At the same time, high yields provide catalysts and cocatalysts, the excess of which does not need to be removed from the product.

Preferred catalysts and co-catalysts for the polymerization of ethylene are a trialkylaluminum such as a cocatalyst and a titanium compound such as a supported catalyst containing magnesium or chromium oxide supported on alumina, silica or a mixture thereof. For the polymerization of propylene, it is preferred to use dialkylaluminum chloride as the cocatalyst and active titanium tetrachloride as the catalyst. However, the process and apparatus described herein are not limited to catalysts and cocatalysts, except that catalysts that provide high yields must be used in the apparatus.

The invention is described in connection with the individual examples below, and it is to be understood that these examples are given for illustrative purposes only. All modifications and variations which are within the scope of this invention are within the scope of the appended claims.

He did

The titanium tetrachloride catalyst is suspended in isopentane at a concentration of 30 mg / L and continuously pumped into the reactor at a rate of 300 ml / h. Triethyl aluminum diluted to 1000 ml / l with isopentane is pumped continuously at a rate that maintains the desired weight ratio of triethyl aluminum to catalyst of 3: 1 to 15: 1. Ethylene is fed continuously at a polymerization rate maintaining a pressure of 200 psig. A continuous gas stream of 9.4 l / h is withdrawn from the reactor for gas chromatographic analysis. The hydrogen concentration in the reactor was maintained by 34 mole% by intermittent introduction of hydrogen to control the molecular weight of the polymer. The polymer bed in the reactor is maintained at 73 ° C by continuous spraying with isopentane, the polymerization bed having approximately 30 rpm. The evaporated isopentane is condensed and recirculated. The uncondensed gas (4.5-10 ° C) is continuously recirculated back to the bottom of the stirred polymer bed. The level of the polymer bed is maintained by the open position of the containment overflow. The polymer overflows into the melting cell where the temperature is maintained at 177-204 ° C by a combination of polymerization heat and external electrical heating. The molten polymer is emptied from the bottom and is guided through a horizontally positioned tubing of 19 m diameter and 101 mm length at 204 to 260 ° C under reactor pressure. Water is injected continuously into the molten polymer between the melter and the catalyst deactivator at a rate of 10 ml / h. The molten polymer is extruded from the catalyst deactivator through a 9.5 mm diameter hole and passed into a water bath and cut into pieces. The polymer is produced at a rate of 0.45 to 1.36 kg per hour at a yield of 100,000 grams of polymer per gram of catalyst. The physical properties of the polymer obtained from the melter are shown in Table 1 below. Some properties of the powdered polymer obtained from the reactor are shown in Table 2.

T a b u 1 k a 1

Conditions: 71 ° C, 2.2 MPa mole of hydrogen weight ratio of triethyl aluminum to catalyst = 13: 1 to 15: 1 1. weight ratio of triethyl aluminum to catalyst = 2.6: 1 to 3.75: 1

Obeoné Properties Experiment A Experiment B

Melt density, g / cm ^ Annealed melt density, g / cm ^ Viscosity limit number, dl / g Melting index, MFj.g / 10 min Melting index, MF ₁₀ , g / 10 min Flow rate ratio, MF ^ q / MF ^ Hexane extractable component, fi bm. Volatile component in oven, fi hm. Stiffness, MPa

0.961 0.977 1, 87 0.92 38 41, 0.47 0.20

160

0,959

0,977

2.29

0.44

54.5

0.41

0.28

120

Molecular weight parameters, GPC

Attempt A

Attempt B

Molecular weight distribution, Mw / Mn 7.6 10.5 Tensile properties Tensile strength at permanent deformation MPa at 5? mm / min 3.18 3.22 Tensile strength, MPa at 52 mm / min 2.38 1, 97 Elongation at permanent deflection,% at 52 mm / inin 10 11 Elongation limit,% at 52 mm / min 1 200 659 Impact toughness 2 Tensile strength J / cffi 13.6 , 18,1- Impact toughness, Izod. J / cm 5.0 5.3 Thermal properties Vicat softening temperature, ^V C 130 127 Brittle temperature, ° C - - Table 2 Conditions: 71 ° C, 2.2 MPa 34 mol% hydrogen, weight ratio of triethyl aluminum to catalyst - 13: 1 to 15: 1 Number of fractions Attempt A Attempt B 5K 8S JOR Total polymer produced, g 3,628 5,509 6 637 1 952 Bulk density, g / enP 0.36 0.37 0.37 0.41 MF _j0 28.7 38.7 46.2 MF, 0,89 1,0 1.3 MF, ₀ / MF, -32.3 38.7 37.1,

Example 2

A carbon steel reactor with a diameter of approximately 610 mm and a length of 915 nor: is used for the measurement of propylene and ethylene under the following conditions:

The temperature at one end of the reactor is 83 ° C, the temperature in the middle of the reactor is 77 ° C, and 83 ° C is the temperature near the exit baffle, with a total reactor pressure of 2.9 MPa. Ethylene is fed to the reactor at a rate of 9.29 kg per hour and propylene is added at a rate of 0.13 kg per hour. The recirculated gas velocity is 65 N l / min. Isopentane is used as the recirculated liquid at a rate of 1.1 liters per minute. The supported titanium catalyst is added in an amount of about 0.3 g per hour in toraP of the diluted slurry in isopentane. The amount of suspension added per hour is approximately 11.4 liters. The triethyl aluminum is used as a cocatalyst in the form of a solution in isopentane, at a rate of 35 ml / h, at a concentration of 0.025 g of triethyl aluminum per ml of solution.

A gas analysis of the gases recirculated to the reactor is carried out continuously and the following typical values are found:

hydrogen 37 molar ethane 0.3 molar propen 1.1 molar isopentane 1 molar ethylene 60.6 molar

The melt index of the product was about 0.58 g / 10 minutes.

Ethylene is polymerized in the same manner as described in Example 1. 2.0 wt. of chromium trioxide on silica (W.R. Grace 952 SiOg) The catalyst was cured at 631 ° C with dry oxygen for 12 hours. The catalyst, triisobutyl aluminum and ethylene are continuously fed into the reactor at 99 ° C at a pressure of 2.2 MPa. The molar ratio of triisobutyl aluminum to chromium trioxide was 3. The polymer yield relative to the catalyst was 4600 grams per gram. The polymer is continuously removed in the form of a melt. The produced polymer has the physical properties listed in Table 3.

Table 3

Try

Melting index

Melting index MF, q

Flow rate ratio MF, q / MF ^% lim. extractables% wt. volatile components

Molecular weight distribution Mw / Κϊη

Example 4

6 7

0.20 0.12 0.12

22.2 16.6 20.2 111 138 168

1.5 1.6 1.8

0.65 0.87 0.98

14.7 17.0 15.4

Propylene is continuously polymerized using active titanium tetrachloride as a catalyst and diethylaluminum chloride as a cocatalyst in the gas phase under the conditions set forth in Table 4. Propylene also serves as the cooling liquid itself to remove heat. The polymer is periodically removed in particulate form via a double shut-off chamber equipped with a ball valve at the downstream end of the reactor.

Table 4

Polymerization of propylene

Catalyst: TiCl4

Cocatalyst: diethylaluminum chloride

Conditions: 71 ° C, 2.2 MPa mole% hydrogen

Steam loading time, minutes 145 270 Type of catalyst addition Šaržov you too šaržovitý Et / AlCl / TiCl- ratio 2.8 2.8 2 3 Amount of TiCl 2 added, mg / h 48 <” 24-48 ⁽²⁾ Total quantity produced polymer, grams 165 486 Polymer yield, grams / gram (0 to 145 min) 1,970 (0 to 270 min) 3 120 (0 to 60 min) 1 225 (0 to 60 min) 640 (60 to 120 min) 3 800 (60 to 145min) 4600 (120 to 180 min) 5 300 (180 to 240 min) 4 700 (240 to 270 min) 3 000

(1) 12 milligrams of catalyst are added every 15 minutes up to the 90th minute after which no catalyst is added.

(2) 12 milligrams of catalyst are added every 15 minutes up to the 90th minute, then 12 milligrams of catalyst are added every 30 minutes up to 270 minutes.

Table 4- continued

Steam introduction time minutes 153 ' 225 162 The type of adding of ca. analyzer Continuous Saržovitý Continuous Et ₂ / AlCl / TiCl ₃ ratio Amount added 3.0 2.8 2.9 TiCl 2, mg / h The total amount of polymer produced, 45 24 to 48 ( ²⁾ 46 grams Polymer yield, 296 358, 300 grams / gram (0 to 153 min) 2600. (0 to 225 min) (C to 90 min) (90 to 225 min) 2 9S0 172 7 200 (0 to 162 m

(2) 12 milligrams of catalyst are added every 15 minutes up to 90 minutes, then 12 milligrams of catalyst are added every 30 minutes up to 270 minutes.

Example5.

The deposited titanium tetrachloride catalyst and triethyl aluminum as cocatalyst were used in the same manner as described in Example 1 using about 3 mole% propylene contained in the reaction gas to copolymerize with ethylene. Liquid propylene is added continuously at a rate. 30 ml / h, maintaining a concentration of 3 mol% in the reaction gas. The copolymer is removed in particulate form through a double capping chamber equipped with a ball valve which is connected to the outlet end of the reactor. The catalyst and the cocatalyst were deactivated by treating the copolymer with steam at 121 ° C. An inhibitor is added to the copolymer and the product is then molten extruded in the normal manner in the form of pellets produced. The conditions of the two experiments are shown in Table 5 below.

Table5

Try 1 2 3 4 • Steam loading time, h, min 5.12 3 5.20 4.22 Temperature ° C 82 81 82 80 Total pressure, MPa 2.2 2.2 . 2.2 2.2 Adding speed lysator, mg / h 37.0 29.1 30.9 33.3 ^X TEA / CAT 7.5 7.5 7.5 7.5 Composition, recirculated gas, molar% Hydrogen 38 35 36 31 Ethylene 52 44 52 61 Ethan 6.6 20.5 7.8 4.2 Propylene 2.3 3.2 3.2 3.2 Isopentan 1 1 1 1 Reactor discharge rate, 1 / h 24.5 24.3 16.7 17.3 Polymer produced, grams 500 690 822 1 357

Re-circulated gas composition, molar% 1 2 3 4 Catalyst yield, grams / grams 2 .600 ~ 8 D00 4 9SÚ 5 ~ 32O Melt index, gram / 10 minutes 0.17 0.2 0.2 0.17 to 1.0 ^X TEA / CAT denotes the weight ratio of triethyl aluminum to the catalyst used Table 5 - continued Try 5Δ 58 6 7 Steam loading time, h, min 3.9 3.8 6.37 7.10 Temperature ° C 81 81 82 83 Total pressure MPa 2.2 2.2 2.2 2.2 Adding speed lysator, mg / h ' 40.2 40.2 42 37 ^X TEA / CAT 7.5 15 Dec 7.5 7.5 Composition of recirculated gas, molar% Hydrogen 40 40 42 41 Ethylene 48 48 41 46 Ethan 8.6 8.6 12.6 8.8 Propylene 2.6 2.6 3.1 2.9 Isopentan 1 1 1 1 Reactor discharge rate l / h 19.5 19.5 17.7 18.1 Polymer produced, grams 0 165 339 1 416 Catalyst yield, grams / grams 0 620 1 150 5 345 Melt index, gram / 10 minutes - - 6 to 7 ·

^X TEA / CAT denotes the weight ratio of triethyl aluminum to catalyst used Table 5 continued

Try 8 9 10 11 Steam loading time, h, min 6.55 4.22 3.15 2.45 Temperature ° C 86 ' 85 97 97 Total pressure, MPa 2.2 2.2 2.2 2.2 Adding speed lysator, milligrams / hour 33.3 37.9  39.2 41, 0 ^X TEA / CAT 7.5 15 Dec 15 Dec 7.5

Recirculated gas composition, molar%

Hydrogen 39 36 3f> 36 Ethylene 50 55 52 52 Ethan 7.0 5.1 8.3 8.3 Propylene 3.4 2.9 3.2 3.2 Isopentan 1 1 1 1 Reactor discharge rate, l / h 17.7 7.5 16.7 16.7 Polymer produced, grams 1 015 1 764 754 348 Catalyst yield, grams / grams 4 410 10 660 5 9.5 3 130 Melt index, gram / 10 minutes 6 to 7 6 to 7 6 to 7 6 to 7 ^X TEA / CAT denotes the weight ratio of triethyl aluminum to catalyst used

Table 5 - continued

Try 1 2 Steam introduction time, h min 4.53  5.15 Temperature ° C 90 93 Total pressure, MPa 2.2 2.2 Addition rate, additional catalyst, mg / h 40 28 ^X TEA / CAT 7.5 7.5 Recirculated gas composition, molar% Hydrogen 44 45 Ethylene i 45 46 Ethan 7.0 8.0 Propylene 2.9 2.95 Išopentan 1 1 Reactor discharge rate 1 / h 17.6 18.9 Polymer produced, grams 1 055 1 539 Catalyst yield, grams / grams 5 375 . 8 800 Melt index, gram / 10 minutes 12 to 20 17 to 19

^X TEA / CAT denotes the weight ratio of triethyl aluminum to catalyst used

Example 6

Titanium (III) chloride catalyst and triethyl aluminum as cocatalyst are used for the polymerization of ethylene in the same manner as in Example 1. The polymer is removed in particulate form through a double capping chamber equipped with a ball valve. The catalyst is deactivated by steam treatment at 121 ° C. An inhibitor is added to the polymer and the resulting substance is molten extruded in the normal manner in the form of pellets. The conditions for product polymerization and product properties from some experiments are set forth in Tables 6 and 7 below.

Table 6

Polymer! Start the conditions

Temperature, Section 1 ^U C éž 71 to 96 IN to 96 71 to 96 Temperature, section 2 ° C 79 71 to 96 71 sž 96 71 to 96 Temperature, outlet ° C 74 77 77 77 Solvent reservoir, ° C 58 66 66 63 Pressure, MPa 2.2 2.2 2.2 2.2. Composition, reaction gas, molar% Hydrogen 25 22nd 22nd 20 May Ethylene 74 77 77 79 Ethan 0.2 0.3 0.3 0.2 Isopentan 1 1 1 1 Reactor discharge rate, 1 / h 18.9 t8.9 18.9 54.3 Catalyst Dose concentration, mg / l 125 125 62.5 62.5 Dosing rate, mg / h 31, 9 25.2 10.6 8.7 Cocatalyst Dose concentration of AlEt 4, ml / L 1 250 1 250 625 625 Dose concentration of AlEt,, mg / h 319 252 106 87 Weight ratio AlEt 4 / catalyst 10 10 10 10 Results of polymerization Total reaction time, hours 9.8 .14.8 1,8 á.Ž Total polymer, grams 663 2 107 781 619 Polymer yield per catalyst grams / gram 2 000 5 660 41 700 11 600

J

Polymerization conditions

Temperature, section 1, ° C 71 to 96 96 88 91 Temperature, section 2, ° C 71 to 96 96 87 89 Temperature, outlet ° C 77 77 78 79 Solvent reservoir, ° C 66 66 67 67 Pressure, MPa 2.2 2.2 2.2 2.2 Reaction gas composition, molar% Hydrogen 25 25 60 35 Ethylene 73 72 39 64 Ethan 0.4 0.9 0.3 0.6 Isopentan - - - Reactor discharge rate, 1 / h Catalyst 29.7 5.6 18.4 20.4 Dose concentration, mg / l 62.5 62.5 62.5 125 Dosing rate, mg / h Cocatalyst 1 ', 9 4.85 21, 8 17.2 Dose concentration of AlEt 4, mg / L 625 625 525 1 250 Dose concentration of AlEt,, mg / h 119 485 218 172 Weight ratio AlEt 4 / catalyst Results of polymerization 10 10 10 10 Total reaction time, hours 7.5 7.8 20.9 7.5 Total polymer, grams 1 146 749 52 366 Polymer yield per catalyst, grams / gram 12 800 19 Dec 700 - 2 830 Polymerization conditions Temperature, section 1, ° C 91 85 88 88 Temperature, section 2, ° C 88 83 86 88 Temperature, outlet ° C 78 77 79 77 Solvent reservoir, ° C 67 67 75 60 Pressure, MPa 2.2 2.2 2.2 2.2 Reaction gas composition, molar% Hydrogen 42 40 44. 55 Ethylene 56 59 55 41 Ethan 0.6 0.4 3.0 0.4 Isopentan - - - - Reactor discharge rate, 1 / h 21, 8 21, 2 22.6 20.4 Catalyst Dose concentration, mg / l 80 62.5 31.2 40 Dosing rate, mg / h Cocatalyst 9.1 2.9 11, 6 11.0 Dose concentration of AlEt 4, mg / L 800 625 313 200 AlEt dosing rate ≥ mg / h Weight ratio AlEt 4 / catalyst 91 29 116 55 10 10 7.5 5 Results of polymerization Total reaction time, hours á, 5 M 6.5 22.9 Total polymer, grams 429 3 335 2.05 3 077 Polymer yield per catalyst, grams / gram 19 Dec 240 204 000 2 715 12 200

Severopnfta. 7 'Mwl \

Table 7

General properties Section 13 to 22 Section 23 to 39 Annealed Melt Density, g / cnp 0.9734 0.9737 Limit viscosity number, dl / g 1.99 1.26 Melt Index, MF ₁ , g / 10 min 1.1 7.3 The melt index, _{MF), 0} g / 10 min 35 234 Flow rate ratio, MFjq / MP ^ 32 32 Hexane extractable component,% wt 0.30 0.70 Volatile component in oven,% wt. 0.04 0.33 Stiffness, MPa 962 1 258 Tensile properties The tensile strength not between the deformations lasted, MPa at 52 mm / min - Tensile strength, MPa at 52 mm / min 2.06 3.38 Elongation at permanent deformation limit,% at 52 mm / min 11 - Elongation limit,% at 52 mm / min 1 100 9.9 Impact toughness Impact tensile strength, J / om 17, t 4.6 Thermal properties Vioat softening temperature, ° C 128 126

Example 7

Propylene is polymerized in substantially the same manner as described in Example 1. Propylene is used as the recirculated gas and the coolant. The melting point temperature of 177 ° C, the catalyst decomposition section operates at 204 ° C. Active titanium tetrachloride, as a catalyst (33 mg) and diethylaluminum chloride, as the cocatalyst (77 mg), whereby the molar ratio of aluminum to titanium is 3, are introduced into the reactor every 30 minutes. Hydrogen is introduced as needed to maintain 2.9 mol% in the reaction gases in the cap. The reaction temperature was maintained at 71 ° C. The reactor pressure is adjusted to 2.2 MPa by controlling the temperatures in the recirculating condensers to 49 ° C. The polymer yield per catalyst was 10,000 grams per gram. The polymer is removed from the reactor as a melt. The polymer has a melt index of 16.4 g / 10 min at 230 ° C at a load of 2060 g. The extractable fraction on n-hexane at 68 ° C is 4.0 wt%.

Example 8

Ethylene is polymerized in the same manner as in Example 1, except that in this case the two reactor sections are maintained at different temperatures. The first reaction section operates at 71 ° C, while the second reaction section operates at 99 to 110 ° C. This is achieved by varying the amount of isopentane, as a coolant, added to each section. The titanium compound is used as the catalyst and triethyl aluminum as the cocatalyst, wherein the weight ratio of cocatalyst to catalyst is 3: 1. The pressure in the reactor is adjusted to

2.2 MPa and hydrogen concentration was maintained. 40 mole%. A yield of 62,000 g of polymer per g of catalyst is achieved. The melt index of the polymer was 5.5, q / MF, about 40 and the spiral flux was 457 mm. A polymer of the same melt index produced under uniform temperature conditions j exhibits a MF, q / MP value of about 34 and a spiral flux of about 406 mm.

Spiral flow is an experimental method for determining the difficulty of processability of the polymer flow length measurements at a single melt-specific ⁰ * ¹ temperature and pressure conditions, the longer the spiral flow, the easier -is workability.

Further examples illustrate the invention using a two-compartment reactor.

Examples 9 to 11

A carbon steel reactor having a diameter of approximately 610 mm and a length of 915 mm is used. Isopentane is used as the coolant. Titanium tetrachloride supported on the magnesium compound is used as the catalyst, triethyl aluminum is used as the cocatalyst at a weight ratio of about 6 cocatalysts to the catalyst, with ee added at a rate of about 0.2 g per hour. Production takes place at a rate of approximately 5.4 kg per hour. The catalyst and cocatalyst are added separately to the (first zone and the product is removed from the second reactor zone. Both zones are separated by a separation element as described above).

The melt and intrinsic viscosity parameters are measured according to ASTM Standard D 1238-72 (condition E) and D ^ 2857. The ratio of weight average (molecular weight to number average molecular weight Bw / Bn) is determined by gel chromatography.

Examples 9, 10 and 11 illustrate the effect on the molecular weight of two-chamber processing at two different hydrogen levels compared to reactor production at one hydrogen level.

Example 9 represents the production of a product under a uniform hydrogen treatment at a total pressure of 2.9 MPa when the polymerization is carried out at a temperature of 99 ° C with 25 mole% hydrogen in recirculated flesh / Product my viscosity limit number | (9) 2.0 dl / g a melt index of 0.97 g / 10 min and a relatively narrow molecular weight distribution Mw / Bn of 6. Similarly, when the reactor is operated at 99 ° C and 57 mole% hydrogen, the product has the following characteristics: 9 = 1.02 dl / g, a melt index of 28.6 and a molecular weight distribution of Bw / Bn = 6. When the reactor is operating at 99 ° C and 5 mole% hydrogen, the product has a 9 = 4.5 dl / g. At high molecular weight, accurate determination of the melt index is difficult and sometimes has not been performed at all.

Table 8 shows the polymerization results of Example 10, maintaining a temperature of 99 ° C and 26 mole% of hydrogen in the first reactor chamber and a temperature of 99 ° C and 12 mole% of hydrogen in the second chamber. The relative production of the polymer produced in the first and second sections is 42:58, expressed as a weight ratio. The product leaving the reactor has a viscosity limit of 2.1 dl / g and a melt index of 0.68. However, the product Bw / Bn measured increases to about 9, which improves the rheological properties.

Example 11 in Table 8 shows the polymerization results in which the first chamber of the reactor was operated at 99 ° C and 57 mole% of hydrogen and the second chamber maintained a temperature of 99 ° C and 5 mole% of hydrogen. The relative ratio of the substances produced in the first and second chambers is 70:30. The product leaving the reactor has a viscosity limit of 1.99 dl / g and a melt index of 0.67 g / 10 min. However, the measured value Bw / BN product has increased to approximately 12. Changes rheology at two production conditions with hydrogen exhibits a decrease in viscosity at 5 sec ^_1, from 5.5 to 5.2 x 10 ^ Pa s, increase the shear rate at the beginning the oscillation of the flow 650 at 1560 s ^-1 shear rate and an increase in the tearing of the melt / gamma (MF) / z 2400 at 6900 s ^- '.

Table 8

Example number 9 10 11

Component 1 (<j) dl / g 2,0 1,02 1,02 Component 1, melt index 0.97 28.6 28.6 Component 2, (9) dl / g - 2.83 4,5 Component 2, melt index - ’0.16 X First split / second band 100/0 42/58 70/30 Product (<9) dl / g 2,0 2.10 1.99 Melting index (g / 10 min) 0.97 0.68 0.67 Molecular weight distribution Bw / Bn J 5.6 9.1 11.7

Rheology

Xi

5.5

5.6

650 to 2,100 2,400

928 to 1 940 5 100

560 to 2,630 6,900 hodnota Value too low for accurate measurement

Claims (6)

SUBJECT OF THE INVENTION. A process for the continuous vapor phase polymerization of at least one polymerizable monomer selected from the group consisting of ethylene, prooylene, 1-butene, 4-methyl-1-pentene, butadiene, styrene and vinyl chloride, comprising introducing vapor monomer monomer into at least one horizontal polymerization zone. temperature controllable agitated polymer particles, wherein the polymerization of the monomer is carried out in the presence of a catalyst in the zone and preferably in at least two zones in series, wherein the polymer particles are optionally fed to at least one additional zone while removing the monomer containing gas stream from All zones and the removal of polymer particles as product from the zone or the last of the zones connected in series, characterized in that monomer vapors, optionally together with hydrogen, are introduced below the surface of the particles in the polymerization zone and preferably all zones under temperature control. By rapidly and rapidly evaporating the coolant from the surface in the polymerization zone and preferably all zones, wherein a gas stream containing monomer and coolant vapors is removed from the zone and preferably all zones, and the gas stream removed is condensed to form a recirculated coolant stream and recirculated gaseous stream. a stream containing monomer vapors and a recirculated coolant stream, optionally with coolant replenished, is recirculated to this zone and preferably to each zone where the recirculated gas stream with the monomer in the vapor phase is also recirculated, 2. A process according to claim 1, wherein the coolant is selected from the group consisting of propane, propylene, butane, isobutane, pentane, isopentane and hexane. 3. A horizontal cylindrical reactor for the continuous polymerization of at least one polymerizable vapor phase monomer according to any one of items 1 and 2, comprising at least one polymerization zone, a central longitudinally disposed drive shaft to which are attached internally a plurality of adjacent blades extending transversely and further comprising inlets for introducing a gas stream consisting of monomer vapor into the polymerization zone of the reactor, outlets for an outgoing gas stream consisting of monomer and coolant vapors from the polymerization zone of the reactor, outlet of polymer particles to be removed from the reactor; liquid into the polymerization zone, characterized in that the mixing device comprises flat rectangular vanes (106, 108, 122, 132), at least one inlet (175, 177, 179, 181) for introducing a gas stream into the polymerization zone is located at the bottom of the reactor, at least one inlet for introducing the catalyst into the reactor is introduced into the polymerization zone, for introducing coolant into the polymerization zone there is at least one inlet (153, 155, 157, 159) connected at the top of the reactor and at least one outlet ( 183, 185, 187, 189) is located in the upper part of the reactor to remove the gas stream from the polymerization zone (105). 4. The reactor of claim 3, wherein there is at least one partition (128) filling the reactor cross-sectional area to form at least two polymerization zones (105) in the reactor, the partition having an opening (130) in the bottom portion. for conveying polymer particles between zones. A reactor according to claim 3 or 4, characterized in that there is at least one overflow (110, 112, 114) forming at least one polymerization section (167, 169, 171, 173) with a controllable polymerization temperature in the polymerization zone. 6. A reactor according to any one of claims 3 to 5, characterized in that an outlet zone (107) separated by a baffle (116) is provided to fill the reactor cross-sectional area, provided with an opening (118) in its upper part for gas flow and controlled movement. of polymer particles in the direction of the exit between the polymerization and the exit zone (107), the exit zone (107) having an outlet (103) for removing polymer particles from the reactor. 5 sheets of drawings