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    • 专利摘要:
    A continuous process and an apparatus for the polymerization of vinyl chloride in aqueous emulsion wherein the liquid reaction mixture is fed into the lower part of a vertical, cylindrical vessel, the liquid level in the vessel is adjusted to at most 97% of the total interior height of the vessel, the reaction mixture is stirred with a stirrer which is totally immersed in the liquid and extends over 15 to 60% of the total interior height of the vessel and the produced polymer emulsion is laterally discharged from the upper part of the vessel.
    公开号:SU856389A3
    申请号:SU772488546
    申请日:1977-06-02
    公开日:1981-08-15
    发明作者:Кастнер Пауль；Хайнце Кристоф
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    This results in the further processing of polymers into molded objects, the formation of shells or flakes. Plate agitators, especially in reactors with a large height-to-diameter ratio, have an effect in the upper part of the reactor, while zones, there is only slight mixing of the liquid.
    The aim of the invention is to prevent the formation of deposits of polymer on the inner surfaces of the reactor.
    This goal is achieved by the fact that in a known method of producing vinyl chloride polymers by aqueous emulsion homopolymerization, copolymerization or graft copolymerization of vinyl chloride in the presence of radical initiators and surfactants in a vertical reactor with a ratio of height to diameter of at least 3 and a capacity of at least 5 m, c. By controlling the level of the liquid phase, the polymer emulsion formed is removed from the reactor at a height equal to 30-90% of the total internal height of the reactor above the input of the initial mixture at least 15 cm below the liquid phase mirror; the contents of the reactor are mixed with at least one stirrer equal to over the length of 15-60% of the total internal height of the reactor and set at a distance of at least 15 cm from the wall of the reactor, the upper end of the mixer is at a distance of no more than 20 cm below the liquid phase mirror, and the level of the liquid phase is not equal to more than 97% of the internal height of the reactor
    In addition, the process can be carried out in a reactor equipped with an additional stirrer, located at least 15 cm from the wall, a reactor occupying no more than 10% of the total internal height of the reactor and rotating in the same direction as the stirrer mentioned above.
    This goal is achieved by using a device for carrying out the method of producing vinyl chloride polymers, which contains an installed vertically cylindrical jacketed reactor, an opening for supplying liquid in its lower part, with an opening for discharging gases in the upper part
    the reactor and a side drain hole made in the top of the reactor at a distance of 30-90% of the internal height of the reactor from the hole for. fluid supply, and the mixer, the latter is made in the form of at least one
    plate mounted on the shaft and lying in the plane of the shaft axis, the plate height being 15-60% of the internal height of the reactor, and width 25-80% of the internal diameter of the reactor.
    The ratio of the height of the reactor to its diameter is 4-16,
    In addition, the device can be equipped with an additional mixer with a diameter of 25-80% of the internal diameter of the reactor installed in its lower part.
    In this description, the term internal height of the reactor means the size inside the vessel from the lowest point of the bottom to the highest point of the lid, and the holes or protrusions whose cross section is less than 1/5 of the internal diameter of the reactor are not taken into account.
     The predetermined height of the liquid in the reactor is measured by previously known methods as well. the fluid outlet is controlled by measuring signals so that the liquid mirror in the reactor is at least 15 cm above the edge of the outlet
    The polymerization raw materials are supplied in liquid, dissolved or dispersed form to the bottom or laterally through the shell of the reactor in its lower third. The starting materials, for example, an aqueous solution of surface-active materials, as well as a solution of radical-forming catalysts, can be separately fed to the reactor, or mixed up or pre-emulsified near the entrance to the reactor. For mixing, for example, doses, rapidly rotating or vibrating mixers, ultrasonic devices, colloid mills are used. The circumferential speed of the agitator in the reactor can vary widely depending on the type of polymerization, in particular, the type and amount of surface active substances used, as well as on the desired values and the shape of the grains (granules). Circumferential velocities of 0.2-10 m / s are used.
    The polymerization is carried out at 1090 ° C, preferably 30-80 ° C, in particular 40-75 ° C. Can be used for copolymerization of ninyl chloride, giving 0.1-99% by weight (relative to the weight of vinyl chloride), for example, or several of the following monomers: olefins, such as ethylene or propylene, vinyl esters, having a straight or branched chain of carboxylic acid atoms of 2-20, preferably 2-4, carbon atoms, such as vinyl acetate-propionate, butyrate, -2- ethylhexoate,. isotridecanoic acid vinyl ester; vinyl halides, such as vinyl fluoride, vinylidene fluoride, vinylidene chloride, vinyl ether, vinylpyridine, unsaturated acids, such as maleic acid.
    fumaric, acrylic, methacrylic, and their complex mono- and di-esters with mono or dispersants with 1–20 carbon atoms; maleic acid imide, as well as N-products of substitution with an aromatic, cycloaliphatic and optionally branched aliphatic substituent; acrylonitrile, styrene. - - -.
    For graft copolymerization, for example, elastomeric polymerization products may be used, which, by polymerization, contain one or more of the following monomers: dienes, such as butadiene, cyclopentadiene; olefins, such as ethylene, propylene, styrene; unsaturated acids, such as acrylic or methacrylic, as well as their esters with mono- and dihydric compounds with 1-10 carbon atoms, acrylonitrile, vinyl compounds, such as vinyl esters of carboxylic acids having a straight or branched chain of atoms, from 2-20, preferably 2-4 carbon atoms, vinyl halides, such as vinyl chloride, vinylidene chloride. The polymerization can be carried out with or without the use of granules of the product, preliminary polymerization. In this case, the polymerization occurs in an aqueous solution in the presence of, 001-3 wt.%, Preferably 0.010, 3 wt.% Of pi relative to the monomers of the radical-forming catalysts, such as persulfates, perphosphates, potassium perborates, sodium or ammonium, hydrogen peroxide, tertiary butyl hydroperoxides or other water-soluble peroxides, as well as mixtures of various catalysts, and the catalysts can also be used in the presence of 0.01-1 wt.% in relation to the monomers of one or more reducing substances which are suitable for and redox catalyst systems such as sulfates, bisulfates, dithionites, thiosulfates, sulfoksalaty aldehyde such as formaldehyde sulfooksalat sodium. If necessary, polymerization can be carried out in the presence of soluble and poorly soluble metal salts, for example copper, silver or iron, in an amount of 0.0510 ppm based on the ratio of metal to monomer. In addition, the polymerization is carried out in the presence of 0.01-5 weight. in relation to the monomer of one or more emulsifiers. Anionic, amphoteric, cationic, and non-ionic emulsifiers can be used as emulsifiers. Suitable anionic emulsifiers may be used, for example, alkali metal salts, alkaline earth metal, ammonium, fatty acids such as lauric, palmitic or staarinova esters parafinsulfonovoy acids, alkyl aryl sulphonic acid such as dodecylbenzene sulfonic dibutilnaftalin, complex or dialkilbenzol- dibutilnaftalin sulfonic acid dialkyl esters of sulphattic acid, as well as alkaline and ammoniumBEJX salts of fatty acids containing epoxy groups, such as epoxystearic to acid, with unsaturated fatty acids, such as oil or linoleic acid, or with unsaturated fatty hydroxy acids, like ricinoleic acid. As amphoteric or cationic emulsifiers, for example, alkyl beetines, such as dodecyl betaine, -a also alkyl pyridine salts, such as lauryl pyridine hydrochloride, alcohol salts of ammonium, such as hydroxyethyl dodecyl ammonium chloride, can be used. Non-ionic emulsifiers include, for example, the esters of the fatty acids of polyvalent alcohols, such as glycerin monostearate, sorbitol monolaurate, α-oleate, or α-palmitate, polyoxyethylene ethers from fatty alcohols or aromatic hydroxyl compounds; polyoxyethylene fatty acid esters; and polypropylene oxide-polyethylene oxide condensation products.
    Along with catalysts and emulsifiers, polymerization can be carried out in the presence of buffering (intermediate) substances, such as alkyl acetates, borax, alkaline phosphates, alkali carbonates, alkaline bicarbonates, ammonia or ammonium carboxylic salts, as well as multimolecular compounds, such as aliphatic aldehydes. with 2-4 carbon atoms, chloride or bromide hydrocarbons, such as di- and tri-lorethylene, chloroform, bromoform, methylene chloride, and mercaptan.
    The proposed method is particularly suitable for the continuous polymerization of vinyl chloride a with an emulsion of polymereates with a content of at least 80% by weight (relative to the pure polymerization) of the units being polymerized (quantitative) of vinyl chloride. The heat generated during the reaction can be removed by cooling the reactor wall with the help of cooler inserts or by cooling with reflux condensers, and the cooling intensity can be controlled by measuring the temperature of the reaction mixture. To reduce sedimentation, special substances may be added to the mixture to be polymerized, or the inner surfaces (walls) of the reactor and the inserts are chemically treated, coated with a KaKoro-Tiire substance or varnished. Polymerization can also be carried out by creating an electric potential difference between internal parts of the reactor and inserts insulated from one another and, if necessary, with additional spraying with water or an aqueous solution of reactor walls that are not covered with liquid. With this method, the formation of grit (undesirably large particles of polymerizate) and the deposition of crusts on reactor parts and inserts in the upper surface area (mirror) of the liquid are significantly reduced compared to the usual movement of liquid with feed materials from the top and bottom emulsion containing polymers. The clogging of the output of the emulsion, as it happens with the known methods, occurs with this method much less frequently. Filters (grids) for grits that are common to known methods and installed in an outlet pipe for an emulsion containing polymers may be missing. The duration of polymerization is significantly lengthened, so that no significant labor costs occur and productivity increases. In addition, the emission of vinyl chloride associated with cleaning operations is greatly reduced. The method can also be applied in shear-sensitive emulsions. Compared with the known methods, this method is characterized by higher operational reliability; When the polymerisation reactor is out of commission, measure a predetermined height of the liquid and the regulator of this predetermined height of the liquid only small losses, while with conventional methods it can lose so much liquid that it will not be immersed in the liquid or immersed to an insufficient amount . Due to deteriorated mixing and too little cooling surface, temperature and pressure can quickly rise in the polymerization reactor, which leads to an immediate threat to the operating personnel and loss of the product being polymerized. A device for carrying out the process consists of an installed vertically ticly-cylindrical reactor with an aspect ratio of height to diameter (measured inside the reactor) - 3 to a total capacity of 5 m, which has at least one agitator, and one hole located in the lower part of the reactor for supplying a liquid, and in the upper part of the reactor at least one hole for removing liquid and gas, revolutor the position of the liquid mirror in height, and a double shell separated in the lower zone, if necessary, and e for liquid removal is located laterally in the shell of a cylindrical reactor at a distance of 30-90% of the internal height of the reactor above the liquid inlet located in the lower third reactor and the fact that an agitator is provided inside the reactor that runs up to the maximum height of the opening liquids, occupies a height of 1560% of the internal height of the reactor, and maintains a gap of at least 15 cm from the wall of the reactor. The proposed device has a measuring device for monitoring specified heights s liquid using the signal received from it is governed by the amount of fluid removed; and, if necessary, other measuring devices are also needed, for example, for measuring temperature and pressure. Supply pipelines 1 in the lower part of the reactor can be installed in the bottom as well as at a distance of at least 33% of the internal height of the reactor, calculated from the bottoms 1, laterally in the reactor shell, and it is advisable to arrange holes in the bottom of the reactor for cleaning the internal cavity. These supply lines contain the necessary devices. A, for example, check valves or check valves, which reduce the back flow of the mixture being polymerized from the reactor into the supply lines with an overpressure in the polymerization reactor. The lateral opening in the shell of the reactor should have a clear cross section of 1.5 times greater (in area) the sum of all free cross sections of the feed holes in the bottom of the reactor. This outlet is located at a distance of 50-90%, most often 70-85% of the internal height of the reactor from the opening or openings for the supply of liquid. The device has at least one opening for supplying or discharging gas, which must be placed on the roof of a cylindrical reactor close to its point of view. An inert gas, FiaripHMep nitrogen, can be supplied to adjust the pressure through this opening, when the reactor is emptying or prior to congestion, as well as if necessary. In addition, the device contains at least one stirrer, for example a plate stirrer, whose plate may have a different geometric shape. It can be square, rectangular, triangular, trapezoidal, or oval, it can be assembled from several geometric shapes: their figures, for example, from two triangles or trapeziums, can carry windows along the contour of a notch of various shapes on their surface. The mixer can also consist of several plates with parallel axes, which are arranged relative to each other, at an angle. Other agitators are also suitable, for example agitators with curved surfaces. The agitator can be supplied with water both from above and below. Usually, for design reasons, the drive is selected from above. A plate stirrer can be used as a stirrer, whose maximum width is 25-80% of the internal diameter of the reactor, however, a gap of at least 15 cm from the internal wall of the reactor must be ensured. This agitator occupies 20-40% of the internal height of the reactor and ends at the top about 5 cm below the liquid outlet. If the raw materials of the dL polymerization process in this method are supplied separately via different pipelines, it is advisable that the device have a second agitator in the zone of these supply lines, which may be driven by the agitator described above, but must rotate into the same side, like the first. This mixer should have a diameter of 25-80% of the internal diameter of the reactor, but it is placed relative to the internal wall of the reactor with a gap of 15 cm and occupies 10% of the height of the internal plane of the reactor. It is especially rational to apply the proposed device when it has a ratio of height to diameter of a cylindrical reactor (both values are measured inside) 4-16, and the total capacity of this reactor is at least 25 m. In FIG. 1 shows the proposed device, a general view; in fig. 2 and 3 - the same options; in fig. 4 — times cut A – A in FIG. The device consists of a vertically installed cylindrical reactor 1 with a double shell 2, which has several supply openings 3 for the polymerized liquid raw materials, at a distance of 70% of the internal height of the reactors, a hole 4 for removing the emulsion containing polymerizables, near the bottom (in the shell) on the lid - hole 5 dl from water or gas supply. The device is equipped with a plate-type agitator 6, completely immersed in the liquid, the agitator ends below the opening 4 to drain the emulsion containing polymerizates and occupies over 28% of the total internal height of the reactor. A second agitator 7 / diameter of which is 42% of the internal diameter of the reactor and which extends to 9% of the internal height of the reactor is installed in the lower part of the reactor in the zone of feed lines for raw materials. This mixer has a separate drive independent of the drive of the mixer b located in top of the reactor. The position of the liquid mirror in the reactor is measured by the device 8, and the measured value is controlled by means of the valve 9 to discharge the emulsion containing the polymerizate. The ratio of height to diameter of the reactor (measured inside) is 4.6. Example 1. A vertically standing cylindrical polymerization reactor with a capacity of 5 m is used, which is equipped with a double sheath for liquid flow, which controls the temperature of a plate stirrer located in the lower third in the reactor shell by the inlet and in the upper third by the outlet for the liquid as well as a hole in the reactor lid for supplying or discharging the gas and a device for measuring and adjusting the predetermined height of the liquid level, which is regulated by the removal of the liquid. The reactor has the following dimensions: the ratio of the height of the reactor to the diameter (measured inside the reactor) is 4.7. The height of the supply (loading) of the liquid is 2.0% of the internal height of the reactor. The height of the liquid outlet (load) is 80% of the internal height of the reactor. . Plate agitator length - 37% of the internal height of the reactor. Plate blender diameter 55% of the internal diameter of the reactor; The distance from the vertical edge of the plate mixer to the wall of the reactor is 33 cm. The upper edge of the plate mixer is equal to the same height, then the liquid output. In%, a polymerization agent after flushing with nitrogen and heating the solution at about 50 ° C. The mixture is continuously fed through the bottom opening: 100 parts by weight / h of vinyl chloride; 122 parts by weight per hour of water; 0.15 parts by weight per hour of potassium persulphate; 0.4 weight, h / h E - sodium salt from mixture of scylsulfonic acids, - which contains 80 weight. % alkyl sulfonic acids of 14 and 16 C atoms; 1.6 parts by weight per hour; E - salt salt sodium diisodec sulfonate ester; 0.1 parts / h sodium carbonate. The predetermined height of the liquid level of the reactor is maintained at a level of 92.6% of the internal height of the reactor by regulating the removal of liquid through the upper opening, the mass of the mixture is ejected at a peripheral speed
    1.7 m / s. The emulsified polymer containing emulsion is freed from unreacted vinyl chloride by depressurization and dried by spraying in hot air.
    The polymerization reactor is operated continuously for 840 hours, then stopped, emptied and opened. There is a uniform coating of polymerizate 2 cm thick during operation of the components of the apparatus. Hai: At the bottom of the reactor, there is a precipitated layer of granular polymerizate - with a grain size of 0.1 mm, which is removed, washed, dried for 2.5 hours while in a drying cabinet when blown with hot air and vzvelevayus. The measured values, as well as the data on the maintenance work required during the polymerization process with the time resources required for this, in hours, are shown in Table 1.
    Comparative Example A. A vertical cylindrical polymerization reactor of the same capacity as used in Example 1, equipped with a DUAL shell for passage of a thermostatic fluid (refrigerant), plate agitator, an outlet on the bottom of the reactor and located on the lid. a liquid inlet / as well as a second hole in the lid of the reactive gas supply and exhaust; a device for measuring and adjusting a given liquid level.
    iPeaKTop has the following dimensions: the ratio of the height of the reactor to the diameter (measured-inside the reactor) 4,7,
    Plate agitator length - 12% of the internal height of the reactor,
    Plate diameter stirrer 55% of the internal diameter of the reactor. . The gap from the vertical edge of the stirrer plate to the wall of the ZZ reactors, see
    The upper end of the lamellar mail - 7.4% of the internal height of the reactor, removed from the highest point (inside) of the reactor lid.
    The polymerization reactor closes at the same intensity (the same / hour) with the same reaction mixture as in Example 1. Through the hole in the reactor lid, and the mixture polymerizes at 50 ° C. The liquid level in the reactor is kept at 92.6 times the internal height of the reactor by adjusting the liquid outlet 53 bottom of the reactor, and the liquid is mixed at a peripheral speed of 1.7 m / s. The bleed emulsion containing the polymers is filtered with a 6 mm mesh screen, released from the unreacted vinyl chloride by depressurization and
    dried by spraying in hot air. The polymerization reactor can be operated only for 372 hours, then it must be stopped, emptied and opened for the purpose of cleaning.
     Along with a precipitate of polymerizates with a thickness of about 4 cm on liquid-covered parts of the apparatus is formed on the stirrer and the walls of the reactor in the zone of the upper surface (mirror)
    . liquids dense precipitate of polymerizates, which grows to such an extent that the agitator sediment during rotation polishes the fixed sediment on the reactor wall. The sieve at the -emul5 outlet, downstream, must be cleaned frequently, and the large particles of polymers that are retained on the sieve are collected, washed, dried at 150 ° C in an oven with air for 2.5 hours, and weighed. The measured values, as well as the data on the maintenance work required during the polymerization process, together with the time spent for this in the operating hours of the staff, are shown in Table 1.
    Example 2. A vertically mounted cylindrical reactor is used for polymerization with a capacity of more than 5 m, which is equipped with a double
    0 sheath for the passage of thermostatic fluid, plate stirrer, located in the lower third of the shell of the reactor outlet for the liquid, as well as the hole
    5 on the lid of the reactor for supplying and discharging gas and devices for measuring and adjusting the predetermined height of a level that is controlled by the liquid flow.
    e - The reactor has the following dimensions: the ratio of the height of the reactor to the diameter (according to measurements inside the reactor) / 7.
    The height of the liquid inlet is 2.9% of the internal height of the reactor.
    Output height - 81% - 5 Mixer length - 20% - Mixer diameter - 28% of the internal diameter of the reactor.
    The gap of the vertical edge of the plate agitator from the wall of the reactor
    0 52 cm
    Top. The edge of the flat for the stirrer is located 20 cm below the liquid outlet.
    5 To the reactor, after rinsing with Azo2 and heating the internal cavity to 54 ° C, the mixture is continuously fed through the lower opening:
    4, 4 weight, h. / h v. vinyl acetate; Q 87.5 w / h vinyl chloride; 115 parts per hour water; 0, .1 parts per hour of potassium persulphate; 0.4 parts by weight / P-E (see Example 1); 1.4 wt. h / h EL, -. 0.1 parts / h sodium carbonate.
    The predetermined liquid level in the reactor is maintained at 92.6% of the internal height of the reactor by adjusting the flow of liquid through the top opening, and the liquid is mixed at a peripheral speed of 1.6 m / s. The effluent emulsion is released by depressurizing unreacted vinyl chloride and dried by spraying in hot air.
    The reactor is operated for 768 hours, then stopped, emptied and opened. A uniform film of about 2.5 cm thick polymer is formed on the parts of the apparatus covered with liquid. A granular polymerizate with a grain size of 0.1 mm is deposited on the bottom of the reactor, which is removed, washed, dried for 2.5 hours while in an oven with air supply and weighed. The measured values, as well as the data on the maintenance work required during the polymerization process, together with the data on the time spent at the same time in operating hours, are given in Table 1.
    Comparative example B. A vertically mounted cylindrical reactor of the same capacity as Example 1, is used; It is equipped with a double shell for passage of a thermoregulating fluid, a plate agitator, an outlet inlet on the bottom of the reactor and an inlet for liquid on the reactor cover, as well as a second inlet on the reactor gas inlet and outlet, a device for measuring and adjusting the level, which regulated by fluid flow.
    The reactor has the following dimensions: the ratio of the height of the reactor to the diameter (measured inside) is 4.7.
    Plate agitator length - 12% of the internal height of the reactor.
    The diameter of the plate agitator is 28% of the internal diameter of the reactor.
    The gap from the vertical krcht agitators to the wall of the reactor; and 52 cm.
    The upper end of the plate mixer at 7.4% of the internal height of the reactor is removed from the highest point of the reactor lid. The reactor is filled through the hole in the reactor lid with the same reaction mixture with the same intensity (number / h) as in Example 1 and at 54 ° C polymerizes. As in example 1, given
    0 the liquid level in the reactor is maintained at a distance equal to 8% of the internal height of the reactor from the highest point of the reactor lid, using the liquid drain through the opening in the bottom of the reactor, and the liquid is mixed with a peripheral speed of 1.6 m / s. The outgoing emulsion is filtered on a mesh with a mesh size of 6 mm, released when pressure is removed.
    0 from unreacted vinyl chloride and spray dried in hot air.
    The reactor is operated for 408 hours, then, for the purpose of cleaning, it is stopped, emptied and opened.
    five
    Along with a precipitate of polymerizate about 5 cm thick on liquid-coated parts of the apparatus is formed on the mixer and the wall of the reactor in the zone of the liquid mirror a dense precipitate of
    0 polymers of such thickness that the precipitate of the stirrer during rotation grinds a non-mobile sediment on the wall of the reactor,
     The sieve installed in the outlet for discharge of the emulsion during operation is often cleaned, and the coarse particles of polymerisates retained there are collected, washed, dried at 150 ° C in an oven under air flow, and weighed. The measured values: and, as well as the data on the maintenance work required during the polymerization process, together with the data on the time spent for this in the operating hours of the staff, are given in Table 5 below.
    Table 1
    840
    50
    744
    50 54 768
    3.8
    1.20
    2x
    7x
    70,6
    1x
    1.8
    8x 1.8 0.63 1x
    ..iep,
    .816
    54 64 960
    vinyl chloride K72 homopolymerisate according to D1Y 53726 vinyl chloride-vinylacetate copolymer K70 vinyl chloride chloropolymer homopolymerisate K 59 homopolymerisate of vinyl chloride K 78: primer and measure 3. A standing vertical reactor with a volume of more than 5 meters is provided and supplied with a double cabinet with a volume of 5 meters and provided with a double box. liquid, plate agitator, an inlet opening for the third of the reactor shell and an outlet for the liquid located in the upper third of the reactor shell, as well as a hole on the reactor lid for supplying and gas exhaust and devices for measuring and adjusting a given level of gas. . The reactor has the following dimensions: the ratio of the height of the reactor to the diameter (measured inside) is 4.5; The height of the liquid inlet is 17% of the internal height of the reactor; height of the liquid is 87% of the internal height of the reactor; Plate agitator length - 37% of the internal height of the reactor; Plate blender diameter - 61 inner diameter of the reactor; The gap is from the vertical edge of the TINCHAT mixer to the wall of the reactor 29. See the Top end of the plate mixer 10 cm below the liquid outlet. After flushing with nitrogen and heating the internal plane of the reactor, the mixture is continuously fed to the reactor through the bottom opening: 100 parts by weight of vinyl chloride; 100.h.p./h water; 0.08 parts by weight per hour of potassium persulphate; : 2.1 parts by weight .. h of Eo, (sodium salt from dodecylbenzene sulfonic acid); .
    - Continuation of the table. one
    55,6
    1x
    1D6
    6 x 7 0.7 7 x 0.07 parts by weight per hour of secondary sodium phosphate. The predetermined liquid level in the reactor at 96% of the internal height of the reactor is maintained by controlling the flow of liquid through the upper opening, and the liquid is mixed at a peripheral speed of 1.6 m / s. The slurry emulsion is relieved of unreacted vinyl chloride by pressure relief and dried by spraying in hot air. The reactor is operated for 960 hours, then stopped, emptied and opened. A uniform residue of about 2 cm thick polymer is formed on parts of the apparatus covered with liquid. A granular polymer is deposited on the bottom of the reactor with a grain size of 0.1 mm, which is removed, washed, dried for 2.5 hours while in an oven with air flow and weighed. The measured values, as well as the data on the maintenance work required during the polymerization process, together with the data on the time spent for this in the staff working hours are given in Table 1. Comparative Experience B. A vertically standing cylindrical reactor of the same capacity as the reactor of the example is used. 1, which is equipped with a double shell for the passage of thermoregulatory fluid, plate agitator, located on the bottom of the reactor input «| liquid hole, as well as the second hole on the core of the reactor for the supply and
    gas exhaust and a device for changing and adjusting a predetermined level set by adjusting the flow of liquid.
    The reactor has the following dimensions: ratio of reactor height to diameter (measured in the interior of the reactor) 4.3 j
    Plate agitator length - 12% of the internal height of the reactor;
    Plate blender diameter 61% of the internal diameter of the reactor;
    The gap between the vertical edge of the lamellar sac and the wall of the reactor is 29 cm.
    The upper end of the plate agitator removed 8.8% of the internal height of the reactor from the highest point of the reactor lid.
    The reactor is filled with the same reaction mixture at the same flow rate (quantity / hour) as in example 1, through the hole in the keyhole, and the mixture is polymerized at, as in example 1. Preset. the height of the liquid in the reactor is maintained by adjusting the flow of liquid through the opening in the bottom of the reactor at a distance of 10.3% of the internal height of the reactor from the highest point of the reactor lid, and the liquid is mixed with a peripheral speed of 1.6 m / (as in example 1). The effluent emulsion is filtered through a 6 mm mesh sieve, shielded by removing pressure from unreacted (unreacted exchange decomposition) vinyl chloride, and dried by spraying in a mountain than air. The reactor is operated continuously for 528 hours, then it is stopped, emptied and opened for the purpose of cleaning.
    Along with the precipitate of polymer bricks with a thickness of about 6 cm on liquid-covered apparatus parts, a dense precipitate of polymers is formed on the mixer and the walls of the reactor in the mirror zone of the liquid, which has grown to such thickness that the precipitate on the mixer during rotation grinds stationary residue on the reactor wall. The sieve installed in the flow path of the emulsion must often be cleaned during operation, the large particles of polymerizate trapped on the filter are collected and washed and dried at 150 ° C in an oven with air flow and weighed. The measured values, as well as the data on the maintenance work required during the polymerization process, together with data on the time spent for this in the service hours of the staff, are given in Table 1.
    Example4. A vertically mounted cylindrical reactor with a capacity of more than 25 m is used, which is equipped with a double shell for a thermostatic thermostat, a plastic stirrer, located in the lower third of the reactor shell with an inlet (loading) opening and located in the upper third of the reactor shell with an output (discharge) opening for liquid, as well as a gas inlet and outlet, and a device for measuring and adjusting a predetermined height, which is regulated by the liquid flow.
    The reactor has the following dimensions:
    0 the ratio of the height of the reactor to the diameter (measured inside) is 8.5
    liquid feed - 11.5% of the internal height of the reactor fluid
    five
    The height of the liquid supply 80% of the internal height of the reactor;
    The diameter of the plate mixer - 39%;
    Plate blender diameter - 67% of the internal diameter of the reactor;
    0
    The distance between the vertical edge of the plate agitator and the wall of the reactor is 27 cm.
    The upper edge of the agitator is 10 cm below the liquid.
    To the reactor after flushing with nitrogen
    5 and heating the internal cavity of the reactor to 43 ° C continuously feeds through the lower opening of the mixture:
    166 parts per hour of vinyl chloride;
    195 parts by weight per hour of water;
    0
    0.13 parts by weight per hour of potassium persulphate;
    0.035 parts by weight of sodium bisulfite;
    4.2 parts by weight / P E-1 (see example 1);
    0.27 parts by weight per hour of sodium carbonate;
    0,00035 parts by weight per hour of copper sulphate
    five
    The predetermined height of the liquid in the reactor is maintained by adjusting the flow of liquid through the upper opening at a level of 86% - the internal height of the reactor, and the liquid is stirred at a peripheral speed of 1.5 m / s. The effluent emulsion (containing by; Limerizates) is freed from the reacted vinyl chloride and dried by spraying in hot air. The reactor is operated continuously for 840 hours, then stops, empties, and opens, forming a uniform precipitate of polymerizate about 1 cm on the liquid-covered parts of the apparatus. At the bottom of the reactor, granular polymerizate is deposited with a grain size of 0.1 mm, which is removed, washed, dried for 2.5 hours while in a drying oven with a duct
    5 air and weighed. The measured values, as well as the data on the maintenance work required during the polymerization process, together with the data on the time spent for this in the staff working hours are given in Table 1.
    Comparative Example G. A vertically standing cylindrical polymerization vessel of the same capacity as that used in Example 4, equipped with a double jacket, through which a tempering liquid flows through a plate lamella, is located in the lower third of the vessel opening and is located near the vessel. vessel cracks with a liquid outlet and also a hole in the vessel's container for supplying or discharging gas and measuring and adjusting the level regulating the discharge of the liquid with the following Dimensions: vessel height to diameter ratio h / d (measured in) 8.5. Plate agitator length - 39% of the total internal height of the vessel; The diameter of the plate mixer is 67 inner diameter of the vessel. The distance from the vertical edge of the plate mixer to the wall of the vessel is 27 cm. . The upper end of the plate agitator is 10 cm below the liquid outlet. In the polymerization vessel B of the same quantity, the same reaction mixture is fed through the loading opening per hour as in example 4 and polymerized at 43 ° C (same temperature as in example 4),
    840
    43
    192
    43 50 432
    paper56
    528 O50 500
    650 650
    743
    254 768 Comparative tel10 Because of the VE 54
    Example5. A vertically standing cylindrical polymerization vessel with a capacity of over 5 m, equipped with a double jacket, through which the tempering liquid flows through a plate stirrer, located in the bottom
    3.3
    0.85
    1x 3x
    1.0
    0.3
    1x 5.5 1.3 Sx
    82.3
    3.1
    10x
    1.0 3.2
    2x 2.5 0.9
    2x 1.8 0.63
    1X
    the thirds of the vessel’s jacket, the inlet and the outlet for the liquid in the upper third of the vessel’s jacket, as well as the inlet or outlet of gas in the vessel lid and measuring and adjusting the level regulating the level of the liquid in the vessel by controlling the outlet of the liquid through the upper opening 99% of the total internal height of the vessel and the liquid is stirred at a peripheral speed of 1.5 m / s (as in Example 4). The discharge polymer emulsion is released from the unreacted form by pressure relief. ilhlorida and by spraying in hot air dried. The polymerization vessel operates continuously for 192 hours, then, due to strong pressure fluctuations and interference during the polymerization, it is stopped, released and opened. Along with polymer deposits about 1 cm thick on a liquid covered part of the apparatus on the mixer and on the lid of the apparatus surrounded by the surface of the liquid, thick polymer deposits formed, which on the mixer grew to such a thickness that it interfered with the container on the vessel wall, of which particles Peeling off, they are partially colored and contaminate the polymer emulsion. The measured values obtained are listed in Table 2. T a b e and c a 2 very KOpoTjcoro working time data does not make sense
    liquid water, with the following dimensions:
    The ratio of height to diameter (measured inside) is 4.7
    The height of the fluid supply - 2.9% of the total internal height of the vessel;
    .The height of the liquid outlet - 70% of the total internal height of the vessel;
    Plate agitator length - 20% of the total internal height of the vessel;
     The diameter of the plate mixer - 55 inner diameter of the vessel;
    The distance of the vertical edge of the plate agitator from the vessel wall is 33 cm; .
    The upper end of the plate agitator is 20 cm under the liquid outlet.
    After purging with nitrogen and tempering the contents of the vessel to 50 ° G, the mixture is continuously introduced into the polymerization vessel through the bottom opening:
    20% w / h of butyl acrylate;
    80% w / h vinyl chloride;
    115 parts per hour water; .
    0.1 parts by weight per hour of potassium persulphate;
    2.4 w / h sodium salt of a mixture of alkylsulfonic acids containing 80% by weight of alkylsulfonic acids with 1,416 carbon atoms;
    0.1 parts / h sodium carbonate.
    The fluid level in the vessel is maintained by adjusting the drainage of fluid through the top opening to 92.6% of the total. the internal height of the vessel and the liquid is stirred at a peripheral speed of 1. 3 m / s. The exhaust polymer emulsion due to pressure release is freed from unreacted vinyl chloride and collected in containers for later use. The polymerization vessel runs continuously for 432 hours, then stopped, released and opened. On the liquid-coated part of the apparatus, a uniform deposition of polymer with a thickness of about 2.5 cm was formed. At the bottom of the polymerization vessel, the polymer was deposited, which was removed, washed for 2.5 hours, dried in an air drying oven and weighed. The measured values, as well as data on the maintenance work required during the polymerization process with the required for. this time spent in working hours are given in table 2
    Comparative Example D: Vertically standing iindriders-g. curing polymerization vessel ta-. The same vessel as in Example 5, equipped with a double jacket, through which the tempering liquid flowed, with a plate agitator, an orifice in the vessel bottom and an inlet for the liquid located in the vessel bottom, as well as a second opening in the vessel lid for leading, or gas discharge and measurement and level control, which is regulated by
    It discharges fluid, with the following dimensions:
    The ratio of vessel height to diameter (measured from the inside) is 4.7;
    Plate agitator length - 12% of the total internal height of the vessel;
    The diameter of the plate agitator is 55% of the internal diameter of the vessel;
    The distance of the vertical edges of the plate mixer from the vessel wall is 33 cm;
    0
    The upper end of the plate agitator is 7.4% of the total internal height of the vessel, removed from the highest point of the vessel lid.
    The polymerization vessel was fed with the same amount of reaction mixture per hour as in Example 5 and polymerized at 50 ° C (the same temperature as in Example 5) through a hole in the lid of the vessel; The level of fluid in the vessel due to
    By adjusting the discharge of liquid at the bottom of the vessel, it is maintained at a distance of 8% of the internal height of the vessel from the highest point of the vessel lid and the liquid is stirred at a radial velocity of 1.3 m / s (as in Example 5). The withdrawn emulsion of the polymer is filtered through a 6 mm mesh mesh, and is released from the unreacted pressure by depressurizing.
    0 vinyl chloride and is collected in containers for future use.
    The polymerization vessel worked continuously for 264 hours, then it was stopped for cleaning, released and opened.
    5 Along with the deposition of polymer with a thickness of about 5 cm on the liquid-coated parts of the apparatus of the stirrer and on the vessel wall, surrounded by the surface of the liquid
    0 thick deposition of polymer, which has grown to such a thickness that the deposition on the mixer during the rotation of the third on the fixed deposition on the walls. vessel.
    . The screen during the passage of the emulsion of 5 liters during operation must often be cleaned, the remaining particles of the polymerized mass are collected, washed, dried in an air drying cabinet at 150 seconds and weighed.
    0 All the measured values, as well as the data on the necessary during the polymerization process of the maintenance work with Tpe6yeNttJMH for this purpose, are shown in Table 2.
    five
    Example 6. A vertically standing cylindrical polymerization vessel with a capacity of more than 5 m, equipped with a double jacket, through which a tempering liquid, with a plate stirrer, located in the lower third of the jacket, is used. vessel leading otve to; tiy and. an outlet for liquid located in the upper third of the jacket of the vessel, as well as an opening for S
    cottages and gas outlet in the lid of the vessel and measurement and regulation of the level that regulates the discharge of liquid, with the following dimensions:
    From the height of the vessel to the diameter (measured inside) - 4.7;
    The height of the fluid supply is 2.0% of the total internal height of the vessel;
    The height of the liquid outlet is 80% of the total internal height of the vessel;
    Plate agitator length - 57% of the total internal height of the vessel;
    Diameter - 79.5% of the internal diameter of the vessel.
     The distance of the vertical edges of the plate agitator from the vessel wall is 15 cm;
    The upper end of the plate agitator is 20 cm under the liquid mirror. . The polymerization vessel, after purging with nitrogen and tempering the contents of the vessel to 50 ° C, continuously feeds the mixture through the bottom opening:
    100 parts per hour vinyl chloride;
    122 parts by weight per hour of water;
    0.15 parts by weight per hour of potassium persulphate;
    0.4 parts by weight per hour of sodium salt of a mixture of alkylsulfonic acids containing 80% by weight of alkylsulfonic acids with 1,416 carbon atoms
    1.6 pbw sodium diisodecyl sulfonate ester;
    0.1 parts / h sodium carbonate.
    The fluid level in the vessel by adjusting the fluid outlet through the upper opening is maintained at 92.6% of the total internal height of the vessel and the mass is stirred at a circumferential speed of 1.7 m / s. The released polymer emulsion is released from unreacted vinyl chloride by pressure release and dried by spraying in hot air. The polymerization vessel was continuously operated for 500 hours, then stopped, released and opened. A uniform layer of deposited polymer was formed with a thickness of about 1.5 cm on the liquid-coated parts of the apparatus. At the bottom of the polymerization vessel, a granular pselymer with a grain size of 0.1 mm was deposited, washed, dried in an air oven at 150 ° C for 2.5 hours and weighed. The measurement of the value as well as the data on the safety of the 1st during the polymerization process of maintenance work with the time required for this in working hours is given in Table 2.
    Example 7. A 25 m vertical cylindrical polymerization vessel equipped with a double jacket, through which the tempering liquid flows, with a plate stirrer, an inlet opening for the lower third of the jacket of the vessel and an outlet for the liquid, as well as a hole for supplying and discharging gas on the lid of the vessel and measuring and adjusting the level that regulates the discharge of the liquid, with the following dimensions:
    The ratio of vessel height to diameter (measured inside) is 8.5;
    The height of the input fluid - 11.5% of the total internal height of the vessel;
    The height of the liquid outlet is 45% of the total internal height of the vessel;
    Plate agitator length - 39% of the total internal height of the vessel;
    The diameter of the plate mixer - 6 from the inner diameter of the vessel;
    The distance of the vertical edges of the plate mixer from the vessel wall is 27 cm;
    The upper end of the plate agitator is 10 cm under the liquid outlet.
    After purging with nitrogen and tempering the contents of the vessel to 43 ° C, the mixture was continuously introduced into the polymerization vessel through an opening:
    166 parts per hour of vinyl chloride; 195 parts by weight per hour of water; 0.13 parts by weight per hour of potassium persulphate; 0.035 parts by weight per hour of sodium bisulfite 4j2 parts by weight per hour of sodium salt of a mixture of alkylsulfonic acids, as in Example 6;
    0.27 parts by weight per hour of sodium carbonate; 0,00035 weight.h 1 / h copper sulfate. The level of the liquid in the vessel is maintained by regulating the discharge of the liquid through the upper opening to 86% of the total internal vyst of the vessel and the liquid is stirred at a peripheral speed of 1.5 m / s. The released polymer emulsion is released from unreacted vinyl chloride by pressure release and dried by spraying in hot air. The polymerization vessel operates continuously for 650 hours, then stopped, emptied and opened. A uniform deposition of polymer with a thickness of about 1 cm is formed on the liquid-coated parts of the apparatus. At the bottom of the polymerization vessel, a granular polymer with a grain size of 0.1 mm is deposited, washed, dried in an air oven at 150 sec. 2.5 hours and weighed. Measured values, as well as data on maintenance work required during polymerization for this, the time spent in working hours is given in Table 2.
    Comparative example F. A vertically standing cylindrical polymerization vessel with a capacity of 5 m is used, as in example 2, equipped with a double jacket, through which a tempering liquid flows through an inlet opening in the lower third of the jacket of the vessel and a liquid outlet above it on the jacket of the vessel as well as a hole for supplying or discharging gas on the lid of the vessel and measuring and regulating the level regulating the discharge of liquid, with the following dimensions: The ratio of the height of the vessel to the diameter of the vessel (from measured inside) 4,7; The height of the input fluid - 2.9% of the total internal height of the vessel; The height of the liquid outlet is 8-1% of the total internal height of the vessel. After purging with nitrogen and tempering the contents of the vessel to 51 ° C, the mixture is continuously introduced into the polymerization vessel through the lower opening: 4.4 parts by weight vinyl acetate; 87.5 weight, h / h vinylchloride 115 weight.h. water; 0.1 weight. h / h potassium persulfate; 0.4 parts by weight per hour of sodium salt of a mixture of alkylsulfonic acids containing 80% by weight of alkylsulfonic acids with 1,416 carbon atoms; 1, 4 weight. . sodium diisulfuryl sulfate; sulphonate; 0.1 parts / h sodium carbonate. The level of fluid in the vessel is controlled by 92.6% of the total internal height of the vessel by regulating the drainage of fluid through the upper opening. The reaction mixture is not stirred. Shortly after the mixture was fed into the reactor, temperature fluctuations and pressure shocks began to occur, and an emulsion was formed on the surface, and liquid vinyl chloride EID was collected. Initially, the homogeneous emulsion is decomposed with the separation of the polyvinyl chloride grains, so that after 10 h the experiment must be interrupted. In the examples described, the distance n-ie of the liquid mirror from the outlet orifice is determined from the example data. The height of the liquid outlet and the level of the liquid in the vessel are indicated respectively in percent of the total internal height of the vessel. In the region of the difference of these two quantities there is a hole for draining the liquid below the surface of the liquid. In each example, the minimum volume (V) and the ratio of height to diameter (h: d Q) are indicated, hence the internal height of the vessel is calculated: Hmm-Q1-4 For a curing vessel with a precisely cylindrical internal space with the specified minimum volume calculated for applications 1-7 the following minimum distances are the mirrors of the fluid from the excretory body (see table 3). Table 3 Distance Difference of the liquid glass of a liquid liquid minus height Example, No. of the output hole,% minimum hole, cm Example 8. A vertical cylindrical polymerization reactor (vessel) with a volume of 5.1 m, equipped with a double jacket through which the liquid flows, is used. with a temperature setting, a paddle stirrer, an inlet opening in the lower third of the reactor vessel and an outlet for the liquid in the upper third of the reactor vessel, a hole for odachi or gas outlet of the reactor cover and the meter and level regulator which is controlled stroke liquid with the following dimensions: The ratio of reactor height to diameter (measured in) 4.7; Vysotata input fluid - 2.0% of the total internal height of the reactors; The height of the liquid outlet - 91% of the total internal height; Blade stirrer length - 37% of total internal height; The diameter of the paddle stirrer is 55% of the internal diameter of the reactor; The distance of the vertical edges of the paddle stirrer from the wall of the reactor is 33 cm; The upper end of the paddle stirrer is 65 cm below the liquid mirror; The discharge of liquid lies at a distance of 20 cm below the mirror of the liquid. After washing the Nf polymerization reactor, a mixture of the following two latexes is continuously introduced through the lower opening: latex A is prepared as described in Example 3, and the polymerization proceeds to pre-transformations of 85%. Latex B is a fine latex, which is polymerized from 20 parts by weight. acrylonitrile and 60 weight.h. butadiene at 70 ° C until the pressure drops to 0.3 MPa in water, and contains 33 wt.%, in terms of latex, of the polymerized solid. Both latexes A and B are mixed in such a way that the final product has an amount of elastomer in a total polymerized product of 5.0 weight. The latex mixture is heated in the reactor described above until it is maintained at this temperature, and the mixing is performed at a circumferential speed of rotation - 1, 0 m / s and the liquid level in the reactor by controlling the flow of liquid through the top opening is maintained at 94.8% of the total internal height of the reactor. The influx of the latex mixture in the reactor is regulated so that the degree of conversion of vinyl chloride during the copolymerization by grafting increases 57
    Example 8
    981
    The proposed method prevents the formation of polymer deposits on the inner surfaces of the reactor.
    权利要求:
    Claims (5)
    [1]
    1. A process for preparing vinyl chloride polymers aqueous emulsion gbmopolimeriz atsiey, copolymerization or graft copolymerization of vinyl chloride in the presence of radical initiators and surfactants akTivn1a1h vertikashnom substances in a reactor with a height to diameter ratio not menoe 3 and capacitance not less than 5 m, the regulation of the level of the liquid phase, This is due to the fact that, in order to prevent the formation of polymer deposits on the internal surfaces of the reactor, the polymer emulsion formed is removed from the reactor at a height of 30-90% The height of the reactor above the input of the initial mixture and at least 15 cm below the liquid phase mirror, the contents of the reactor are mixed
    2x
    0.5
    3.5
    less than one stirrer equal to 0 along the length of 15-60% of the total internal height of the reactor and set at a distance of not less than 15 cm from the wall of the reactor, the upper end of the stirrer is located no more than 5–20 cm below the liquid phase mirror, the liquid phase is at a height equal to not more than 97% of the internal height of the reactor.
    [2]
    2. A method according to claim 1, characterized in that the process is carried out in a reactor equipped with an additional stirrer located at least 15 cm from the wall of the reactor, occupying no more than 10% of the total internal height of the reactor and rotating in the same direction that the agitator is listed in item 1.
    [3]
    3. A device for carrying out the method according to claim 1, comprising a vertically mounted cylindrical reactor with a jacket, an opening for supplying liquid in its lower part,
    with an opening for removal of gases in the upper part of the reactor and an opening for removal of liquid, made on the side. 5 at the top of the reactor, at a distance of up to 95%. The effluent of the polymerizate is released by lowering the pressure of the unconverted vinyl chloride and is spray dried on hot air. Polymerization reactor works for 981 hours, then it is continuously and empty, and it is depleted. It forms a uniform closure. polymer coating about 1 cm thick, O cm on liquid-coated parts of the apparatus. At the base of the polymerization reactor, a granular polymerizate with a grain size of 0.1 NM is precipitated, which is removed, washed, dried in an air-flow chamber dryer for 2.5 hours and weighed. The measured values and data of the maintenance work required during the polymerization process with the time required in man-hours for this are given in Table 4. I Table 4
    Research institutes constituting 30-90% of the internal height of the reactor from the fluid inlet, and the agitator, is due to the fact that the agitator is made in the form of at least one plate mounted on the shaft and lying in the plane of the shaft axis, the plate height is 15-60% of the internal height of the reactor, and its width is 25-80% of the internal diameter of the reactor.
    [4]
    4. The device according to p. 3, of t l ich and y u her, with the fact that the ratio
    the height of the reactor to its diameter is 4-16.
    [5]
    5. The device according to PP. 3 and 4, differing in that it is equipped with an additional agitator with a diameter of 25-80% of the internal diameter of the reactor, installed in its lower part, to a dim.
    Sources of information taken into account in the examination,
    1. Nikolaev A.F. Synthetic polymers and plastics based on them .. M.-L., Himi, 1964, p. 213-215.
    1
    类似技术:
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    同族专利:
    公开号 | 公开日
    FR2353574A1|1977-12-30|
    BE855433A|1977-12-06|
    US4125574A|1978-11-14|
    ES459218A1|1978-03-01|
    ATA396277A|1979-05-15|
    DE2625149A1|1977-12-08|
    IT1074532B|1985-04-20|
    DE2625149C3|1981-01-08|
    PL104110B1|1979-07-31|
    BR7703569A|1978-03-28|
    DD130860A5|1978-05-10|
    GB1580747A|1980-12-03|
    CA1094748A|1981-01-27|
    HU176398B|1981-02-28|
    CH628908A5|1982-03-31|
    PL198569A1|1978-02-13|
    AT354088B|1979-12-27|
    ZA773356B|1978-05-30|
    DE2625149B2|1980-04-30|
    YU138277A|1982-08-31|
    NL7705867A|1977-12-06|
    YU39009B|1983-12-31|
    FR2353574B1|1982-09-10|
    SE7706484L|1977-12-05|
    SE422215B|1982-02-22|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2625149A|DE2625149C3|1976-06-04|1976-06-04|Process and device for the continuous production of vinyl chloride polymers in aqueous emulsion|
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