• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Granular polymers having a relatively uniform fine particle size as small as about 10 mu m can be produced in high yield by suspension polymerization by conducting the polymerization of one or more crosslinkable polymerizable monomers, non-crosslinkable polymerizable monomers or a mixture thereof in the presence of a suspension agent, and if necessary, together with a suspension assistant and/or a non-reactive organic solvent, under stirring accompanying high speed shearing until the percentage conversion becomes 1 to 50% and continuing the polymerization under stirring without the accompanying high speed shearing and mechanical cutting.
    公开号:SU1058507A3
    申请号:SU802864203
    申请日:1980-01-09
    公开日:1983-11-30
    发明作者:Мукояма Есиюки；Тиказуми Нобутоси
    申请人:Хитачи Кемикал Компани,Лтд (Фирма)；
    IPC主号:
    专利说明:

    ate
    00
    The invention relates to a process for the preparation of copolymers of a granular line c. uniformly small particle size, for example, about 10 microns, by carrying out suspension polymerization in an aqueous medium, first with shear mixing at high speed, and then with stirring, not accompanied by mechanical shearing or grinding. For various dyeing modifiers, stationary stationary elements of the phases and separation media for various types of chromatography, in particular in aggregates for chromatography on permeable gels, ion exchange resins for analysis. amino acids, and the like. where high separation properties and high resistance to pressure are required, spherical porous granular polymers with a uniform particle size of about 10 microns are used. Closest to the proposed technical essence and the achieved result is a method of obtaining copolymers of fine-grained structure by polymerization in an aqueous medium a mixture of styrene, monovinyl ethyl benzene and divinyl benol or a mixture of monovinyl ethyl benzene and divinyl benzene in the presence of a suspending agent at 70-85 ° C and mixing. Water-insoluble phosphate and water-soluble alkyl cellulose or hydroxyalkyl cellulose are used as a suspending agent, and an anionic surface-active agent, such as ammonium lauryl ammonium ij, is used as a suspending agent. I. However, to obtain the desired polymer 1st beads with a particle size of about 10 microns with a high yield and increase the yield for the desired granulated polymer with a size. particles of 5–15 µm are difficult, which is due to the fact that it is impossible to obtain a completely even distribution of oil droplets at the initial stages of polymerization and to completely inhibit the uneven growth of oil droplets due to a discrepancy in their coalescence and dispersion rates. The purpose of the invention is to enhance you. Soda ssrolimerov fine-grained structure. This goal is achieved by the fact that according to the method of obtaining fine-grained copolymers by polymerization in an aqueous medium a mixture of styrene, monovinyl ethylbenzene and divinylbenzene or a mixture of monovinylisylbenzene and divinylbenzene in the presence of a suspending agent at 70-85 ° C and stirring. the process is carried out before donsversion of monomers 20–40% with stirring with a shift at a rate of 1,. stirring without shearing with. speed of 400-600 rpm Soluble phosphates, such as medium calcium phosphate, hydroxyapatite, magnesium pyrophosphate, and the like, can be used as a suspending agent. and water soluble high molecular weight. polymers such as alkylzellulose, polyvinyl alcohol, and the like. individually or mixtures thereof. From the point of view of ease of processing of the resulting suspension and ease of synthesis of suspending agents, it is preferable to use insoluble phosphates. The suspending agent is preferably used in an amount of 3200% by weight. Since if the amount is too small, the suspension becomes unstable, and if the quantity is too large, a tendency arises that prevents even dispersion. Suspension agents are used to stabilize the polymerization system, such as one or more anionic surfactants, non-ionic surfactants, amphoteric surfactants such as sodium dodecylbenzenesulfonate, sodium lauryl sulfonate, alkyl naphthalene sulfonate. sodium, salts of dialkyl sulfosuccinate, salts of polyoxyethylene L-alkyl: phenol ether, and so on. From the point of view of stability of a dispersion system, the use of anionic surface-active agents is preferable. The anionic surfactant may preferably be used in the range of 0.0005-0. 01% by weight. For example, when styrene, monovinyl ethylenebenzene and divinylinbenzene are used as monomers, and sodium polymerization agent is used as an agent for promoting polymerization. The latter takes a precursor in the amount of 0.0005-0.003% by weight. Sometimes the agent is called the salinating agent. , such as sodium sulfate, sodium chloride, calcium chloride, together with a suspending agent. The shear rate can be defined as the value obtained by the absolute value of the difference between the speeds of two planes and the distance between two planes, when the olimerization system is between two or two cylindrical planes at a sufficiently small distance (for example, 5 or 6 mm or less) . Shearing velocity bolyiry create devices with peremeshivakzhipii stvami environments such as cell phones, .snabzhennye turbine pump, such as walls 1DOVY .gomogenizator M-type mixer (manufactured by Tokushu Kika now Koge co., Ltd., Japan), pipes wire homogenizer-mixer (Tokushu Kika Kogyo Co., LTD., Gsmogenizatogz-mixer (Steco Inc., USA, Turbine agitator companies (Tsukishima Kikai Co., LTD., Japan). Mixers with a stationary pipe can also be used. Since they can create shear rate from 1 0 5 to 5x10 for example. Static mixer. (Kenix Co., USA), large shear mixer (Torey Indus., Inc., Japan) stirrer without proper movement. (Ches. Ross, End Son Co., Inc., SIL), and so on. P., -.: If mixing without shearing with high speed is performed in the initial period of polymerization (i.e., if polymerization is carried out with usual mixing, using prior art), then the shear rate is small and drops tlasla increases from 5 or 6 microns to 5 or b by g (mainly from -50 or 60 microns to 500 or 600 mK and are distributed mainly by at once, in particles of larger size. . Slurry polymerization, followed by shearing at high speed, takes place from the beginning of the polymerization until the time when the conversion reaches 1-50%. If the polymerization of the mixture, accompanied by stirring and cutting at high speed, ceases before the conversion reaches 1%, then the resulting oil droplets with small particles combine to form oil droplets with larger particles. The degree of conversion can be identified by gas chromatography. I When the polymerization is carried out with mixing, followed by cutting at high speed, the particle size of the oil droplets in the initial period of polymerization becomes small and can be maintained at this level as long as the mixing continues, shredded) at high speed. With the further development of polymerization i. when the conversion becomes 1-50%, oil droplets with a small particle size increase their viscosity and can be kept in a relatively stable state in the suspension system. which are weakly influenced by coalescence and particle separation, even if it is palmerization. the system is transferred to a mixing system, followed by shearing at high speed. After such a stage, if the polymerisation continues with stirring using mixing devices, equipped with a turbine pump, such as a homogenizer-mixer, particles having a small particle size that can be relatively stable under stirring, not accompanied by shearing at high. the speeds are cut off or and; they are ground mechanically by turning blades that rotate at high speed and cut at high speed, which makes the particles smaller. Therefore, j after small particles (oil droplets) increase. its viscosity can be relatively stable without cutting or grinding. In addition, since small particles can separate if the polymerization is carried out with stirring, followed by cutting at high speed, and be relatively stable with stirring without cutting at high speed, it is preferred to continue the polymerization with stirring without cutting at high speed after the degree of conversion will be 1-50%. Therefore, polymerization, with stirring, followed by shearing — at high speed — is stopped before the conversion is no more than 50% and the polymerization is continued, with agile stirring, without shearing, at high speed. According to the proposed method, the polymerization system is treated in such a way that, ultimately, to obtain a copolymer of a granular structure with a particle size of about 10 µm with a good yield by applying polymerization with stirring, followed by shearing at high speed. Therefore, adding one or more monomers or polymers or copolymers to the polymerization system at the stage or after the stage of applying the usual mixing, not accompanied by shearing at high speed, is not preferable, since the particle size of the final copolymer of the granular structure greatly changes or does not make sense. On the other hand, it is preferable to add one or more suspending agents and suspending agents in such a step so as to reliably prevent the particles from joining while maintaining the size distribution, if necessary. The polymerization is carried out at 6590 ° C. As a polymerization catalyst, radical initiators, polymerizations such as erekis, for example benzoyl peroxide, p-tert-butyl perbenzoate, etc., azo compounds, can be used. for example, azobisisobutyronitrile, etc., in an amount of about 0.53 wt. % . It is preferable to use an aqueous medium in a five-fold or large; If the amount is less than five times, then in the initial period of polymerization, coalescence or coagulation of the oil droplets easily occurs and it is very possible to obtain 30 copolymer of granular structure. : uniform small particle size. On the other hand, if the amount of the aqueous medium is too large, then the productivity decreases. .35 Example 1. In a four-necked separable flask with a capacity of 1 l, equipped with a thermometer, a bimetallic type rel., A reflux condenser, and a homogenizer-mixer type M are placed: g: styrene 67.2 60% divinylbenzole 17.2 (mixture 60% divinylbenzene and 35% monovinyl ethylbenzene), benzoyl peroxide 0.52, suspension of 10% sparingly soluble 5% calcium phosphate 23.4; 1% sodium dodecylbenzene sulfonate 1.26 and demineralized water 420 ml: and mixed with cutting at high speed (recovery rate is about min. Soder sym is heated to | 70–7 ° C using a gas kaline grid while dispersing. Polymerization is carried out 2 hours at this temperature (degree of conversion is 30%). Then the reaction solution is quickly poured into another four-necked separable flask, 1 liter, equipped with a thermometer, a bimetallic type relay, a reflux condenser and an agitator with a blade type H / and the polymer is continued at a temperature of 80–85 ° C for 4 hours at a stirring speed of 500–600 rpm, during the polymerization from Pr for by the right to 40 Pa Spas at the bottom. The reaction solution is often sampled to observe the size of the granulated particles. polymer using an optical microscope, p the reaction solution is periodically added to 15Qg of medium calcium phosphate in order to make the dispersion system stable and to maintain a small particle size. The spherical beads thus obtained are filtered, washed with dilute hydrochloric acid solution and dried. Micrographs of the beads are taken and particle size distributions (proportions) are measured (Table 1) .-. Table 1 Particle size, micron Amount,%. Example 2 (comparative). the process is carried out analogously to example 1, except that during the limerization, a stirrer is used with a lotion of the H-type Spray, and no mogenizer-mixer is used. The particle size distribution of the product is presented in table 2. .Table 2 particle size, micron Quantity,% Example 3 (comparative). Individuals are carried out similarly to Priori 1, except that during the whole operation the mixer is used and the mixer is not used with an H type blade. After 3-4 hours after temperature increase, a conversion degree of 60) a destruction of spherical balls with a homogenizer-mixer is detected, leads to an increase in the contamination of the apparatus and further complicates the conduct of the reaction. The increase in the hardness of the balls as the polymerization develops and their destruction by shearing with the sharp blades of the mixer-homogenizer, resulting in the formation of small broken pieces, leads to clogging of the apparatus. Therefore, polymerization using a homogenizer-mixer alone is unsuitable and the conditions of mixing of the polymerization system must be changed to conditions without shearing force and mechanical shearing or grinding at the proper time after the degree of transformation of the balls reaches 1-50 P and m a p 4. A flask and apparatus analogous to example 1 are used. In a flask, g: styrene 70, divinylbenzene 40, benzoyl peroxide, 1,2, suspension of 10% average calcium phosphate are placed. 60, 1% aqueous solution of sodium dodecylbenzenesulfonate sodium 2.4. The polymerization is carried out at 10-15 ° C for 1.5 hours with stirring followed by cutting at high speed (cutting speed 1.3x10 min using a homogenizer mixer (conversion rate 30%). Then the reaction solution is quickly poured into another flask equipped with a stirrer with a blade of type H, and the polymerization is continued at 80-85 ° C for 5 hours at a stirring speed of 400,500 rpm. During the polymerization, the average calcium phosphate and sodium dodecylbenzenesulfonate are periodically added to maintain a small particle size The particle size distribution of the obtained balls is measured using micrographs of Table 3. Table 3 - "- Particle size, µm Quantity,% Example 5 (comparative). The method is carried out analogously to example 1, except that during the whole operation use an agitator with a blade type H, and do not use a homogenizer-mixer.The size distribution of the product is shown in Table 4. Tables a4 Particle size, μm Quantity,% Example P 6. Use a flask and apparatus similar to Example 1, Place in a flask, g, styrene 96; 60% divinylbeneol 24, benzoyl peroxide 0.75; ammonium salt of a copolymer of styrene and maleic acid 6.9, sodium chloride 8.9 and demineralized water 550 ml. Polymerization is carried out at 70-75 s for 1.5 h. Under stirring, followed by shearing at high speed (shear rate, about 2x ny) using a homogenizer-mixer (conversion rate 20%). Then, the reaction solution is quickly poured into another flask equipped with a stirrer with a H-type blade, and the polymerization is continued at 80-85 ° C for 5-6 hours at a stirring speed of 500-600 rpm. The particle size distribution of the product is shown in Table 5. T a b l and c. A 5 Particle size, µm I Amount,%
    PRI me R 7 (comparative). The method is carried out analogously to example 3, except that during the whole operation a mica-bar with a type H blade is used, and the homogenizer-mixer is not used. In the process, the resulting particles become larger and do not form particles with a small particle size. Example 8. In a four-necked, 1-liter flask equipped with a homogenizer-mixer as in example 1, were placed: g: 60% divinylbenzene 100J benzoyl peroxide 5, aqueous suspension of 10% average calcium phosphate. 100 | aqueous 0.5% methylcellulose solution 800 ml toluene 36, diethylbenzene and isoamyl alcohol., 15 Polymerization, carried out at 70-75 ° C for 3 hours with stirring, followed by shearing at high speed t shearing speed of about 7xlo MJjH Mc using a homogenizer -smixers (degree of conversion 20%). Then the reaction; The solution was quickly poured into a four-necked 1L flask equipped with a stirrer with a H-blade and the polymerization was continued at 80-85 ° C for 5 hours at a stirring speed of 500-600 rpm. . The particle size distribution is given in table. 6. Table 6 Example9 (comparative. In a divided flask with a capacity of 1 l, equipped with a homogenizer-mixer, are placed the ingredients similar to example 1, and mix them with cutting at a high speed (cutting speed 1.3x10 normal temperature for 20-30 min-for pre-dispersion. Then the resulting dispersion is transferred into the same quadruple 1st section of a 1-liter flask equipped with an agitator with a blade type H, and polymerization is carried out at 70-75 s for 2 hours and at 80-85 ° C in for 4 hours with stirring speed 506-600 obA-in. During the polymerization. 200 g of average phosphate is observed for the size of the particles of the beads using an optical microscope and a periodicity. The resulting balls are processed as in Example 1. The distribution of the size of the particles of the balls is given in Table. 7. Table 7 particles, µm Quantity,% PRI me R 10. Ingredients, g: 64 Styrene 60% divinyl 6eH30J Benzoyl peroxide 10% sparingly soluble tricalcium phosphate 1% sodium, 0.15 (instead of lauryl sulfate sodium dodecylbenzene sulfonate) 500 ml demineralized water 28, 8 Toluene n-Daude can28.8 The above ingredients polymerized in a manner analogous to example 1, except that the polymerization is carried out, accompanied by its high-speed shift for .1 h shear rate is 1.3x10 min; temperature 70-75 Pc (k.inverse 30%). Then, polymerization is carried out with stirring i (500-.60 O rpm for -CH. The resulting granulated polymer has a particle size distribution as shown in Table 8. Table 8 Particle size, µm%,% Table 11. Example 11. Ingredients, g Styrene42.0 60% divinylbenzene 30.0 Toluene - 57.6 Benzoyl peroxide 5 10% sparingly soluble calcium triphosphate 60 1% sodium dodecylbenzenesulfonate 1,3 Demineralized water 576 Polymerizable ingredients in a manner analogous to Example 1, except that the poly Accompanied by high-speed shear at a shear rate of 1.5 x min at 72-77 ° C for 2 h until a conversion reaches 40%, followed by polymerization at a stirring speed of 400 rpm, polymerization tegherture 80-85 ° C, polymerization time 4 h The resulting granulated polymer has a particle size distribution shown in Table 9. Table 9 Particle Size, µm Quantity,% --- - The conversion is measured by taking 1 MP of the sample from the reaction solutions (suspensions), adding 1 ml of mixed solution of methylate equeton, methanol and n-propanol in an equilibrium ratio, which gives a homogeneous solution, which is analyzed by gas chromatography to measure the proportion of monomers. Thus, the invention makes it possible to obtain copolymers of a granular structure with a relatively uniform and small particle size, about 10 microns in high yield.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING FINE-GRAIN COPOLYMERS by aqueous polymerization of a mixture of styrene, monovinyl ethylbenzene and divinylbenzene or a mixture of mono-vinyl ethylbeneol and divinylbenzene in the presence of a suspending agent at 70-85 ° C and stirring, which yields a process to increase the yield is carried out until 20-40% conversion of the monomers under stirring at a speed shift 1,510 -1,3h x10 5 L min '4, followed by the product obtained by depolymerization with stirring without shearing at a speed of 400-600 rev / min.
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    同族专利:
    公开号 | 公开日
    FR2446294B1|1982-11-12|
    GB2039921A|1980-08-20|
    JPS6244561B2|1987-09-21|
    US4323664A|1982-04-06|
    GB2039921B|1983-04-13|
    FR2446294A1|1980-08-08|
    DE3000596A1|1980-07-17|
    DE3000596C2|1985-07-11|
    JPS5594902A|1980-07-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2014016C3|1970-03-24|1978-05-18|Hoechst Ag, 6000 Frankfurt|Process for the production of vinyl chloride polymers|
    GB1393678A|1971-06-25|1975-05-07|Bp Chem Int Ltd|Polymerisation process|
    JPS49105890A|1973-02-08|1974-10-07|
    CH593304A5|1975-03-04|1977-11-30|Lonza Ag|Fine-particle suspension polymers with uniform size - prepd. under specified conditions in presence of polyvinyl alcohol|
    DE2629467A1|1976-06-30|1978-01-05|Wacker Chemie Gmbh|Aqueous CATALYST CONFECTION|
    US4071670A|1976-08-02|1978-01-31|Xerox Corporation|Method of sizing monomer droplets for suspension polymerization to form small particles|
    JPS53105586A|1977-02-25|1978-09-13|Asahi Chem Ind Co Ltd|Suspension polymerization|US4539380A|1983-07-14|1985-09-03|Formosa Plastics Corporation|Process for producing homopolymers or copolymers of olefinically unsaturated monomers|
    JP2534979B2|1984-12-27|1996-09-18|東ソー株式会社|Filler for liquid chromatography|
    JPH0572923B2|1985-03-30|1993-10-13|Nitto Denko Corp|
    JP2700189B2|1988-02-13|1998-01-19|出光石油化学株式会社|Method for producing styrenic polymer|
    US5292836A|1990-04-05|1994-03-08|Shin-Etsu Chemical Co., Ltd.|Preparation of vinyl chloride polymers using high-speed and low-speed shear agitation|
    JP2747843B2|1990-04-05|1998-05-06|信越化学工業株式会社|Method for producing vinyl chloride polymer|
    JP2008214532A|2007-03-06|2008-09-18|Sumitomo Chemical Co Ltd|Method for producing fine particles of resin|
    CN103467645B|2013-08-30|2016-03-16|南京大学|A kind of anti-Organic pollutants ion exchange resin and its preparation method and application|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP54002422A|JPS6244561B2|1979-01-11|1979-01-11|
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