• 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:
    A novel and improved method for polymerizing a vinyl monomer in a polymerization reactor is provided. The inner walls of the polymerization reactor and other surfaces coming into contact with the monomer are coated with an aqueous liquid containing at least one alkali metal or ammonium salt of an anionic dye of the sulfonic carboxylic acid form and having a pH value adjusted not to exceed 7 by aid of a pH adjusting agent, and the thus coated surfaces are dried with heat before the polymerization is conducted. The method serves to greatly reduce the deposition of polymer scale on those surfaces and, consequently, improve the productivity as well as the quality of polymer product.
    公开号:SU791249A3
    申请号:SU782567998
    申请日:1978-01-25
    公开日:1980-12-23
    发明作者:Коянаги Сунити；Хасегава Ниитиро；Симизу Тосихиде；Кацусима Сенсаку；Канеко Итиро
    申请人:Син-Эцу Кемикал Ко.,Лтд (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to the technology of obtaining chain-chain polymers and can be used in the chemical industry.
    A known method for producing carbo-5-chain polymers by radical polymerization or copolymerization of ethylene-unsaturated monomers in bulk, solution, aqueous emulsion or suspension 1 .to
    The disadvantages of this method are associated with the deposition of a polymer film on the inner walls of the polymerization reactor and the surfaces of equipment such as agitators.
    A number of disadvantages caused in the known methods by the deposition of a polymer film on the inner walls of a polymerization reactor and the surfaces of the mesh, etc., which contact the monomer or monomers, include losses in polymer yields, a decrease in the productivity of the cooling unit of the polymerization reactor and an undesirable decrease the quality of polymer products due to the separation of the polymer film from the surface and its possible inclusion in the product i, as well as too much labor-intensiveness and duration of the process
    the removal of the polymer film from the surfaces after each polymerisation cycle, and the health problem of workers associated with the inhalation of volatile monomers such as vinyl chloride.
    The purpose of the invention is to reduce the degree of deposition of the polymer film on the inner surfaces and parts of the reactor.
    This goal is achieved in that according to the method of obtaining chain-chain polymers by radical polymerization or copolymerization of ethylenically unsaturated monomers in mass, solution, aqueous emulsion or suspension, the inner surfaces and parts of the reactor are treated with 0.01-5% by weight of an aqueous solution of alkali salts before starting the polymerization. Metals or ammonium salts of water-soluble anionic dyes in sulfoxide or carboxyl form at a pH of 1-7 with subsequent drying of surfaces at 40-100 C.
    Processing the aqueous solution further comprises water-soluble cationic dyes containing at least one pair of conjugated double bonds and at least one nitrogen atom in the molecule when they are
    weight ratio to the indicated compounds is from 100: 1 to 100: 0.1, as well as silicic acids, silicates or water-soluble metal salts other than alkaline, with their weight ratio to the specified compounds from 100: 1 to 100: 0.1 .
    The processing aqueous solution additionally contains 1-20 wt.% Of C-Su-alkanol.
    The anionic dyes (component a) in the sulfonic acid forms or carboxyl forms used in the proposed method as an alkali metal or ammonium salt are represented by the following dyes.
    Sulphonic acid dyes
    0.1. Acid yellow 38,0.1. Food yellow 3,0.1. Reactive Yellow 3.0. Pr my orange 2,0.1. Pr my orange lOyO.l. Acid Red 18.0.1. Acid Red 52.0.1. Acid Red 73.0.1. Pr my red 186,0.1. Pr my red 92,0.1. Pr my purple 1.0.1. Pr my purple 22,0.1. Acid violet 11,0.1. Acid violet 78,0.1. Mordant purple 5,0.1, Pr my blue 6,0.1. Pr my blue 71,0.1. My blue is 106.0.1. Reactive Blue 2.0.1. Reactive blue 4,0.1. Reactive blue 18,0.1 Acid blue, 116,0.1. Acid Blue 158.0.1. Acid Black 1, 0.1. Acid black 2,0.1. Pr my black 38,0.1. Soluble vat black 1.0.1. Fluorescence show agent 30.0.1. Acid Blue 1.0.1, Acid Blue 40.0.1. • Aloe blue 59,0.1. Acid blue 113,0.1. Acid Orange 7.0.1. My Blue 1.0.1. Pr my blue 86,0.1. Pr my orange 26,0.1. Pr my red 31,0.1. Pr mo black 19,0.1. Pr my black 32,0.1. Pr my black 77,0.1. My green 1.0.1. Acid Orange 3.0. Acid Black 124.0.1. Acid Red 52 and 0.1. Acid Red 80.
    Dyes in carboxyl forms and dyes in both sulphonic and carboxyl forms:
    0.1. My yellow 1.0.1. My red 1.0.1. Protravnoy black 5, 0.1. Azo dye brown 2,0.1. Pr my brown 1,0.1. Pr my brown 101,0.1. Pr my green 26,0.1. Acid Red 87.0.1 Precious Yellow 26.0.1. Pr my brown 37 and 0.1. Pr my orange 97.
    The pH of aqueous solutions of component a in a relatively low concentration of about 0.1 to 1% by weight is about 10. Such an aqueous alkaline solution of component a does not have a satisfactory effect of preventing the deposition of the polymer film when applied to the inner walls of the reactor, followed by drying to form protective films on the surface. Use a pH adjusting agent to adjust the pH of the aqueous solution of component a to a value of about 7 or below this value, and most preferably, about 5 or less than that value.
    PH adjusting agents that should be used to: adjust the pH of the aqueous dispersion or solution of component a are represented by a number of different organic and inorganic acids, such as sulfuric, hydrochloric, phosphoric, nitric, carboxylic, clone, molybdenum, tungsten , formic, acetic, oxalic, lactic, maleic, glycolic, thioglycolic, phytinic and acid salts of these acids, if they exist. Among these compounds, the most preferred are sulfuric, phosphoric, nitric, molybdenum, molochna, glycolic, thioglycolic, phytic acids and their acid salts, if they exist, in terms of obtaining the best results in preventing the deposition of a polymer film. PH adjusting agents are usually used in the form of aqueous solutions.
    The aqueous solution of protective fluid to be applied to the inner walls of the reactor is prepared, diluted or dispersed in water and then the agent is added, adjusting the pH until the aqueous solution is 7 or less. The concentration of compound a in a protective solution is preferably in the range of from about 0.01 to about 5% by weight, taking into account the solubility of component a in water, the ease of applying the coating of the protective solution and improving the solubility of component a in water when the pH value drops to 7 or lower. .
    The protective coating solution thus obtained with a pH value of about 7 or lower is applied to the inner walls of the reactor and other surfaces. to form a protective film that prevents the deposition of a polymer film. It is recommended to increase the convenience of working with a pacTBOpiOM protective coating, or to apply a protective liquid to the surface, to dab a small amount from about 1 to 20% by weight of a monohydric alcohol containing from 3 to 5 carbon atoms in the molecule. Examples of monohydric alcohols suitable for this purpose include n-propyl, isopropyl, tert-butyl, n-amyl, tert-amyl, iso-amyl, sec, am-amyl, etc., among which the most preferable is iso-butyl alcohol having the least unpleasant smell.
    The addition of a monohydric alcohol to the protective liquid is effective not only in that it facilitates the coating operation, but also improves the layer’s ability to prevent deposition of the polymer film.
    Methyl or ethyl alcohols as monohydric alcohols are not recommended for these purposes due to the fact that a greater amount is required to obtain the expected results, whereas monohydric alcohols with more than 5 carbon atoms are not suitable for use because of their low solubility in water,
    In another embodiment, the effectiveness of the proposed method is increased by adding a single-soluble cationic dye (component b), the molecule of which contains at least one pair of conjugated double bonds and at least one nitrogen atom, water-soluble silicic acid or a water-soluble metal salt ( component c) other than alkali metals in combination with component a.
    Adding the component in to the protective liquid is effective in reducing the amount of substance needed for applying the POKEYALTY and in terms of reducing the drying temperature necessary to obtain a sufficiently solid protective film with full effectiveness in preventing the deposition of the polymer film. On the other hand, component c added
    protective fluid is effective in increasing the strength of the protective film deposited on the surface.
    Water-soluble cationic dyes suitable for use as a component in include Water-soluble azine dyes, such as 0.1. Basic red 2, 0.1. Primary blue 16, 0.1. Basic black 2, etc .; Water soluble acridine dyes such as. Basic orange 14, 0.1. Basic orange 15, etc .; harsh water soluble triphenylmethane dyes as 0.1. Primary blue 1, 0.1. Main purple 3, 0 ,. one . Primary blue 26, 0.1. Basic purple 14.0.1 Basic blue 5.0.1. Primary blue 7, etc .; Water soluble triazine dyes such as 0.1. Basic blue 9.0.1. Primary yellow 1, 0.1. Primary blue 24, 0.1. The basics are blue 25, .0.1. Basic green
    5 and so on; Water soluble methine dyes such as 0.1. Primary red 12, 0.1. Primary yellow 11, etc .; Water-soluble diphenylmethane dyes such as 0.1. Primary yellow 2, etc .; water-soluble dyes such as xanthene dyes About L. Basic purple 10, 0.1. Basic red 1
    etc.; Water soluble azo dyes such as 0.1. Basic orange 2, 0.1. Main brown 1, etc .; and Water-soluble oxazine dyes, such as 0.1. Primary blue 12, 0.1. Basic blue
    6 etc.
    The compounds, according to the present invention, are illustrated with water-soluble silicic acids or silicates like ortho-silica, meta-silica, meso-dikremnev, meso-trikremnev, meso-tetrakremnev, sodium metasilicate, sodium orthosilicate, sodium disilicate, etc., and the same; potassium disilicate, lithium orthosilicate, hexalithiorthodisilicate, liquid glass, 12-silicon-tungsten, from-12-silicon-tungsten, 10-silicon-tungsten acid, 1-silica-potassium potassium, from-12-silicon-potassium tungstate 10-silicon. potassium alframate, sodium 12-tartanate, silicon molybdic acid, potassium molybdate, sodium molybdate, etc .; and such water-soluble salts of hydroxy acids, acetic, nitric acids, hydroxides and halides of metals belonging to alkaline earth metals, such as magnesium, calcium, barium, etc .; metals of the zinc group, for example zinc and the like; metals of the aluminum group, for example alcumini; me1; allov of the tin group, for example, tin, titanium, etc .; metals of the iron group for example iron, nickel, etc .; metals of the manganese group, for example manganese; mettschlov group of copper, such as copper, silver, etc .; and platinum group metals, such as platinum.
    If, in combination with component a, components b or c are used, then the weight ratio of the component b or c to component a should be preferably in the range 100: 0.1-100: 1.0 or, more preferably, 100: 3-100: 100 to obtain a strong adhesion of the protective film on the inner walls of the polymerization reactor. The total concentration of the components, in and with the component a in the aqueous solution of protective fluid is preferably in the same range (0.01-5 wt.%), As in the protective fluid with component a. Anyway, the pH value of the aqueous solution of protective liquid should be about
    7 or lower. This is due to the fact that protective films made with alkaline protective liquids with pH values higher than 7, say 10 or so, with subsequent drying, can dissolve when contacted to prevent deposition of the polymer film. If the ingredients of an eucite fluid, such as component a or c, are used as an organic solution, the resulting protective films are also soluble when in contact with the aqueous medium, which leads to a decrease in the effectiveness of preventing the formation of a polymer film.
    The inner walls of the polymerization reactor and other surfaces coming in contact with the monomer or monomers are first coated with aqueous protective liquid and then dried to 40-100 ° C. In another embodiment, an aqueous solution of the protective liquid is applied to surfaces previously heated to 40-100s. in any case, the surfaces to which the coating is applied must dry sufficiently before they are washed with water, followed by a polymerization cycle. The thickness of the protective coating on the walls of the reactor and other surfaces according to the proposed method should be approximately the same as in other known methods, in which a protective coating of some materials was used. Namely, a sufficiently strong effect to prevent the formation of a polymer film can be obtained using an amount of protective coating greater than 0.001 g / m after drying on the walls of the reactor and the surfaces of the stirrer and the like.
    The effectiveness of the proposed method is not limited to any particular polymerization method. Accordingly, the proposed method is effective for any type of polymerization — in suspension, esulsions, and in bulk. The effectiveness of preventing the deposition of a polymer film is also independent of additives normally introduced into the polymerization mixture, such as suspending agents, for example, partially bound polyvinyl alcohol, methylcellulose, etc .; anionic surfactants, for example, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dioctyl sulfosuccinate, and the like; nonionic surfactants, for example, sorbitan monolaurate, polyoxyethylene alkyl ethers, and so on; naphlates, for example, calcium carbonate, titanium dioxide and the like; stabilizers, such as tribasic lead sulfate.
    Calcium stearate, dibutyl tin dilaurate, dioctyl tin marcaptide, and the like; lubricants, such as rice mastic; stearic acid, etc .; plasticizers, for example dioctyl phthalate, dibutyl phthalate and the like; chain transfer agents such as trichlorethylene, mercaptans, and the like; pH adjusting agents — polymerization initiators, for example diisopropyl paroxycarbonate, o (., o1-azobis-2,4-dimethylovalent nitrile, lauroyl peroxide, potassium persulfate, cumene hydroperoxide, hexahydroparacymol hydroperoxide, etc.
    The vinyl monomers to be polymerized include those vinilgaloidy as vinyl chloride, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid, methacrylic acid and their ester anhydrides, maleic acid, fumarinovuyu acid and their esters and anhydrides, diene monomers, the same as the butadiene, chloroprene and isoprene, styrene, acrylonitrile, vinylidene halides and simple vinyl ethers.
    The proposed method is particularly suitable for. heterogeneous free radical polymerization, in which the polymer formed is released from the polymerization mixture as the polymerization reaction proceeds. A typical case of this type of polymerization is the production of homo- and copolymers of vinyl halide, vinylidene halide, or a mixture of monomers, mainly consisting of them, by polymerization and suspension or emulsion in an aqueous medium.
    The method is also effective due to the prevention of the deposition of a polymer film on the walls of a polymerization reactor made of stainless steel, in which the methyl methacrylate styrene, acrylonitrile, etc., are suspended and polymerized; obtaining SBRH NBR rubber latexes by emulsion polymerization and obtaining ABS - acrylonitrile butadiene styrene resins (N8R.- butadiene acrylonitrile rubber and SBR - styrene butadiene rubber). ,
    Table 1 lists some parameters illustrating the method of the invention. The experiment marked with an asterisk () is a control. "
    Example 1-6. In the examples, a one-hundred-cure polymerization reactor made of stainless steel U1 equipped with a stirrer is used. An aqueous solution of the protective liquid is prepared, a solution of 0.1. Acid black 2 in conc. 1% by weight and adjusted pH in accordance with the knowledge given in Table 1 with sulfuric acid. Internal
    the walls of the polymerization reactor and the surface of the stirrer are covered with a protective liquid prepared in an amount corresponding to 0.1 g / m (after drying), followed by drying and washing of the table.1. 26 kg of vinyl chloride monomer, 52 kg of deionized water / 26 g of partially saponified polyvinyl alcohol and 3 g of oC, o.-azobis-2, 4-dimethylvsheronitrile are loaded into the polymerization reactor thus treated, after which the polymerization mixture is heated at 57 ° C for 8 h, with stirring.
    After the end of each polymerization cycle, the amount
    the polymer film deposited on the walls of the reactor, and the results obtained are given in the table in the form of g / m. The results shown in Table 1 demonstrate the effect of pH adjustment in the drying condition (temperature and time) on the formation of a polymer film. Referring specifically to examples 5 and 6 and comparing them with each other, it can be seen that the extension of drying from 10 to 30 minutes leads to a decrease in the deposition of the polymer film from 300 to 200 g / m. The obtained data are interpreted as evidence that insufficient drying leads to unsatisfactory data in terms of preventing the deposition of a polymer film. Table 1
    Pri.me h an. T. Examples 7-37. The inner walls of a thousand stainless steel polymerization reactor made of stainless steel and the agitator surface are coated with an aqueous solution of protective liquid obtained by dissolving the anionic dye (protective compound) in 45 conc. 1 wt.% With a pH value achieved by adding a pH regulating agent, followed by drying and heating in a quantity corresponding to a layer of 0.1 g / m (dry 50 form), after which the reactor is washed with water (Table 2) .
    The polymerization reactor thus treated is charged with
    - room temperature. 200 kg of vinyl chloride monomer, 400 kg of deionized water, 40 g of diisopropylperoxyl sarbonate, 250 tons of partially oxidized polyvinyl alcohol and 25 g of hydroxypropylmethylcellulose, after which they are polymerized at 57 ° C for 12 hours with vigorous stirring with a stirrer. After the polymerization reaction is complete, the polymerization mixture is discharged from the reactor, it and the reactor are washed with water and dried to determine the amount of polymer film deposited on the wall. The results are shown in
    Table 2. „
    table 2
    Continued table. 2
    Examples 38-43. The inner walls of a thousand stainless steel polymerization reactor and the surface of the agitator are coated with an aqueous solution of protective liquid at the end. 1 wt.% In an amount corresponding to a layer of 0.1 g / m after drying (Table 3).
    200 kg of vinyl chloride monomer is charged to the polymerization reactor thus treated.
    note; DMUN -, D1-azobis-2,4-dimethyl, vinyl alcohol; Na-LS - lauryl. Continuation of table 2
    400 kg of deionized water and other ingredients, including a polymerization initiator and a dispersing agent, after which the polymerization reaction is carried out with stirring for 10 hours. After the polymerization time has elapsed, the polymerization mixture is removed from the reactor and the amount of polymer film deposited on the walls of the reactor is determined. The results are shown in table 3. Table 3
    valeronitrile; KPS - potassium persulfate; APS - ammonium persulfate; ERD — Partially Saponified Sodium Polysulfate; Ma-DV5 is sodium dodecylbenzenesulfonate.
    Examples 44-48. The inner walls and other surfaces of the combined unit, consisting of a two-liter vertical-type polymerization reactor of stainless steel and a four-liter, horizontal stainless-type polymerization reactor in contact with the monomer, are coated with an aqueous solution of protective liquid at the end. 1% by weight in an amount of 0.1 g / m after drying is poured with water and finally dried (Table 4).
    800 g of vinyl chloride monomer and O, 3 g of diisopropyl peroxydicarbgiate are charged into a two-liter polymerization reactor and the polymerization is carried out at about 60 ° C for 2 hours with vigorous stirring at a rate of 900 O6. / MIN. The polymerization mixture from this polymerization reactor is then transferred to a 4 l polymerization reactor, which is preloaded with 800 g of vinyl chloride monomer and 0.4 g of diisopropyl peroxydicarbonate, in which the polymerization is continued by heating at 57 ° C for 10 hours with a stirrer speed 100 VOLUME After completion of the polymerization reaction, the polymerization mixture is discharged from the reactor and the amounts of polymer film deposited on the inner walls of both polymerization are determined. Reactors. The results are given in Table 4.
    Table
    Examples 48-Ы. The inner walls of a 100-liter enameled polymerization reactor and the surface of the mesh / Eki are coated with an aqueous solution of protective liquid at the end. 1% by weight in an amount corresponding to 0.1 g / m after drying, followed by drying at 90 ° C for 10 minutes and thorough washing with water. The polymerization reactor thus treated is charged
    20 kg of vinyl chloride monomer, 40 kg of deionized water, 13 g of potassium persulfate and 250 g of sodium lauryl sulfate, after which the polymerization reaction is carried out at 50 ° C for 12 hours with stirring. After the polymerization time has elapsed, the polymerization mixture is discharged from. reactor and determine the amount of polymer film deposited on the walls of the reactor. The data obtained are given in table.5.
    Table 5
    Examples 52-54. The inner walls of a 100-liter polymerization reactor made of stainless steel and the stirrer mounted in it are preheated, and then protective liquid is applied to them at the end. 1% by weight in an amount corresponding to 0.1 g / m after drying, then after drying the protective liquid, the surfaces are washed with water, and the polymerization reactor thus treated is subjected to the same polymerization reaction as in Example 1. Upon completion of the polymerization reaction, the amount of polymer film - deposited on the walls of the reactor is determined. The results are shown in tab. B.
    Table
    Examples 55-58. Internal steaks and agitator surface of a full mororization reactor made of stainless steel of 400 l with a capacity of 400 liters
    protective liquid in conc. 1 wt.% In an amount corresponding to a layer thickness of 0.1 g / m in the dried state, followed by drying and washing with water. 200 kg of deionized water, 100 kg of styrene monomer, 1 kg of calcium phosphate are loaded into the polymerization reactor thus processed, 10 g of sodium dodecylbenzenesulfonate and 100 g of benzoyl peroxide, and a polymerization reaction is carried out at 90 ° C for 11 hours with stirring. After the completion of the polymerization reaction, the amount of polymer film deposited on the walls of the reactor is determined. Tavlya in Table 7.
    Table 7 Examples 59-61. The inner walls and the surface of the agitator of the polymerization reactor used in Example 7 are covered with a layer of protective liquid at the end. 1% by weight in an amount corresponding to a layer thickness of 0.1 g / m in the dried state, and then dried with heating and washed with water. Under the same conditions as in Example 7, the polymerization of styrene was carried out, and after completion of the polymerization reaction, the polymerization mixture was discharged from the reactor, which was then washed with water. Then, all operations are repeated and a whole series of polymerization processes are carried out in which the amount of polymer film deposited on the walls of the reactor does not exceed 1 g / m. 1 g / m. Results are presented in t-abl. 8. Table
    Examples 62-66. The inner walls and the surface of a 400 L stainless steel polymerization reactor are coated with a layer of protective liquid at the end. 1% by weight in an amount corresponding to 0.1 g / m in the dried state, after which they are dried and dried with water (Table 9). 190 kg of deionized water, 75 kg of 1,3-butadiene monomer, 25 kg of styrene monomer, 4.5 kg of sodium lauryl sulphate, 280 g of tert-dodecyl mercaptan and 300 g of potassium persulphate are loaded into the polymerization reactor thus treated, after which the polymerization is reacted for 12 hours with stirring. After the polymerization reaction is completed, the amount of polymer film deposited on the walls of the reactor is determined.
    0 The results are shown in Table 9.
    Tablntsa 9 PRI m e-s s 67-70. The inner walls and the surface of a 400 L stainless steel polymerization reactor are coated with a layer of protective liquid at the end. 1% by weight in an amount corresponding to 0.1 g / m of the dried state is then dried with heating and washed with water (Table 10). 180 kg of deionized water, 74 kg of 1,3-butadiene monomer, 26 kg of acrylonitrile monomer, 4 kg of 1,3-butidiene monomer, 26 kg of acrylonitrile monomer, 4 kg of sodium oleate, 1 kg of oleic acid, are loaded into the polymerization reactor thus treated; 500 g of tert-dodecyl mercaptan, 100 g of sodium pyrophosphate and 300 g of potassium persulfate, followed by a polymerization reaction at 40 ° C for 12 hours with stirring. After the polymerization reaction is completed, the amount of polymer film deposited on the walls of the reactor is determined. The results are shown in table 10.
    l p and merys 71-73. The inner walls and the agitator surface of a 400 l enamelled polymerization reactor are covered with a layer of protective liquid at the end. 1 wt.% In an amount corresponding to the thickness of the O layer, 1 the dried state, followed by drying with heating and water boiling (Table 11). 180 kg of deionized water, 40 kg of 1,3-butadiene monomer, 54 kg of methyl methacrylate monomer, 4 kg of styrene monomer, 4.5 kg of laurylbenzenesulfonate sodium, 280 g of tert-dodecyl mercaptan and 300 g of potassium persulfate, after which carried out the polymerization reaction for 10 hours with stirring. Upon completion of the polymerization reaction, the amount of polymer film deposited on the walls of the reactor is determined and expressed as g / m. Results are presented
    in tab. 11.,. ..
    T a blitz 11
    130
    71
    ny 2
    lot
    That °
    76
    Also
    same
    77
    Examples 74-90. Aqueous solutions of protective liquids are prepared, the solution in water is water soluble. E. Anionic dyes (protective compound) in conc. 1% by weight, followed by adjustment of the pH by adding the pH adjusting agent, monohydric alcohol is added in an amount given in parts by weight. per 100 parts by weight of a water solution obtained by dissolving the dye in water (Table 12).
    the inner walls of a 1000 liter polymerization reactor of stainless steel and the surface of the agitator are covered with a layer of protective liquid in an amount corresponding to a layer of 0.1 g / m in the dried state, followed by drying and heating. 200 kg of vinyl chloride monomer, 400 kg of deionized water, 250 g of partially saponified polyvinyl alcohol, 25 g of hydroxypropylmethylcellulose and 75 g of diisopropyl methylcarbonate are loaded into the polymerization reactor thus treated, followed by a polymerization reaction for 10 hours with stirring.
    t
    After completion of the polymerization reaction, the amount of polymer film deposited on the walls of the reactor is determined, the results are expressed in g / m and are presented in Table. 12.
    Examples 87 and 88 show that the use of methanol or ethanol leads to a somewhat larger formation of a polymer film as compared to the cases when other alcohols with a large number of carbon atoms are used. From examples 89 and 90, where surface active agents were used instead of monohydric alcohols, it can be seen that surface active agents have an adverse effect on the prevention of film formation.
    Table 12
    6.0 OO-Butyl 1 O alcohol
    5.0
    90
    P j5 and meds 91-110. Each of the anionic dyes (compound a according to the pointer 0.1.) F cationic dyes (compound in the pointer 0.1) and agents regulating the value of .рН in such quantities that it is complete dissolve in water. the concentration of the three compounds is about 0.1% by weight, and the pH of the solution reaches the value indicated in the table by adding an agent that regulates the pH (Table 13). Internal walls of polymerization
    Ly 2
    Continued table. 12
    sodium fat, 0.02
    500
    Polyethylene glycol, surfactant, 10
    A stainless steel reactor with a capacity of 100 liters is covered with a layer of adherent protective liquid and the vinyl chloride monomer is polymerized in suspension under almost the same conditions as in Example 1, with the exception that the amount of protective layer is 0.01 g / m
    0 instead of 0.1 g / m after drying. After completion of the polymerization reaction, the amount of polymer film deposited on the walls of the reactor was determined. The results are shown in Table. 13.
    Table 13. Note:
    Examples 111-129. Each of the anionic dyes (compound a at the pointer 0.1), cationic dyes (compound c of the pointer Q.1) and pH-adjusting agents are dissolved in water in such quantities that the total concentration of these three components reaches about 1.5 times. 13
    It was 0.1 wt.%, and the pH value of the solution was adjusted as indicated in the table by adding an agent regulating the pH value (Table 14).
    Internal walls and surface of a 120 L stainless steel polymerization reactor agitator
    65 cover with a protective layer of liquid in the column; pH regulating agent: P - phytic acid; Р-2 - sodium salt of phytic acid; T-2 - triethanolamine salt phytic acid.
    in amounts corresponding to 0.01 g / m in the dried state, followed by drying by heating and thorough washing with water.
    50 kg are loaded into the polymerization reactor thus treated. styrene monomer, 43.2 kg of deionized water, 120 g of oxyapatite, 0.62 g of acidic sulfite
    sodium, 125 g of benzoyl peroxide and 225 g of tert-butylperbenzoate, after which the polymerization is carried out at 90 ° C for 7 hours with stirring. After completion of the polymerization reaction, the amounts of polymer film deposited on the wall of the reactors are determined. The obtained results are shown in table 14.
    Table 14 Note; in the column of tin to phytin fitin Examples 130-139. Each of the anionic dyes (compounds a according to the pointer 0.1), cationic dyes (compounds in the pointer 0.1) and pH regulating agents are dissolved in water in such quantities that the total concentration of these three compounds is about 0.1 wt.%, and the pH value of the solution is set equal to the value indicated in the table by adding an agent that regulates the pH value (Table 15). The inner walls and the surface of the stirrer of a 400-liter polymerization reactor made of stainless steel are covered with a protective layer of the liquid thus prepared in the amount of
    P - phytic acid; P ,, - 2-natriene salt of phytic acid.
    Continued table. 14 staling agent pH: P - FIA; P - 2-ethylamine salt; PC - 2-amino salt salt. A veil corresponding to a layer of 0.01 g / mV dried state, then dried with heating and washed with water. 80 kg of vinyldechloride monomer, 20 kg of vinyl chloride monomer, 200 kg of deionized water, 150 g of benzoyl peroxide, 125 g of partially saponified polyvinyl alcohol and 25 g of methylcellulose are loaded into the polymerization reactor thus treated, then the polymerization reaction is carried out for 12 hours while stirring . After the end of the reaction: the polymerization determines the amount of polymer deposited on the walls of the reactor. The results are shown in Table 15. Table 15.
    Examples 140-151. The inner walls and the surface of the agitator of a 200 l polymerization reactor made of stainless steel are covered with a layer of protective liquid at the end of 0.1 wt.% In an amount corresponding to a layer of 0.01 g / m in the dried state, then dried by heating and washed with water (Table .sixteen).
    50 kg of styrene monomer, 50 kg of deionized water, 125 g of partially saponified polyvinyl alcohol, 25 g of methylcellulose and 150 g of benzoyl peroxide are loaded into the polymerization reactor thus treated, followed by polymerization at 7 hours with stirring. After completion of the polymerization reaction, the amounts of polymer film deposited on the wall of the reactor are determined. The results are shown in table.
    Table 16
    60 kg of washing monomer, 40 kg of acrylonitrile monomer, 100 kg of deionized water, 2 kg of hydroxyapatite, 40 g of sodium lauryl sulfate, 300 g of tert-dodecyl mercaptan and 400 g of lauroyl peroxide are loaded into the polymerization reactor thus treated.
    The polymerization reaction is carried out at a stepwise rise in temperature, starting at 1 h at 70 s, then the temperature is raised from 70 to 80 ° C for 2 h, and finally, at 1 h at, with the result that a copolymer of styrene and acrylonitrile is obtained. After the polymerization reaction is completed, the amounts of polymer film deposited on the walls of the reactor are determined. The results are shown in Table. 17
    Table 17
    This is washed with water and the polymerization process is repeated under the same conditions as already indicated, then the number of polymerization cycles that are carried out without intermediate removal of the polymer film is recorded until its thickness reaches 1 g / m. . The results are shown in .tabl. 18.
    Table 18
    PRI me R s 167-170. Repeat the same experimental procedure as in Examples 91-110, with the difference that protective fluids mixed with monohydric alcohol are used. The data obtained on the amount of polymer film deposited on the walls of the reactor are given in Table. 19. In these experiments, surfaces covered with a layer of liquid fluid and heated at during ID min. It turned out that the addition of a monohydric alcohol and a protective liquid is effective in improving the distribution of the protective liquid over the surface of the stainless steel jacket, encompassing the process of applying a protective coating.
    T a
    persons 19
    5 of the bone used in example 94, and 10% isobutyl alcohol
    168 The mixture of protective liquid of Q Q bone used in example 101,
    and 5% -Hfcift-butyl alcohol
    169Mixed protective liquid used in Example 103, and 10% TRET butyl alcohol2
     The mixture of protective liquid used in Example 110 and 10% sec-amyl alcohol3
    Note: All percentages
    o are indicated by weight.
    Examples 171-191. The inner walls and the surface of a 100 l stainless steel polymerization reactor are coated with a protective layer of liquid obtained by dissolving each of the anionic dyes (compound a according to pointer 0.1) and metal salts (compound c) in a weight ratio of total conc. 1% by weight, followed by adjustment of the pH by the addition of hydrochloric acid, followed by drying with heating, and washed thoroughly with water (Table 20).
    26 kg of vinyl chloride monomer, 52 kg of deionized water, 26 kg of partially molded polyvinyl alcohol and 8 g of dL, o (azobis-2, 4-dimethylvaleronitrile) are loaded into the polymerization reactor thus treated, and then polymerization is carried out at 57 ° C for 8 hours with stirring. After the completion of the polymerization reaction, the amount of polymer film deposited on the walls of the reactor is determined.
    Table 20
    Silicate nat - 100/20 5, X) 90; five
    Pr my red ri
    Silicate, nat / 0/100 10.0 - rize (II) chloride iron (III) chloride 185 Acidic cherlezo (II) chloride 186acid chercallium 2 copper acetate 187Pr my blue b (and) gele nitrate189 prostitute siza (I) 1 Chloris-Guy Qi 189 Pr my orange 10
    Chloride jelly 190 Acid iron (I) 100/7 4.0 90; 5th 38 191 Acid black- Chloride 100/3 nyloe (I)
    Examples 192-201. The inner walls and the surface of the sack of the polymer reactor are covered with a layer of protective liquid at the end. 1 weight,% in such quantity, which corresponds to a layer thickness of 0.1 g / m in the dried state, followed by drying under the conditions indicated in the table (Table 21).
    200 kg of vinyl chloride monomer is loaded into the polymerization reactor thus treated.
    Prolongation of tab. 20
    900
    one
    one
    400 kg of deionized water and other ingredients, followed by polymerization at 57 ° C for 10 hours with vigorous stirring. After the completion of the polymerization reaction, the amount of polymer film deposited on the walls of the reactor is determined and expressed in g / m. The data obtained are given in table. 21.
    Experiments 223 and 224 were conducted in order to demonstrate 0/100 100/3 100/8 5.0 90; 10 100/7 5.0 40; 120 100/13 3.0. 90; 10,100/7 5.0 - 5, 0 90; 10 o
    the effectiveness of the proposed method for the copolymerization of vinyl chloride and vinyl acetate. The amount of vinyl chloride used is 200 kg.
    192
    flMVN 0.05
    174
    60; 120
    70; 60
    1-76
    flMVN 0.05 80; 30 178 LPO 1.3 180 90; 5
    190
    DMUM 0.075
    186
    down 0.05
    189
    LPO 1,3
    191 dPP 0.05
    Octyl vol “p saptid 1.75 + polyethylene wax 0.25. flMVN - otjdL -azobis-2,4-dimethylvaleronitrile; LPO - lauroyl peroxide; PP - diisopropyl peroxydicarbonate; KPS - potassium persulfate; HPMC - hydroxypropyl methylcellulose; SML - sorbitan monolaurate; PVA - partially saponified polyvinyl alcohol; NaLS - sodium lauryl sulfate.
    Examples 202-206. The inner walls and other surfaces of the combined unit, consisting of a vertical-type polymerization reactor of stainless steel with a capacity of 2 liters and a horizontal polymerization reactor of 4 liters with a capacity of 4 liters, which are in contact with the monomer, are coated with a protective liquid in the end. 1 weight. in an amount of 0.1 g / m in the dried state, followed by drying and heating each experiment, while the amount of vinyl acetate is 10 kg in experiment 223 and 37.5 kg in experiment 224.
    Table 21
    HPMC 0.25 + + SML 0.25
    0.25
    About About About 0.25
    Stearinova-Oh, ° 25
    Oh oh
    Stearinova to-0,25
    they are then washed with water and finally dried,
    800 g of vinyl chloride monomer and 0.3 g of diisopropyl peroxydicarbonate are loaded into the vertical-type verticalization reactor so processed, and the monomer and polymerization are reacted at 60 ° C for 2 hours with vigorous stirring at a speed of 900 rpm. Then the polymerization mixture is transferred to the reactor of the horizontal type, which is pre-loaded
    800 g of vinyl chloride monomer and 0.4 g of diisopropyl peroxydicarbonate, and the polymerization reaction is continued at about 57 ° C for an additional 10 hours while operating the stirrer at a speed of 100 rb / min. After the polymerization reaction is completed, the amounts of polymer film are determined by deposition on the inner walls of both polymerization reactors and expressed in g / m. The data obtained are given in table.
    Table 22
    Examples 207-211, The inner walls and the surface of the agitator of an enameled polymerization reactor with a capacity of 100 liters are covered with a protective liquid at the end, 1 weight,% in such an amount that the thickness of the layer corresponds to O, 1 g / m in the dried state, then dried with heating and washed with water (tab. 23).
    20 kg of vinyl chloride monomer, 40 kg of deionized water, 13 g of potassium persulfate and 250 g of sodium lauryl sulfate are loaded into the polymerization reactor thus treated, after which the polymerization is carried out at 50 ° C for 12 hours with stirring. After the polymerization reaction is completed, the amount of polymer film deposited on the walls of the reactor is determined. The results are shown in Table 23.
    Table 23
    Continued tpl. 23
    Examples 212-217. The inner walls and other parts of the polymerization reactor of stainless steel with a capacity of 100 liters, coming into contact with the monomer, are preheated and these heated surfaces are covered with a layer of liquid liquid at the end. 1 wt.% In an amount that corresponds to a layer thickness of 0.1 the dried state, then directly washed with water (Table 24). 1 The polymerization of vinyl chloride is carried out under substantially the same conditions as in Example 20. After the polymerization reaction is completed, the amount of polymer film deposited on the walls of the reactor is determined. The results are shown in Table 24.
    Table 24
    35

    45
    50
    P, p and m ery s 218-225. The inner walls and the agitator surface of a 400 L stainless steel polymerization reactor, which come into contact with the monomer, are coated with a layer of protective liquid at the end. 1 wt.% In an amount corresponding to a layer thickness of 0.1 g / m in the dried state, then dried by heating and washed with water (Table 25).
    200 kg of deionized fluids, 100 kg are loaded into the polymerization reactor thus worked.
    styrene monomer, 1 kg of calcium phosphate, 10 g of sodium dodecylbenelesulfonate and 100 g of benzoyl peroxide, after which the polymer is reacted: ation at 90 ° C for 11 hours with stirring. Upon completion. polymerization reactions determine the amount of polymer film deposited on the walls of the reactor. The results are shown in Table. 25
    Table 25. Examples 226-230. The inner walls of the same polymerized reactor as used in Examples 218-225 and the surface of the agitator coming in contact with the monomer are coated with a protective liquid at the end. 1 wt.% In an amount such that it corresponds to the thickness of the O layer, 1 g / m in the dried state, and then dried with heating and washed with water (Table 26). The polymerization reaction is carried out in almost the same way. the same conditions as in example 25. After completion of the polymerization reaction, the polymerization mixture is removed from the reactor, which is then washed with water and again the polymerization cycle is carried out, then the number of polymerization cycles is recorded. , by and the thickness of the polymer on the surface ylenki otklonivsheys not .dostigaet 1 g / m. The results are shown in Table. 26
    Table 26 Examples 231-235. The inner walls of a 400 L stainless steel polymerization reactor and the surface of the agitator coming in contact with the monomer are coated with a layer of protective liquid at the end. 1 vs.% In an amount corresponding to a layer thickness of 0.1 dried state, then dried with heating and thoroughly washed with water (Table 27). 180 kg of deionized water, 75 kg of 1,3-butadiene monomer, 25 kg of styrene monomer, 4.5 kg of sodium lauryl sulphate, 280 g of tert-dodecyl mercaptan and 300 g of potassium persulphate are loaded into the polymerization reactor thus treated, followed by polymerization at 50 ° C for 12 hours with stirring. After verifying the polymerization reaction, the amount of polymer film deposited on the walls of the reactor is determined. The results are shown in Table. 27. Table 27 Examples 236-239. The inner walls and the surface of a 400 L stainless steel polymerization reactor are coated with a layer of protective liquid at the end. 1 wt.% In an amount corresponding to a layer of 0.1 dried state, then dried with heating and washed with water (Table 28). 180 kg of deionized water, 74 kg of sodium oleate, 1 kg of oleic acid, 500 g of tert-dodecyl mercaptan, 100 g of sodium pyrophosphate and 300 g of potassium persulfate are loaded into the polymerization reactor thus treated, followed by a polymerization reaction for 12 hours at stirring. After completion of the polymerization reaction, the amount of polymer film deposited on the walls of the reactor is determined. The results are shown in Table 28. Table 2 Forms 240-243. The inner walls and surface of the polymerization reactor mixer made of 400 l steel with a capacity of 400 liters are covered with a layer of protective liquid at the end of 1 wt.% In an amount corresponding to the 0.1 layer of the dried state, then dried by heating and washed with water. 180 kg of deionized water, 40 kg of 1,3-butadiene monomer, 54 kg of methyl methacrylate monomer, 4 kg of styrene monomer 4.3 kg of laurylbenzenesulfonate sodium 280 g of tert-dodecyl mercaptan and 300 g of potassium persulfate are loaded into the polymerization reactor thus treated; the polymerization reaction is carried out for 10 hours during the transfer. At the end of the polymerization reaction, the polymerization mixture is discharged and the reactor, which is then washed with water, and the amount of polymer film deposited on the surface is determined nkah reactor and express it as g / m-. The results are shown in table 29. . Table 29 Examples 244-248. The inner walls and the surface of the stirrer of a 200 L polymerization reactor of stainless steel are coated with a layer of protective liquid at the end. 1% by weight in an amount corresponding to the 0.1 dried state, then dried with heating and washed with water. 30 kg of polybutadiene latex with a solids content of 50%, 50 kg of styrene monomer, 20 kg of acrylonitrile monomer, 100 g of tert-dodecyl mercaptan, 500 g of potassium oleate and 500 g of potassium persulfate are loaded into the polymerization reactor thus treated, then polymerization is carried out at 50 ° C for 15 hours with stirring, resulting in a polymer resin emulsion of ABS. After completing the polymerization reaction, the amount of polymer film deposited on the walls of the reactor is determined. The results are shown in Table 30. IT-b l and c a 30 Examples 249-261. Aqueous solutions of the protective liquid are prepared, a solution of each of the anionic dyes (compound a according to pointer 0-1) and a metal salt (compound c)
    With subsequent adjustment of the pH with hydrochloric acid, monohydric alcohol is added in an amount of 10 parts by weight. per 100 weight.h. aqueous solution dye, and. metal salts.
    The inner surfaces of a 100 liter polymerization reactor made of stainless steel and the surface of the agitator coming in contact with the load cell are coated with a protective layer of liquid prepared by the previously described method in an amount corresponding to a layer of 0.1 dried state. 251 The same Silicate nat 100/100 ri
    Note: Alcohol added in the column, A - isobutyl alcohol; Hell -btor -butyl alcohol; AJ-tetor-amyl alcohol; A-TET-amyl SPIET.
    .Example 262-267. Internal mixers that come into contact with the grounds of the polymerization reactor with the monomer are coated with stainless steel and a surface 45 of shield fluid at the end. 1 wt.% In
    then dried with heat and washed with water.
    26 kg of vinyl chloride monomer, 52 kg of deionized water, 26 kg of partially saturated polyvinyl alcohol and 8 g of ai, eC-azo) Is-2,4-dimethylvaleronitrile are loaded into the polymerization reactor thus treated and then polymerization is carried out at 8 h when moving. After the completion of the polymerization reaction, the amount of the polymer film deposited on the walls of the reactor is determined. The results are shown in Table. 31.
    权利要求:
    Claims (4)
    [1]
    T a b i c a 31 3.0 A, an amount corresponding to 0.1 g / m in the dried state, is then dried with heating and curled in water (Table 32) .- The polymerization reactor thus treated is loaded 20 kg of deionized water, 10 kg of styrene monomer, 100 calcium phosphate, 10 g of sodium dodecylbenzene sulfonate and 10 g of benzoyl peroxide, followed by a polymerization reaction at 90 ° C for 11 hours. After completion of the polymerization reaction, the polymerization mixture is extracted from the solution, which is sequentially washed with water, and repeat The polymerisation cycle under the same conditions as before was determined by the number of polymerization cycles that were carried out until the thickness of the polymer film on the surface of the reactor was 1 g / m. The results are shown in table 32. . Table 32 As follows from the above examples, the proposed method allows to significantly reduce the degree of deposited polymer film on the inner surfaces and parts of the reactor. Claim 1. The method of obtaining chain-chain polymers by radical polymerization or copolymerization of ethylenically unsaturated monomers in bulk, solution, aqueous emulsion or suspension, about t-. characterized in that, in order to reduce the degree of deposition of the polymer film on the inner surfaces and parts of the reactor, the latter, before starting the polymerization, are treated with a 0.01–5 weight.% aqueous solution of alkali metal or ammonium salts of water-soluble anionic dyes in sulfoxide or carboxyl form at pH 1-7, followed by drying surfaces at 40-100 0.
    [2]
    2. The method according to claim 1, characterized with TgM, that the treatment aqueous solution additionally contains water-soluble cationic dyes containing at least one pair of conjugated double bonds and at least one nitrogen atom in the molecule with their weight ratio Compounds according to claim 1, ranging from 100: 1 to 100: 0.1.
    [3]
    3. The method according to claim 1, characterized in that the treatment aqueous solution further comprises silicic acids, silicates or water-soluble non-alkaline metal salts, when their weight ratio to the compounds according to claim 1 is from 100: 1 to 100: 0 ,one. 4. The method according to claims 1 to 3, about which the processing aqueous solution additionally contains 1-20% by weight of a C-C-alkanol. The priority of paragraphs 25.01.77 p® PP. 1.3; 11.11.77 according to claim 2; 11.11.77 on para.
    [4]
    4. Sources of information taken into account during the examination 1. Nikolaev.A.F. Synthetic polymers and plastics based on them. ML, Himi, 1964, p. 212-220,273.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU791249A3|1980-12-23|Method of preparing carbochain polymers
    EP0091965B1|1987-03-18|Process for preventing deposition of polymer scale during polymerization of vinyl monomer
    US5292834A|1994-03-08|Method of preventing polymer scale deposition
    JP3091355B2|2000-09-25|Polymer scale adhesion inhibitor and method for producing polymer using the same
    JP3110601B2|2000-11-20|Polymer scale adhesion inhibitor and method for producing polymer using the same
    JP3260962B2|2002-02-25|Polymer scale adhesion inhibitor and method for producing polymer using the same
    US5244986A|1993-09-14|Method of preventing polymer scale deposition
    JP2764654B2|1998-06-11|Polymer scale adhesion inhibitor and method for preventing adhesion of polymer scale
    EP0327202A2|1989-08-09|Use of manganese compound to inhibit polymer build-up on reactor parts
    BE863075A|1978-05-16|VINYL MONOMERES POLYMERIZATION PROCESS
    JPH0617372B2|1994-03-09|Polymer scale adhesion prevention method
    EP0458267B1|1994-10-26|Method of preventing polymer scale deposition
    KR810001533B1|1981-10-27|Method for the polymerization of vinyl monomers
    JP2005082641A|2005-03-31|Polymer scale adhesion inhibitor
    JP3272907B2|2002-04-08|Polymer scale adhesion inhibitor and method for producing polymer using the same
    JPH0615565B2|1994-03-02|Polymer scale adhesion prevention method
    JPH0617371B2|1994-03-09|Polymer scale adhesion prevention method
    JP3276498B2|2002-04-22|Polymer scale adhesion inhibitor and method for producing polymer using the same
    JP2764653B2|1998-06-11|Polymer scale adhesion inhibitor and method for preventing adhesion of polymer scale
    JP3260954B2|2002-02-25|Polymer scale adhesion inhibitor and method for producing polymer using the same
    JPH0617370B2|1994-03-09|Polymer scale adhesion prevention method
    JPH0617410B2|1994-03-09|Polymer scale adhesion prevention method
    JPH0617411B2|1994-03-09|Polymer scale adhesion prevention method
    JPH07116245B2|1995-12-13|Polymer scale adhesion prevention method
    JPH07286001A|1995-10-31|Polymer scale deposition inhibitor and production of polymer with aid thereof
    同族专利:
    公开号 | 公开日
    FR2378045A1|1978-08-18|
    FI64379C|1983-11-10|
    YU9278A|1983-01-21|
    SE439314B|1985-06-10|
    SE7800769L|1978-07-26|
    IE46146B1|1983-03-09|
    GR64894B|1980-06-07|
    PT67571B|1979-06-20|
    DE2801219A1|1978-08-03|
    ES466003A1|1978-10-01|
    DK152656C|1988-08-15|
    IN147427B|1980-02-23|
    NZ186234A|1980-03-05|
    TR20093A|1980-07-08|
    PL118847B1|1981-10-31|
    IE780172L|1978-07-25|
    DK28578A|1978-07-26|
    NO155886B|1987-03-09|
    MX148096A|1983-03-14|
    PL204213A1|1978-09-25|
    DD135285A5|1979-04-25|
    NL178693B|1985-12-02|
    FI64379B|1983-07-29|
    RO76719A|1981-05-30|
    DE2801219C2|1988-12-22|
    NL7800661A|1978-07-27|
    NO780208L|1978-07-26|
    NL178693C|1986-05-01|
    US4173696A|1979-11-06|
    IL53844D0|1978-04-30|
    GB1595566A|1981-08-12|
    CA1102489A|1981-06-02|
    PT67571A|1978-02-01|
    DK152656B|1988-04-05|
    IT1093267B|1985-07-19|
    IT7819557D0|1978-01-24|
    HU178739B|1982-06-28|
    CH638228A5|1983-09-15|
    BR7800427A|1978-08-22|
    CU34859A|1981-04-20|
    FI780218A|1978-07-26|
    AR217275A1|1980-03-14|
    PH14814A|1981-12-14|
    NO155886C|1987-06-17|
    YU39135B|1984-06-30|
    FR2378045B1|1980-09-12|
    ATA51178A|1981-02-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    ES355836A1|1967-08-02|1970-04-01|Dow Chemical Co|A procedure to reduce the accumulation of polymer on the interior surfaces of a reaction vessel. |
    DE94210C|1970-05-07|
    DE2044259C2|1970-09-07|1985-08-22|Shinetsu Chemical Co., Tokio/Tokyo|Process for the suspension polymerization of vinyl chloride|
    JPS5224953B2|1974-12-27|1977-07-05|Shinetsu Chemical Co|
    US4068059A|1977-02-17|1978-01-10|The B. F. Goodrich Company|Internally coated reaction vessel for use in olefinic polymerization|US4272622A|1979-05-22|1981-06-09|Shin-Etsu Chemical Co., Ltd.|Method for preventing polymer scale deposition in the polymerization of an ethylenically unsaturated monomer in an aqueous medium|
    DE2946461A1|1979-11-17|1981-05-27|Hoechst Ag, 6000 Frankfurt|METHOD FOR PRODUCING VINYL CHLORIDE POLYMERISATS|
    JPH0138121B2|1981-10-20|1989-08-11|Shinetsu Chem Ind Co|
    US4451625A|1982-08-05|1984-05-29|Air Products And Chemicals, Inc.|Reduction of wall fouling in the suspension polymerization of vinyl chloride homopolymer|
    FR2535325B1|1982-10-27|1987-10-30|Toyo Soda Mfg Co Ltd|NON-AQUEOUS POLYMERIZATION PROCESS OF VINYL CHLORIDE|
    JPS6356882B2|1983-04-28|1988-11-09|Shinetsu Chem Ind Co|
    IN165525B|1984-07-23|1989-11-04|Shinetsu Chemical Co|
    IT1190641B|1986-05-16|1988-02-16|Enichem Polimeri|PROCESS FOR WATER SUSPENSION POLYMERIZATION OF VINYL MONOMERS CONTAINING HALOGEN|
    IL91230A|1988-08-10|1994-01-25|Shinetsu Chemical Co|Method of preventing polymer scale formation|
    JP3317803B2|1994-11-15|2002-08-26|信越化学工業株式会社|Polymer scale adhesion inhibitor and method for producing polymer using the same|
    US5654198A|1995-06-05|1997-08-05|National Starch And Chemical Investment Holding Corporation|Detectable water-treatment polymers and methods for monitoring the concentration thereof|
    IT1281413B1|1995-08-29|1998-02-18|Cirs Spa|ECOLOGICAL ANTICROST TO COAT THE POLYMERIZATION REACTORS|
    JP3665502B2|1999-04-08|2005-06-29|信越化学工業株式会社|Method for producing polymer of ethylenic double bond-containing monomer|
    JP2001011102A|1999-06-25|2001-01-16|Shin Etsu Chem Co Ltd|Production method of polymer from monomer having ethylenic double bond|
    CN106986957A|2017-05-04|2017-07-28|宜宾天原集团股份有限公司|The anti-sticking kettle production method of bulk polymerizod polyvinyl chloride|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP710077A|JPS565442B2|1977-01-25|1977-01-25|
    JP13535677A|JPS565443B2|1977-11-11|1977-11-11|
    JP14098977A|JPS565444B2|1977-11-24|1977-11-24|
    [返回顶部]