• 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:
    The formation of a polymer crust on the surfaces of a polymerisation reactor in which vinyl chloride is polymerised alone or together with other ethylenically unsaturated monomers is avoided completely or virtually completely by adding a crust preventer to the polymerisation mixture. This additive comprises one or more substances from the following list: iodine, iodine compounds, bromine, bromine compounds, thiocyanates, isothiocyanates, phytic acid and derivatives thereof, and reducing organic compounds. In addition, the reactor surfaces can be treated with polar organic compounds or an organic dye.
    公开号:SU753364A3
    申请号:SU762381452
    申请日:1976-07-16
    公开日:1980-07-30
    发明作者:Коянаги Сунити；Симизу Тосихиде；Фусими Кендзи
    申请人:Син-Эцу Кемикал Ко Лтд (Фирма)；
    IPC主号:
    专利说明:

    one . The invention relates to the technology of producing polymers or copolymers of vinyl chloride and can be used in the chemical industry. A method is known for producing polymers or copolymers of vinyl chloro radical by radical polymerizing it or copolymerising with vinyl monomers in bulk, solution, aqueous emulsion or dispersion 1. However, according to this surface method, The contact is in contact with the monomer, including the inner walls of the reactor and the surfaces of the stirrer, as usual. however, polymer precipitate is precipitated during polymerization, which reduces polymer yield and reactor cooling capacity. In addition, pieces of polymer precipitate are torn off from the surfaces and enter the polymer product, impairing its quality. Cleaning a polymerization reactor for REMOVING a polymer sludge after each polymerization requires a lot of labor and time, and also affects the health of workers due to the toxicity of unreacted monomer sorbed on the polymer sludge. The aim of the invention is to reduce cortex formation on the inner surfaces and parts of the reactor. This goal is achieved by the fact that in a known method of producing polymers or copolymers of vinyl chloride by radical polymerization of it or of copolymerisation with vinic monomers in mass, solution, aqueous emulsion or dispersion, the process is carried out in the presence of 3-5000 parts by weight in the reaction mass. on 10OOOOO weight.h. monomers of at least one of the compounds of the group selected from the group containing iodine, bromine, iodine compounds of Kli bromine, thiocyanates, isothiocyanates Shchitovaya acid, its salts, rongalite and reducing carbohydrates. At the same time, the process can be carried out in a reactor, the internal surfaces and parts of which are coated with IO by at least one polar organic compound of the wedge. Subjects to be added to the polymer mixture of the additive according to the invention, I choose 3 groups consisting of iodine, inorganic 4 iodine salts, such as sodium iodide, potassium iodide, ammonium iodide, calcium iodide, zinc iodide, iron iodide, zinc iodide, iron iodide; hydrogen iodide; opj-anic iodine compounds, such as ethyl iodide and butyl iodide; iodine compounds with a positive valency, for example iodine thiocyanate J (SCN), iodine perchlorate J (ClOi), iodine cyanide J (CN), iodine acetate LSSN.SOO), iodine nitrate JCNOg) and iodine sulfate Jj (SO) g or J ( SO /,); bromine; inorganic salts of bromine, for example potassium bromide, ammonium bromide, calcium bromide, magnesium bromide, zinc bromide, iron bromide and nickel bromide; apt.of.Osh, bhp, for example, ethyl bromide and butyl bromide, thiocyanates, for example, sodium thiocyanate, thiocyanate, ammonium thiocyanate, calcium thiocyanate, iron thiocyanate; chromium isothiocyanate and nickel isothiocyanate; phytic acid; sodium, potassium and ammonium salts of phytic acid; reducing organic compounds, such as rongalite, glycerol aldehyde, ascorbic acid and reducing carbohydrates (for example, glucose, fructose, mannose, maltose and lactose), Carbohydrates, such as sucrose, which do not have reducing properties as such, but are able to impart the reducing properties of their hydrolysis products formed during the polymerization act as reducing carbohydrates. The polar organic compounds used to coat various surfaces in contact with the monomer or monomers in the polymerization reactor, combined with the addition of additives to the polymerization mixture, are organic compounds with one or more atoms or groups with unpaired electrons, for example oxygen atoms. , nitrogen and sulfur and their molecules. Examples of polar organic compounds are nitrogen-containing organic compounds selected from azo compounds, nitro, nitroso or azometinozy E groups or azine ring and an amino compound such as azomethane, azobenzene, nitrobenzene, monoamine, mononitroazobenzol, pyrazine, pyridine, thiazines, oxazines (e.g. , morpholine), aniline, benzaniline, ethylene diamine tetraacetic acid, d-naphthylamine, ethanolamine, diethanolamine, triethanolamine, vitamin B (t. nicotinic acid amide) and chloroform-containing compounds selected from Thiocarbonyl or mercapto groups or thioester bonds, for example thioglycolic acid, thiourea, thiocarbonic acid, thiocarbamic acid, thiobenzoic acid, thioethers and mercaptans; kidlorodsoderzhaschie op ganic compound selected from quinones, e.g., p-benzoquinone, ketones, e.g., acetophenone and benzophenone, aldehydes, e.g., acetaldehyde and benzaldehyde, alcohols with more than 5 carbon atoms such as cetyl alcohol, octyl alcohol and benzilrvy alcohol and carboxylic acids with more than 5 carbon atoms, such as stearic acid and naphthoic acid; and aliphatic or alicyclic polyene compounds with conjugated double bonds, for example vitamin A, vitamin A and U. -, B - and-ji - ka-. ROTINA .; Organic dyes, also used for surface coating, can be represented by methylene blue, black nigrosin, basic nizrosin, oil black, black spirit, black aniline, fluorescein, monoazo and polyazo dyes, for example amaranth; metal containing azo dyes, naphthol dyes, referred to as az or inactive azo dyes, dispersed with azo dyes; anthrahs. new dyes; for example, anthraquinonic acid dyes, anthraquinone cubic dyes, anthrone cubic dyes, alizarin dyes such as alizarin and dispersed anthraquinone dyes; indigo dye, such as indigo diamond b, tren red violet PH and tren black V.pechAtne; sulphide dyes, for example, sulphurous blue GPE and sulphurous black B; phthalocyanine dyes, for example, copper phthalocyanine and metal-free phthalocyanine. compounds; diphenyl-immersed and triphenylmethane dyes, nitro dyes; nitroscale dye; thiazole dyes; xanthene dyes; acridine dyes; azine dyes; oxazine dyes; thiazine dyes; benzoquinone and naphthoquinone dyes, cyanine dyes; and organic dyes related to compounds, for example, complexes or mixtures of resins and tar, as well as some water-soluble organic dyes. Water-soluble organic dyes include: 1) alkali metal salts of sulfonic acids, for example, the first diamond is yellow G (direct dye), light-yellow acidic 2G (acidic dye), yellow-4 yellow levafix (reactive dye), diamond orange C (reactive dye), Direct my fast red GS (right my dye), right my Bordeaux NS (right my dye), brilliant red ER. (sour dye), sour alizarin red B (sour pickle dye), cybron blue 3G (reactive dye), blendofor B (sour dye), nig ozin (acid dye) and Sirius Gray G (direct dye); 2) alkali metal salts of carboxylic acids, for example, chryzamin G (direct dye), direct fast yellow GG (direct dye), chromium yellow G (acid mordant dye), chrome yellow HE (acid mordant dye) and eosin G (acidic dye); 3) Quaternary ammonium salts, for example, the main flavin 8G (main dye), Astrazon yellow 3G (main dye), rhodamine GCCP (main dye), safranin T (main dye), rhodamine B (main dye). And daytofor. AN (main dye); 4) chlorohydrates, such as auramine conc. (main dye), chrysoidin (main dye) and Bismarck brown BG (main dye).
    Of the organic dyes and related compounds, nigrosin black, nigrosin basic, black spirit, and soot oil are most preferred.
    Practically according to the proposed method, the additives are added as such to the polymerization mixture or, if necessary, as a solution or dispersion in a solvent or mixture of solvents. Suitable solvents for this purpose are not limited. but it may be water, alcohols, effects, ketones, hydrocarbons, or chlorinated hydrocarbons. The amount of additives to the polymerization mixture should be at least 3 ppm, mono- by weight. ra or monomers. Any amount in excess of 5000 parts / g-shn. weight leads to various undesirable results of the polymerization process, as well as to the deterioration of the quality of the polymer product. Therefore, it is preferred that the amount of additives is from 3 to 5,000 ppm, preferably from 10 to 2,000 ppm. by weight of monomers. Additives need to be added to the polymerization mixture, preferably before starting the polymerization. However, this is not necessary, they can be introduced during the polymerization process. When using polar organic compounds or organic: their edges. Covers for walls and other surfaces that come into contact with the monomer or mockerers in the polymerization reactor are better to dissolve or disperse the compounds in a solvent or mixture of solvents. Covered surfaces are dried with air or hot air at 60-70 s. If two or more coatings are made with the same or a different coating compound, it is preferable to dry with hot air after each coating. Suitable solvents for dissolving or dispersing organic compounds or dyes when applied to surfaces are ethers, for example tetrahydrofuran and diisopropyl ether; alcohols, for example methanol, ethanol and propanol; esters.
    for example methyl acetate and ethylacetate, ketones, for example acetone and methyl ethyl ketone; hydrocarbons, for example benzene, toluene, xylene and hexane; Chlorinated hydrocarbons, for example, methylene chloride, carbon tetrachloride and trichlorethylene; aprotic solvents, such as dimethylformamide, dimethylacetamide and dimethyl sulfoxide. The amount of opaque binding material applied on the surface is at least 0.0001 g, preferably from 0.004 to 1.0 g per 1 m of surface. In this case, the full effect of preventing the formation of polymer precipitates is achieved. Adding additives to the polymerization mixture without coating the surfaces in most cases rather effectively prevents the precipitation of polymer sludge. This is also advantageous because no contamination occurs, since surface coatings using organic solvents are not excluded, the productivity of the polyvinyl chloride resin is significantly increased, since it does not apply a time-consuming coating. The prevention of precipitation of polymeric precipitates can be enhanced by an additional use of various coatings. In this case, the amount of additives or additives in the polymerization mixture can be significantly reduced, since covering materials are applied to the inner walls and other surfaces of the polymerization reactor, it has surprisingly been found that a large amount of polymerization can be carried out without precipitating polymeric precipitates, this is due to the synergism of additives and coatings The method according to the invention is effective in the polymerization of vinyl chloride regardless of the type of polymerization, i.e. suspension, emulsion polymerization, polymerization in solution or in bulk. The method according to the invention is not limited to auxiliary additives in the polymerization mixture, they can be polymerization initiators, suspending agents, emulsifiers and chain transfer agents. The method according to the invention is also limited by the polymerization temperature and the degree of movement. is he
    gives excellent results in preventing the precipitation of polymer precipitates not only by homopolymerization of vinyl chloride, but also by the copolymerization of vinyl chloride with one or more non-saturated manomers. and their esters, maleic and fumaric acids and their esters, or maleic anhydride, aromatic: vins; monomers, vinyl halides different from vinyl chloride, vinylidene halides and olefins
    The following are examples for the construction of the method of the invention. The heat resistance of the product and the number of eyes (fish eye literally) in the description and in the examples or tables are determined as follows. Heat resistance of the product.
    A mixture of too parts by weight of polyvinyl chloride resin, 1 part by weight of dibutyl tin leach and 1 part by weight of stearic acid was placed on a roller mixer at
    for 10 minutes Received a sheet of tintina 0.7 mm. The sheet was heated in a Gear oven and the time until the beginning of the blackening of the sheet was recorded; it means the thermal stability of the polyvinyl chloride resin. Eye formation. A mixture of 100 parts by weight of polyvinyl chloride resin, 50 parts
    by weight of dioctyl phthalate, 1 part by weight of dilaurate dibutyl tin, I part by weight of cetyl alcohol, 0.25 part by weight of titanium dioxide and 0.05 part by weight of carbon black processed
    on rollers at 150 ° C for 7 minutes and a sheet 0.2 mm thick was obtained. The number of eyes ,. those formed in the sheet were calculated by illuminating 100 cm of the area of the sheet.
    - Example 1. A 1000 l stainless steel polymerization reactor equipped with a partition and an agitator with blades of 600 mm diameter was loaded with 200 kg of vinyl chloride,
    500 kg of deionized water, 200 g of incompletely contained polyvinyl alcohol, 60 g of azobisdimethylvaleronitrile and additives in the amount indicated in the table. one.
    Table
    Not
    Sodium iodide
    Sodium iodide
    Sodium iodide
    Calcium Iodide
    Calcium Iodide
    . .
    Yodi Calcium
    Calcium Iodide
    Yod Yod Yod
    66
    18
    6
    7
    to
    5 8 8 13 3 8
    Note. 1 Passes through a 60 mesh sieve.
    2 Pass through a 100 mesh sieve.
    3 Pass through a 200 mesh sieve.
    753364
    ten
    Continued tabl, 1
    1175
    Then, polymerization was carried out at 57 ° C for 9 hours. The amount deposited on the walls, the distribution of the obtained product according to the particle size and the number of holes formed in the product were determined, all these results are presented in the table. The heat resistance of the obtained resin was 120 min in all experiments from 1 to 34.
    Example 2. In a glass-lined polymerization reactor, 500 l were loaded with 8.5 kg of viyl chloride, 1.5 kg of vinyl acetate, 20 kg of deionized water, 10 kg of incompletely saturated polyvinyl alcohol, 3 g of diisopropyl peroxydicarbonate, 200 g of trichlorethylene. and the additive in the amount indicated in table 2. Then after a preliminary re. stirring for 15 minutes; polymerization was carried out at 58 ° C for 12 hours. 2 gives the amount of polymer precipitate formed in each experiment. Food resins are satisfactory in terms of particle size distribution, heat resistance and eye formation.
    table 2
    1400 О О О
    Not
    Hydrogen iodide300
    Thiocyanate iodine300
    Potassium bromide 300
    Ammonium Thiocyanate - 300
    Oh oh
    Phyto Acid 300
    Sodium isothiocyanate 300
    Butyl iodide 300
    21 6
    Potassium Iodide 100
    Potassium Iodide 100 Phyto Acid 200
    12
    Calcium Iodide 100
    Example 3. In the polymerization reactor of Example 1, the inner walls and surfaces of the stirrer were coated with a solution or dispersion containing 0.1% of the coating compounds and solvents listed in Table. 3, in the amount of 0.05 g / m in the form of a solid, the coated surfaces were dried with hot air at 60 ° C for 70 minutes.
    200 kg of vinyl chloride monomer, 500 kg of deionized water, 200 g of incompletely saponified polyvinyl alcohol, and 60 g of azobons dimethylvadronitrile with or without calcium iodide or glucose, as indicated in Table 2, were loaded into such a coated reactor. 3. The polymerization was conducted for 16 hours with stirring at a speed of too rpm for each batch, then another batch or several batches were polymerized. After the first pargni and each subsequent batch, the internal surface of the reactor walls was visually examined for tarnishing and for the deposition of a polymer precipitate above 1 g. Accordingly, in each experiment, the number of batches that could be processed after the first batch was determined without undesirable precipitation of the polymer sludge. The results of the experiments are given in Table. 3. T and b and-c and 3. Note. 90-IР р and me. 4. Mass polymerization of a polymerization reactor consisting of a first stainless steel reactor for 2 liters of vertical type and a second reactor of stainless steel for 4 liters of horizontal type. 800 g of vinyl chloride monomer and g of azobisdimethylvaleronitrile were loaded into the first reactor with or without calcium iodide iodide, as indicated in Table 4. The preliminary polymerization was carried out at 60 ° C for 2 hours with stirring at a speed of 900 rpm. After the preliminary polymerization in the first reactor, the polymerization mixture was transferred to the second reactor, into which 800 g of vinyl chloride and 0.4 azobisdimethylvaleronitrile were preloaded. The polymerization in the second reactor was carried out at 57 ° C for 10 hours with stirring at a speed of 100 rpm. . In tab. Figure 4 shows the amount of polymer precipitate in the first and second polymerization reactors in the first and second polymerization.
    T a b l and c-a. four
    Example 5: Suspension polymerization of vinyl chloride was carried out in the same manner as in Example 1, but the content of the additive was reduced to 3 or. increased to 5,000 ppm by weight of vinyl chloride monomer. The amount of polymer crust on the reactor walls, the distribution of polymer particles by size and the number of optical defects (fish eye) in the polymer were determined.
    The results are shown in Table. 5. Mixed solvent, by volume 1: 1 Calcium iodide. Glucose. At least 90 mixes. .NOTE .... Passing -, 2. Passing 3. Passing P. Example. 6. Polymerization reactor made of stainless steel with a volume of 30 1.00 liters was loaded with 50 kg of deionized water, 500 g of sodium lauryl sulfate - .. 1 a ps „„ SP - 50 g 2.2- azobis-C2-amndopropane) -hydrochloride, 20 kg of vinylchloride and an additive, the nature and amount of which are indicated in table. 6. Polymerization was carried out with in -. After the completion of each of the polymerization cycles, the polymerization mixture was discharged from the reactor, the walls of the reactor were washed with water, and the amount of polymer crust formed was determined. The results are given in the table. 6. Experience 96, in which soy.45 ..., about "vuiujiuM soy dinene, reducing crusting, dyneni, reducing crust formation, was not added, is given for the right of us and 6 a Number-50 in the crust, g / m2 96 97 additives Acid through 60 mesh sieve. through a 100 mesh sieve. through a 200 mesh sieve. . Continuation of the table 6, 2 3 I (. D§ tyotsyanat. Potassium 99 Glucose too Iodine mt, Iodide alcium Prim R 7. nl;: :;;;;;; -; nil chloride in, the mass was held ° ° Ptmt, Example 4 Registered quantity of polypolycy cycles until the amount of the reactor wall crust reached 10 g / m. As an addition, the calcium carbonate is given in Table 7.
    1975336420
    As can be seen from the above table, dramatically reducing the co-formation on the inside of the inside, the proposed method allows military surfaces and details of the reactor.
    权利要求:
    Claims (2)
    [1]
    1. The method of producing polymers or copolymers of vinyl chloride by radical polymerization of it or by copolymerization with vinyl monomers in bulk, solution, aqueous emulsion or dispersion, characterized in that, in order to reduce crust formation on the internal surfaces and parts of the reactor, the process is carried out in the presence of in the reaction mass of 3-5000 parts by weight per 1,000,000 parts by weight monomers of at least one compound selected from the group consisting of iodine, bromine, iodine or bromine compounds, thiocyanates, isothiocyanates, phytic acid, its salts, rongalite and reducing carbohydrates.
    [2]
    2. The method of pop. 1, they distinguish between them and the fact that the process is carried out in a reactor whose internal surfaces and parts are coated with at least one polar organic compound or organic dye.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU753364A3|1980-07-30|Method of preparing vinyl chloride polymers or copolymers
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    US4105838A|1978-08-08|Method for the polymerization of vinyl chloride
    DE2518260A1|1976-03-04|IMPROVED SUSPENSION POLYMERIZATION OF VINYL CHLORIDE MONOMERS AND MIXED THEREOF WITH OTHER VINYL MONOMERS
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    DE2044259A1|1972-03-09|Suspension polymerisation of vinyl chloride - by method to prevent adherence of the
    GB1559334A|1980-01-16|Polymerisation of vinyl chloride
    EP0019198B1|1983-11-23|Process for preparing polymers of vinyl chloride, composition for coating polymerization vessels and polymerization vessel coated therewith
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    US5432241A|1995-07-11|Process to prevent polymer scale adhesion using an aromatic compound and a salt of polyvinylsulfuric acid
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    KR800000387B1|1980-05-12|Polymerization of vinyl chloride
    EP0029181A1|1981-05-27|Process for preparing polymers of vinyl chloride, composition for coating polymerisation vessels, and derivatives of 1,4-|-benzoxazine useful therefor
    NL8005812A|1981-04-24|PROCESS FOR PREPARING VINYL CHLORIDE RESINS BY SUSPENSION POLYMERIZATION.
    HU211447B|1995-11-28|Polymer scale deposition preventing composition and process for preventing polymer scale deposition with using thereof
    EP0164883A2|1985-12-18|A method for the polymerization of a vinylic monomer
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    同族专利:
    公开号 | 公开日
    DE2631325A1|1977-02-03|
    JPS5321908B2|1978-07-05|
    FR2318177A1|1977-02-11|
    ATA516676A|1979-05-15|
    BE844044A|1976-11-03|
    BR7604676A|1977-08-02|
    AT354086B|1979-12-27|
    GB1543437A|1979-04-04|
    ES449769A1|1977-12-16|
    DK152508C|1988-08-29|
    YU171076A|1982-05-31|
    GB1543438A|1979-04-04|
    SE7608013L|1977-01-19|
    NL7607767A|1977-01-20|
    JPS5212291A|1977-01-29|
    CH624687A5|1981-08-14|
    DK322076A|1977-01-19|
    PL102539B1|1979-04-30|
    YU39216B|1984-08-31|
    HU173654B|1979-07-28|
    FR2318177B1|1978-05-19|
    CU21285A3|1985-12-16|
    PT65375A|1976-08-01|
    DK152508B|1988-03-07|
    CU21285A|1978-09-08|
    PT65375B|1978-01-19|
    NO762472L|1977-01-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2575708C1|2012-01-24|2016-02-20|Аркема Франс|Method of producing halogen-substituted polymers|DE1720481A1|1963-08-01|1971-07-01|Dynamit Nobel Ag|Process for the polymerization and copolymerization of vinyl chloride|
    FR1538572A|1967-07-26|1968-09-06|Pechiney Saint Gobain|Low Temperature Bulk Polymerization Improvement of Monomeric Compositions Containing Vinyl Chloride, and Resulting Products|
    US3631009A|1968-01-15|1971-12-28|Goodyear Tire & Rubber|Polymerization initiator activator salts|
    GB1218155A|1968-05-03|1971-01-06|Gen Tire & Rubber Co|0,2 - dibromo - 1,1,2 - trichloroethane as a molecular weight regulator for vinyl halide polymers|JPS555522B2|1975-08-04|1980-02-07|
    JPS5346236B2|1975-08-28|1978-12-12|
    EP0000430B1|1977-07-15|1981-08-12|Ici Australia Limited|Vinyl halide polymerization process|
    JPS55137108A|1979-04-13|1980-10-25|Nissan Chem Ind Ltd|Production of vinyl chloride resin|
    JPS606361B2|1979-10-22|1985-02-18|Shinetsu Chem Ind Co|
    DE3401158A1|1984-01-14|1985-07-18|Hoechst Ag, 6230 Frankfurt|Process for the polymerisation of vinyl chloride|
    JPH0236602B2|1984-08-17|1990-08-20|Shinetsu Chem Ind Co|
    JPS63127306U|1987-02-13|1988-08-19|
    FR2839724B1|2002-05-17|2005-08-05|Solvay|RADICAL POLYMERIZATION METHODS FOR PREPARING HALOGEN POLYMERS AND HALOGEN POLYMERS|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP8797575A|JPS5321908B2|1975-07-18|1975-07-18|
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