前苏联专利SU1003759A3 Process for producing polymers of ethylene-saturated monomers

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专利摘要:
In the polymerization of at least one ethylenically unsaturated monomer other than vinyl chloride, deposition of polymer scale on the inner walls of a polymerization reactor and other surfaces coming into contact with the monomer is effectively prevented (regardless of the type of polymerization used, so long as it takes place in a heterogeneous phase) by coating the surfaces of the reactor with at least one compound selected from organic electron donor compounds and organic electron-acceptor compounds prior to polymerization; the compound or compounds having been or being brought into contact with an oxidizing agent, a reducing agent, an acid or a base, or having been or being irradiated with ultraviolet light.
公开号:SU1003759A3
申请号:SU762387317
申请日:1976-08-13
公开日:1983-03-07
发明作者:Коянаги Сунити；Китамура Хадзиме；Симизу Тосихиде；Фусими Кендзи
申请人:Син-Эцу Кемикал Ко.Лтд (Фирма)；
IPC主号:

专利说明:

(54) METHOD FOR OBTAINING POLYMERS OF ETHYLENE OTHER
one
This invention relates to the chemistry of high molecular weight compounds, in particular to the polymerization of ethylenically unsaturated monomers in a heterogeneous range.
It is known that polymerization in a heterogeneous medium in an aqueous suspension or emulsion of such monomers as styrene, acrylonitrile, mixtures of acrylonitrile with butadiene and styrene, etc., almost always forms polymer deposits on the walls of the reactor. The inner walls of the polymerization reactor, the surfaces of the agitator and other j equipment installed inside the polymerization reactor that come into contact with the monomer or monomers become coated with polymer deposits forming the process during the polymerization process. This leads to a decrease in the yield of the target polymers, as well as to a decrease in the productivity of the reactor due to the deterioration of the possibility of cooling the reactor. In addition, polymer deposits can get into the target polymers, which leads to a deterioration in their quality. It should be borne in mind that the cleaning work required for
MONOMERS
Moldings of polymer deposits are not only time consuming and working for CJ5J, but also dangerous for workers because of the toxicity of unreacted monomers absorbed by the polymer, and this is one of the most serious problems.
A known method of preventing polymer deposits during the polymerization of vinyl chloride or mixtures of monomers containing mainly vinyl chloride by coating the inner walls of the reactor with a coating composition FROM organic electron donor compound A and from organic electron acceptor compound B which contacts one compound C , selected from the group consisting of oxidative agents, reducing agents, acids and bases, with OO-UOC for 10-30 min. 1J.
The known method is applicable to the polymerization and copolymerization of vinyl chloride, but the addition of an alkali or inorganic oxidant is not applicable to the polymerization of ethylenically unsaturated monomers such as vinyl esters, acrylic and methacrylic acid esters, diene compounds, these substances can be decomposed or oxidized by means of the dyne compounds that can be decomposed or oxidized by means of the diene compounds, they can be decomposed or oxidized by means of the substance can be dispersed or oxidized by means of the dyne compounds, it is possible that these monomers can decompose or be oxidized by means of the diene compounds can be decomposed or oxidized by means of the dyne compounds that can be decomposed or oxidized by means of the diene compounds can be decomposed or oxidized by means of the dyne compounds that cause these monomers to decompose or oxidize. . On the other hand, when emulsion polymerization is carried out in the presence of an emulsifier added to an aqueous polymerization medium, during copolymerization of conjugated dienes with vinyl monomer or during polymerization in the presence of acyl peroxides, such as benzoyl peroxide, lauryl peroxide, etc. .. or molecular weight regulators such as mercaptans, the method of coating the surface with a polar organic compound or dye is not only less effective, but also prevents the formation of deposits of polymeric and for a short time. Thus, the known method is effective only in suspension polymerization of vinyl chloride in an aqueous medium with a simplified formulation, with a non-ionic or non-unsaturated group-containing polymer dispersant, such as partially saponified polyvinyl alcohol or methylcellulose. The aim of the invention is to prevent polymer deposits on the reactor walls during the emulsion or suspension polymerization of ethylenically saturated monomers. This goal is achieved by the fact that according to the method of obtaining polymers of ethylenically unsaturated monomers of free radical emulsion or suspension polymerization of these monomers, before introducing the polymerization mixture into the reactor in contact with the monomer, a composition consisting of Sudan black A and a flame is drawn on a monomer in contact with the monomer, and an anesthetical mixture is applied. taken in a ratio of from 1; 5 to 5: 1 by weight, which is then treated with compound C selected from the group consisting of ethylenediamine, ethanolamine, sodium silicate, rongalite, nit ammonium and phenol in an amount of 0.1-10-fold by weight based on the total number of compounds A and / or B at 60-100 0 for 10-30 minutes, and the total number of applied properties is 0.001-0 , 1 g / m of the surface, after which the monomer is polymerized. The method is carried out as follows. First, the inner walls of the reactor in which polymerization is carried out and other surfaces coming in contact with the monomer or monomers are coated with a solution or dispersion of Sudan's black And nigrozine, after which the vessel is made and treated with a solution of a compound selected from the group consisting of ethylenediamine, ethanolamine, phenol, sodium silicate, ammonium nitrate, at BO-CQ for 1030 minutes. The solution is then removed from the reactor, which is then prepared for the polymerization process in the usual manner. It is possible, but not necessary, in the case of polymerization in an aqueous medium, for example, as is the case during slurry or emulsion polymerization, to use an aqueous solution of compound C as the dispersing medium of the polymerization mixture, and monomer and other additives are introduced into this solution commonly used in polymerization, such as initiators and dispersant. It is also effective to add compound C to the polymerization mixture contained in the reactor for carrying out the polymerization, the inner surface of which is already available with Sudan black B and nigrosin, if the polymerization process is carried out in an aqueous medium. The ratio of Sudan Black B and Nigrosine is between 1: 5 and 5: 1 by weight. The amount of Compound C varies depending on the processing method. In the event that treatment with Compound C P1 is carried out by heating the solution co; Unity C, located in the regactector; for carrying out polymerization, the inner walls of which are already covered with Sudan black B and nigrosin, the total amount of compound C found in the polymerization rector should be quite large and exceed the total amount of Sudan black B and nigrosin 5-10 times, since the effective concentration of the compound C, which is in contact with the inner walls, is relatively low. However, in the case that treatment with Compound C is carried out by adding it to a coating liquid from a sudanic black B and nigrosin in a dissolved or dispersed state, the amount of Compound C may be O, 1-10-Fold by weight of calculating the total number of Sudan black B and nigrosin. The amount of coating material in accordance with the proposed method is more than 0.001 g of the total amount of Sudan black B and nigrosin per 1 m of covered matter to obtain an effect that prevents the deposition of polymer on these walls. You can enhance the effect achievable: in the invention, by adding some alkaline substances to the polymerization mixture, especially when the polymerization is carried out in the aqueous phase at a pH above 8.0. Such substances are selected from the group consisting of oxides, hydroxides, carbonates, phosphates, acidic carbonates and silicates of ammonium, alkali and alkali-earth metals. The amount of alkaline substance added to the polymerization mixture is less than 1% by weight and by weight. by weight of monomer or monomers, so as not to cause adverse effects on the quality of the target polymers. The proposed method is effective in all types of polymerization processes of ethylenically unsaturated monomers, including suspension, emulsion, dissolving and block polymerization, and this method is not affected by additives usually introduced into the polymerization mixture, such as suspension agnets, for example, partially omnified polyvinyl alcohol and methylcellulose, anionic surfactants, for example sodium lauryl sulfate, sodium dodecyl beisol sulfonate, sodium dioctyl sulfosuccinate, non-ionic surfactants substances, for example, monobarinate sorbitan, simple alkyl. polyalkylene oxides, fillers, such as calcium carbonate and titanium dioxide, heat stabilizers, such as tribasic lead sulfate dilaurinate dibutyl tin, and various types of metal soaps, lubricants, such as rice wax, and. stearic acid, plasticizers, such as dioctyl phthalate, dibutyl phthalate, and de-intercalation, a type, a dyutyl phthalate, a dyutyl phthalate, a dibutyl phthalate, and a dearl acid; for example, trichlorethylene and mercaptans, pH regulators and polymerization initiators, for example diisopropyl peroxydicarbonate, lauryl peroxide and dimethylvaleronitrile. The ethylenically unsaturated monomers that can be polymerized by the proposed method include vinyl esters such as vinyl acetate and vinyl propionate, acrylic and methacrylic acids and their esters, papernova and fumaric acids, and their esters, maleic anhydride, diene compounds monomers such as butadiene, chloroprene and isoprene, unsaturated nitriles such as acrylonitrile, aromatic vinyl monomers such as styrene, vinylidene halides, simple vinyl effects and mixtures of monomers. The proposed method is especially effective in free-radical polymerization in a heterogeneous medium, for example, in suspension, emulsion, and some types of block polymerization, in which the polymer precipitates from the reaction mixture. Example 1. Preparing solutions of Sudan black B and nigrosine in methanol or by ethanol-concentration 1% by weight based on the total amount of both compounds taken in the ratios given in the table. Each of the solutions is treated by adding compound C based on that amount, which is also given in this table, by heating to form a coating liquid. This liquid covers the inner walls of the reactor with a volume of 1000 liters of stainless steel and the surface of the agitator type installed in the reactor. The amount of the applied substance is 0.10 g / m of solid; after the application, drying is carried out at 50 ° C to remove the solvent and washing with water. 0.45 kg of tert-dodecyl mercaptan, 11.3 kg of rosin soap, 1.5 kg of sodium phosphate decahydrate, 0.075 kg of tetrasodium salt, ethylenediamine tetraacetic acid, 0.20 kg are introduced into the polymerization reactor coated on its inner walls. sodium formaldehyde sulfoxylate and 500 kg of deionized water, after which the air inside the reactor is replaced with nitrogen and after that 0.23 kg of diisopropylbenzene monohydroperoxide, 73 kg of styrene and 177 kg of butadiene are charged. The polymerization is carried out for 9 hours. Butadiene styrene latex is obtained with a yield of 60%. The amount of polymer deposits deposited on the walls of the reactor is determined for each experiment, the results are shown in the table in which experiments 1-4 and 7 are the control experiments. Example 2. The inner walls of a polymerization reactor with a capacity of 2 liters of stainless steel are coated with a methanol solution of Sudan Black B and Nigrosin in a ratio of 100: 50 by weight based on the relative amounts of the components with a concentration of 1 based on the total content of both substances. Then heat treatment is carried out at 90 ° C for 30 minutes with the addition of ethylenediamine C in a relative amount of 100. 900 g of a 2% aqueous solution of polyvinyl alcohol and 0.2 g of potassium persulfate are introduced into the reactor prepared in this way. Polymerization of 600 g of vinyl acetate is carried out, which is introduced dropwise over 3 hours at 65 ° C, heated for another 2 hours at this temperature. The polymer deposits on the walls of the reactor are generally 2 grams.
In a comparative experiment under the same conditions, when there is no coating on the walls of the reactor, polymer deposits on the walls of the reactor amount to a total of 25 g.
Example 3. The inner walls of a 200 l stainless steel reactor are coated with a methanol solution of Sudan Black B and Nig Rosin, taken in a ratio of 100: 40 by weight based on relative amounts at a concentration of 1% by weight. Based on the total content of both components . Then heat treatment is carried out for 30 minutes by adding ethylene di. Amine in a relative amount of 100.
A reactor prepared in this way is loaded with 20 kg of styrene-butadiene latex containing 23.5% styrene, 76.5% butadiene, 0.5% gel fraction, and 23.5% solid substances (wt.% L The specified latex contains 2.51 g sodium formaldehyde sulfoxylate per 560 g of latex. Latex is heated to a temperature. Then, 70 kg of methyl methacrylate, containing 1% of cumyl hydroperoxide dissolved in monomer, are added dropwise within 2 hours. Polymerization is completed after holding the reaction mixture at this temperature for about 1 h. The amount of sediment poly EPA on the walls of the reactor I is 30 g / m.
For comparison, the experiment is repeated, not in a reactor without coating on the inner walls. The amount of sediment in this case is.
about
100 o
100 100
100 100 100
100
100
100
100 100 100
100
100 100 100
100
100
Without processing 2500
ethanol -1000
- -1500
- -800
Ethylene-O diamine (100) is added. Heating at 90 ° C for 30 minutes
ethanol Ethylene-10 diamine (100) is added. Heating at 30 min
Heating at 90s 500 30 min
Tanol. Sodium silicate (100) is added. Heating at 90 ° C for 30 minutes.
Phenol O (100) is added. Heating at, 30 min
Ammonium nitrate (100) is added. O Heating at 90 ° C, 30 min
Ethanol-O amine (100) is added. Heating at 90 ° C, 30 min
100
100
12
20
100 100
50
100
20
15
100
50
sixteen
100
100
17
100
100
18

权利要求:
Claims (1)
[1]
1. Patent of the USSR No. 359831,
cl. C 08 F 14/06, 1972 (prototype).

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法律状态:

优先权:

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