JPS60137905A - Production of polymer - Google Patents

Abstract

PURPOSE:In the polymerization of an ethylenically unsaturated monomer, the polymerizer is coated with an oxidative condensate of an aromatic amine and an organic compound as an electron acceptor, on its inside walls to prevent the polymer from scaling on the inner walls of the polymerizer. CONSTITUTION:(A) An oxidative condensate obtained by oxidizing an aromatic amine such as aniline with an oxidizing agent such as potassium permanganate and (B) an organic compound as an electron acceptor such as benzoquinone are dissolved or dispersed in an appropriate solvent such as water, preferably at a weight ratio of 1/5-5/1 and the solution of dispersion is coated on the inside walls of the polymerizer. When needed, the coated film is treated with an aqueous solution of a metal salt such as sodium hydroxide, then the polymerization of an ethylencially unsaturated monomer is carried out. EFFECT:The effect is obtained regardless of polymerization process, kinds of monomers and compositions of polymerization systems.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to an improved method for polymerizing vinyl monomers.

Conventionally, known methods for polymerizing vinyl monomers include suspension polymerization, emulsion polymerization, solution polymerization, gas phase polymerization, and bulk polymerization. In either case, there was a problem of polymer scale adhesion on the inner wall of the polymerization vessel.

In other words, when vinyl monomers are polymerized using these methods, polymer scale adheres to the parts that come into contact with the monomers, such as the inside of the polymerization vessel M and the stirring device, and as a result, the yield of the polymer decreases.
In addition to reducing the cooling capacity of the polymerization reactor, this scale flakes off and mixes into the product, reducing the quality of the product. On the other hand, removing this scale requires excessive labor. Not only does this take time, but because unreacted monomers are adsorbed in this scale, there is a risk of injury to the human body due to monomers (vinyl chloride, etc.), which has become an extremely serious problem in recent years. There is a disadvantage that there is

In order to prevent this polymer scale from adhering to the walls of the polymerization vessel, for example, in the suspension polymerization of vinyl chloride, an alkaline substance is added to the polymerization system. A method of maintaining the pH of the polymer at 8 or higher, a method of adding an inorganic oxidizing agent to the polymerization system, or a method of applying a polar organic compound such as an amine compound, a quinone compound, an aldehyde compound, or a dye to the inner wall of the polymerization vessel and the stirrer, etc. The method is known.

However, when the vinyl monomers are vinyl esters, acrylic acid or methacrylic esters, diene compounds, etc., the method of adding the above-mentioned alkaline substances or inorganic oxides to the polymerization system is not suitable for oxidizing or It has the disadvantage of causing undesirable effects such as decomposition, and the method of applying dipolar organic compounds or dyes to the wall surface of the polymerization vessel uses emulsifiers, conjugated diene monomers, and other vinyl monomers. Copolymerization systems with acyl peroxides such as benzoyl peroxide and lactyl peroxide, and lauric acid.

stearic acid or esters or salts of these acids;
For polymerization systems in which mercaptans (molecular weight regulators) and the like are present, they have the disadvantage that not only are they less effective in preventing scale adhesion, but the effects of their application disappear within a short period of time.

The purpose of the present invention is to provide a method for polymerizing vinyl monomers that overcomes these drawbacks, and the gist thereof is as follows.

An oxidative condensate of an aromatic amine compound and an electron-accepting organic compound are applied to the inner wall of a polymerization vessel, and the coated surface is then treated with an aqueous solution of a metal salt as necessary. 1. A method for producing a polymer, which comprises polymerizing a polymer.

According to the method of the present invention, it is possible to extremely reduce the adhesion of polymer scale on the inner walls of the polymerization vessel, stirring blades, stirring shafts, and other parts that come into contact with monomers. In various polymerization methods such as polymerization method and bulk polymerization method, the advantage is brought about that it can be exhibited without being affected by the composition of the vinyl monomer type 1 polymerization system. Particularly, the present invention is characterized in that it is effective even when a water-soluble combined catalyst is used.

Next, the content of the present invention will be explained in detail.

The oxidative condensate of an aromatic amine compound used in the method of the present invention is obtained by mixing an aromatic amine compound capable of oxidative condensation with a suitable oxidizing agent and reacting it, but this oxidative condensate is not strictly defined. It does not have any special meaning, and intermediates leading to the final condensate are naturally included in this oxidative condensate.

Aromatic amine compounds that can form oxidative condensates include:
Aniline, p-phenylenediamine, dimethyl-p-phenylenediamine, toluylene-p-diamine, 1.5
-naphthylene-diamine, 〇-phenylenediamine, 4
-chloro-o-phenylenecyamine, 4-nitro-0-
Phenylenediamine hydrochloride, 24-toluylenediamine, 5-nitrotolylene-2,4-diamine, 4-methoxyleafenylenediamine, 4-methoxy-m-phenylenediamine sulfate, dibase of p-phenylenediamine 7 acid salt, 2-chloro-p-phenylenediamine, 2-
Chloro-p-phenylenediamine sulfate L 2-nitro-
p-phenylenediamine, N,N-dimethyl-p-phenylenediamine sulfate, 3-(p-amino anilino)
-1,2-propanediol, p-aminodiphenyl-
Amine hydrochloride, 0-methoxy-p-aminodiphenylamine hydrochloride, p,p'-diaminodiphenylamine dihydrochloride, p,p'-bisdimethylaminodiphenyl-amine sulfate, 5-amino-2-(3- Amino-p-)luidino)benzenesulfonic acid, copper salt of 0-aminophenol, 2-amino-4-chromitzenol, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, vicula kamotsucnic acid , m-aminophenol, p-
Examples include aminophenol hydrochloride, 4-amino-2-nitrophenol, p-amino-p'-hydroxy-diphenylamine, p-amino-m-methyl-p'-hydroxy-diphenylamine, and the various aromas listed above. Suitable oxidizing agents for oxidative condensation of group amine compounds include permanganic acid and its salts such as permanganic acid and potassium permanganate, chromium dioxide, potassium dichromate, and sodium chromate chloride. Nitric acid and its salts such as nitric acid, silver nitrate, lead nitrate, halogens such as iodine, bromine, chlorine, fluorine, hydrogen peroxide, sodium peroxide, benzoyl peroxide, potassium persulfate, persulfate, etc. ammonium sulfate,
peroxides such as peracetic acid, cumene hydroperoxide, perbenzoic acid, p-menthane hydroperoxide, sulfates such as hot concentrated sulfuric acid, a mixture of fuming sulfuric acid and concentrated nitric acid, iodic acid, potassium iodate, Oxygen acids or salts such as sodium chlorate, metal salts such as ferric chloride, copper sulfate, cupric chloride, lead acetate, ozone, oxygen species such as oxygen, copper oxide, mercury oxide, oxidation Examples include oxides such as cerium, manganese dioxide, and osmic acid.

The production of oxidized condensates is influenced by the amount of oxidizing agent used, p) (, and reaction temperature. The reaction can usually be carried out at room temperature, but
It may be carried out under O''CPl or at a temperature of 50°C or higher.The pH may be either acidic or alkaline.The amount of oxidizing agent used is several pp depending on the reaction time.
It can be arbitrarily selected within the range of pm to several percent.

Next (2) Electron-accepting compounds that can be mixed with a condensate produced by oxidative condensation of an aromatic amine compound and used in coating C1 include σ-electron-accepting compounds and π-electron-accepting compounds, Specifically, benzoquinone, naphthoquinone, and anthraquinone.

Quinone compounds such as diphenylquinone, chloranil, fluoranil, fluoranil, oxidative condensation products of α-naphthalene sulfonic acid, anthraquinone sulfonic acid, aromatic amine compounds, or their intermediate sulfonic acids, or their salts such as sodium, potassium, ammonium, etc. ,α
- Hydroxyl compounds such as naphthol, glucose, cellulose ethers, phenol, paraphenol, pyrogallol, pyrocatechol, naphthalene.

Anthracene, olefins, halogenated hydrocarbons.

Carboxylic acids such as 3-oxy-2-naphthoic acid, naphthalic acid, diphenylic acid, picric acid, thioglycolic acid, benzoic acid, maleic acid, ascorbic acid and their anhydrides or their sodium, potassium, ammonium salts, α- Nitro compounds such as nitronaphthalene, nitrobenzene, and trinitrobenzene, cyano compounds such as α-cyanonaphthalene and tetracyanoethylene, phosphoric acids such as tripolyphosphoric acid and phytic acid, and their sodium, potassium, and ammonium salts, α-naphthol orange, Acidic azo dyes including monoazo, disazo, and polyazo such as Red No. 2, Acid Brown RX, Acid Cyanine OR, Acid Light Yellow, Milling Black VLG, acid mordant azo dyes such as Chrome Black PG, Direct Brown M, Congo Red, Direct Direct azo dyes such as blue, alizarin (anthraquinone mordant dye), anthraquinone violet JD (
anthraquinone acid dyes), indanthrene (anthraquinone vat dyes), other thren, anthraquinone dyes, naphthoquinones such as indanthrene 5GD, Mikegin Brown CHD, benzoquinone vat dyes, indigosol, anthrazole dyes, indigo dyes such as Brilliant Gloss Indigo B, nitro dyes such as Naphthol Yellow S, nitroso dyes, sulfur dyes, acid triphenylmethane dyes such as Acid Milling Green J and Acid Violet 4BN, nigrosine, brilliant alizarin blue 3, etc. Acidic quinone imine dyes with azine rings, oxazine rings, and thiazine rings, Soler Brown RKX, Oil Red RR, Oil Red S
A, azo dyes such as Oil Scarlet 308 and Paris Fast Black 3804, xanthine dyes such as Rhodamine B base, various reactive dyes such as Brilliant Orange G8° Brilliant Blue Re, quinoline dyes, Xylene Fast Yellow 2G (pyrazolone dye),
Examples include chrysofenine (stilbene dye) and diacinlose BD (thiazole dye).

Although the present invention uses an oxidized condensate of an aromatic amine compound and an electron-accepting compound in combination, it is convenient to dissolve or disperse them in a suitable medium in advance. This medium is generally one type of solvent such as water, alcohol solvents, ester solvents, ketone solvents, hydrocarbon solvents, chlorinated hydrocarbon solvents, or aprotic solvents such as dimethylbormamide, dimethyl sulfoxide, and acetonitrile. Alternatively, a mixed solvent of two or more types is used.

This dissolution or dispersion operation is carried out by simultaneous dissolution or separate dissolution and mixing, and is usually carried out at room temperature, but with
It is also possible to operate at temperatures below 50°C or above 50°C.

Therefore, in the method of the present invention (-), the most effective composition for preventing scale adhesion is a composition ratio of an oxidized condensate of an aromatic amine compound and an electron accepting compound in a weight ratio of 1:20 to 20.
:1, preferably 1:5 to 5:1.

When these two are used together, the amount of coating may be the same as when using conventional coating agents, and the surface to be coated as the sum of the oxidized condensate of the aromatic amine compound and the electron-accepting compound,
That is, 0.0% for the inner wall of the polymerization vessel and the surface of the stirrer.
001J'/yn'' or more, the effect of preventing scale adhesion can be sufficiently exhibited.

The coated surface of the oxidized condensate of the aromatic amine compound and the electron-accepting organic compound is formed by the above-mentioned operation, but even better effects can be obtained by further treating this coated surface with an aqueous solution of the metal salt. It becomes like this.

The category of metal salts used in this case shall be interpreted in a broad sense, and in the present invention, it includes metal salts in a narrow sense, metal hydroxides, metal oxides, and metal halide. Compounds include alkali metals such as sodium and potassium, magnesium, calcium,
Alkaline earth metals such as barium, zinc group metals such as zinc, aluminum group metals, soot group metals such as titanium and tin, iron group metals such as iron and nickel, chromium group metals such as chromium and molybdenum, manganese such as manganese group metals,
Silicates, carbonates, bicarbonates, phosphates, sulfates, nitrates, phosphates, acetates, and water of metals selected from copper group metals such as copper and silver, platinum metals such as platinum, etc. Examples include oxides, oxides, and halides.

In order to form a coated surface on the inner wall of the lily container and other parts that come into contact with the mass body, and to treat this coated surface with an aqueous solution of the above components, for example, after the coating, the aqueous solution of the above components is poured into the polymerization vessel. is charged, and the inside is preferably heated to 50 to 100℃ for 10
This is advantageously carried out by heating for more than a minute. After this treatment, the liquid can be extracted and normal polymerization operations can be carried out thereafter. However, in the case of polymerization operations in an aqueous medium such as suspension polymerization and emulsion polymerization, the liquid after the treatment is not extracted, and the polymerization operation is carried out in a normal manner. C dimer and other polymerization C: Necessary components (dispersant, polymerization initiator, etc.) may be charged and the polymerization operation may be carried out.

It is advantageous to heat the coated surface to temperatures above 50° C.; at low processing temperatures, this treatment can sometimes take more than 1110 hours to obtain a sufficient effect. Further, the effective concentration of the metal salt in the treatment liquid may be approximately several ppm to several percent concentration.

When carrying out the method of the invention in particular using an aqueous medium,
When an alkaline substance is added to the aqueous medium to a value of p) (8 or more), the purpose of preventing scale adhesion can be more reliably achieved.

In this case, the alkaline substances that can be used in C1 include alkali metal or alkaline earth metal oxides, hydroxides, carbonates, phosphates, bicarbonates, silicates, acetates, phytates, ethylenediamine tetra Examples include acetate, ammonia, and ammonium compounds exhibiting alkalinity.

These alkaline substances are added in such amounts as to give a pH of 8 or higher, but also in amounts that do not impair the quality of the polymer produced, i.e. monomers or monomer mixtures C: It is preferably 1% or less.

The method of the present invention is an effective means for all polymerizations. Therefore, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, which are effective for polymerizing ethylenically unsaturated monomers, can be employed, and C: Various additives added to the polymerization system, such as partially saponified polyvinyl Alcohol, suspending agents such as methylcellulose, anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzenesulfone, sodium dioctyl sulfonate, sodium laurate, sorbitan monolaurate, polyoxyethylene alkyl ethers. Nonionic emulsifiers, fillers such as calcium carbonate, titanium oxide, stabilizers such as tribasic lead sulfate, metal stearates, dibutyltin dilaurate, lubricants such as rice wax, stearic acid, DOP%DBP , plasticizers such as DAP, trichlorethylene, chain transfer agents such as mercaptans, pH regulators, diisopropyl peroxydicarbonate, dimethyl valeronitrile, potassium persulfate, cumene hydroperoxide, p-menthane 8F.
In a polymerization system in which a polymerization catalyst such as oxide is present, the purpose of preventing scale adhesion is fully achieved.

The method of the present invention involves the polymerization of various ethylenically unsaturated monomers.
: applied, but specific examples of this mft form include vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid, methacrylic acid or their esters or salts, maleic acid or fumaric acid. Examples include acids and their esters or anhydrides, diene threaders such as butadiene, lysobrene, and isoprene, as well as styrene, acrylonitrile, vinylidene halides, vinyl ethers, and the like.

The method of the present invention is particularly suitably carried out in the case of so-called heterogeneous radical polymerization in which the polymer is precipitated from the polymerization phase, such as suspension polymerization, emulsion polymerization, and bulk polymerization. production of vinyl halides or vinylidene halide, or their (co)polymers by suspension polymerization or emulsion polymerization of monomer mixtures mainly composed of them, polystyrene, polymethyl methacrylate,
Production of polymer beads such as polyacrylonitrile, latex, production of synthetic rubbers such as SBR, OR, IRlIIR (these synthetic rubbers are usually produced by emulsion polymerization), production of ABS resin, inner walls of polymerization vessels in C2, etc. scale adhesion is prevented.

Next, examples and comparative examples of the method of the present invention will be given.

However, in the following description C2, all parts simply refer to parts by weight.

Example] Water 1! In a solution of 35% hydrochloric acid 27-
- Dissolve aminodiphenylamine, cool to 0°C with stirring, add 4.7% hydrogen peroxide, and further add 0.1% ferrous sulfate, react for 24 hours, and remove the precipitate formed. The material was filtered, washed with water and made into a base with ammonia, and this base material was filtered, washed with water and dried at 35-40°C. 0.5 part of this product (based product) and 0.5 part of the sodium sulfonic acid salt of the above product were mixed with 10 parts of methanol.
0 parts C was dissolved to prepare a coating agent.

The above-mentioned coating agent was applied to the inner wall of a 10007 stainless steel polymerization vessel equipped with an agitator having a paddle blade having a diameter of 400 mm and the agitator, and then washed with water. Next, 20 (17') vinyl chloride monomers, 4
ooQ and the additives shown in Table 1 were added, the stirrer was rotated at 10 Orpm, and the temperature was 57°C.
Polymerization was carried out for 0 hours. The results of measuring the amount of scale after polymerization are shown in Table 1.

However, Experiment/1611-14 in the same table shows comparative examples,
/1611 is the case where no coating is performed, and Nos. 12 to 14 are the cases where a 1% methanol solution of nigrosine base is used as the coating agent.

Experiments/I66 and 7 marked with * show the case of copolymerization of vinyl chloride and vinyl acetate, and the charging ratios of these monomers are as follows.

Experiment 46: Vinyl chloride 2ooNF Acetic acid and Nyl 10ki Experiment/%7 Vinyl dichloride 200 Instant Vinyl acetate 37.5 marks @1 The meanings of the abbreviations used in the table are as follows,
These were also used in common in Example 2 and subsequent examples.

DMVN: α, α′-Azobisdimethylvaleronitrile IPP: Diisopropyl peroxydicarbonate KPB: Potassium persulfate APE: Ammonium persulfate LPO: Lauroyl peroxide PvA dipartially saponified polyvinyl alcohol Na-DB
S: Sodium dodecylbenzenesulfonate (Na-LS: Sodium lauryl sulfate) TPMO:
Hydroxyprobyl methylcellulose SML: Also sorbitan monolaurate. Notes 1 and 2 in Table 1 are as follows.

Note 1 Calcium nistearate 2.5 mark rice wax 3. OI/ Tin octylate mercaptide 1.7511 Polyethylene wax 0.25 Sand Note 2: Tribasic lead sulfate 31 Calcium carbonate 7.5 DOP 5.0 # Stearic acid 1.25.

:X Calcium thearate” 1.75//Titanium oxide
3.75,.

Example 2 Methanol 1! 100? Dissolve, stir, and cool to 0°C, add 100% of 4.7% hydrogen peroxide, and add 0.5% of hydrogen peroxide.
One portion of ferrous sulfate was added and allowed to react for 24 hours. The generated sediment is filtered, washed with water, and made into a paste with ammonia.
Add 100% of the electron-accepting compound shown in Table 2 to this solution.
was dissolved to prepare a coating solution.

Apply the above coating agent to the inner wall and the stirrer part of a 00J stainless steel polymerization vessel, which is equipped with a stirrer with paddle blades with a diameter of 150 mm inside, and if necessary, coat the coated surface with an aqueous solution of metal salt. Experiment with processing/%17
．． 20.23.26.29.34), this side was washed with water.

Next, add 500 i of sodium laurate, 50 i of t-dodecyl mercaptan, 50 i of filtered potassium sulfate to this polymerization vessel. 20% of water was charged, and after purging with nitrogen gas, 2.5% of styrene and 75% of butadiene were charged, and the reaction was carried out at 50°C for 200 hours to obtain +SBR latex.

The results of measuring the amount of scale after polymerization are shown in Table 2. However, Experiments 431 to 34 in the same table show comparative examples, in which no oxidized condensate of an aromatic amine compound was used.

The treatment of the coated surface with the metal salt aqueous solution in Experiments/1617.20.23.26.29 and 34 was carried out as follows, respectively.

Experiment: Fill the polymerization vessel after coating with a 1% aqueous solution of % 17: Na25in, heat it to 90°C, hold it for 30 minutes, and then remove the liquid from the polymerization.

Experiment/1620: Same as experiment/1617 (conducted in Niji).

Experiment A623: Conducted in the same manner as Experiment 417 except that a 1% aqueous solution of NaHCO2 was used.

Experiment, %26: Performed similarly to experiment 423.

Experiment 429: Conducted in the same manner as Experiment A617.

Experiment/%34: Conducted in the same manner as Experiment 417.

0 0 0 0 n low --C) 0 00 tori ; --
Example 3 Dissolve 100p of aniline hydrochloride in 1.8ml of water and 42% sodium chlorate. , 46.5 points 6 of 33% hydrochloric acid was added, 2 drops of syrupy vanadium chloride was added to the solution, and the temperature was heated to 0°C.
The resulting precipitate was filtered, thoroughly washed with water, and then made into a base with ammonia.

This paste product was filtered, washed with water and dried at 35-40°C, and 0.4 parts of this paste and 0.5 parts of the above-mentioned sodium sulfonate of the above-mentioned starch were dissolved in 100 parts of acetone to form a coating material. And so.

The inner wall of the combination device of a stainless steel vertical polymerization vessel with an internal volume of 2 mm and a stainless steel horizontal polymerization vessel with an internal volume of 4 mm and other parts that come in contact with the vehicle body (2. Apply the above coating agent and wash with water, After drying 2) Add 5ooP of vinyl chloride monomer and 0.3J of diisopropyl peroxydicarbonate to the polymerization vessel.
P was charged, stirring speed was 900 rpm, temperature was 60°C.
After polymerization was carried out for 2 hours, the contents were transferred to a 4-tube polymerization vessel containing 800 grams of vinyl chloride monomer and 0.4 j' of diisopropyl peroxydicarbonate, and the polymerization was carried out at 100 rpm. Polymerization was carried out at 57° C. for 10 hours with stirring. After finishing, check the MN with scale on the wall $
The results shown in 3 tables were obtained.

However, 36. and 37 show comparative examples.

Table 3 Experiment/16 Coating agent Scale 1l()/rrl>(2
(4 polymerization vessels) 35 (This invention) Q.

36 None 1500 2200 37 °g0shi' 120 90 Pace Example 4 Internal C2 type diameter 150III + internal volume 100 equipped with a paddle-wing machine! A coating agent as shown in Table 4 was applied to the inner wall of a small stainless steel mixer and the agitator part, and if necessary, the surface of the fallen cloth was treated with an aqueous metal salt solution, and after the treated solution was drained, it was washed with water.

Next, we will use this polymerization vessel to create 200 small vinyl chloride companies! , 400 KF of ion-exchanged water and the additives shown in Table 4 were added, and the stirrer was rotated at 1100 rpm.
Polymerization was carried out at a temperature of 57° C. for 10 hours.

Polymerization is repeated in this manner, and the amount of scale is i y7
rr? The time point at which scale adhesion occurred was determined by the above or with the naked eye, and the number of polymerizations required up to that point was determined, and the results shown in Table 4 were obtained.

However, in the column of coating agents in the same table, the experiment numbers of those already used in Examples 1 to 3 are shown.

Treatment of coated surface Experiment/164fi: Conducted in the same manner as Experiment No. 17.

Experiment/l650: Same as pure +1') u) I+ ■ To Φ 0 -! 1
＋P groaning and lying Example 5 The coating agent obtained in Example 1 was applied to the wall and agitator surface of a stainless steel polymerization vessel with an internal volume of 5J, and after washing with water, the following was applied to this polymerization vessel. Each component: 180 parts of water, 5 parts of sodium oleate, 1 part of oleic acid, 0.5 parts of mercaptan, 0.37 parts of potassium persulfate, and various alkaline substances shown in Table 5 (types and preparation methods are as follows). After nitrogen substitution, 26 parts of acrylonitrile and 74 parts of butadiene were charged and polymerized at 40°C for 12 hours.This operation was repeated until the amount of scale was ly/rrf or more or scale adhesion was observed with the naked eye. When we investigated the number of polymerizations that resulted in
).

However, Experiments/1655 and 56 are comparative examples; the former is a case where no coating is applied, and the latter is a case where a 1% methanol solution of Nigrosin paste is applied.

Further, the types and addition methods of the alkaline substances are as follows.

Experimental rot 56 Add 0.1% sodium hydroxide before starting polymerization.
(For monomers, the same applies hereinafter) Addition, pH of medium 12, 0° Experiment 458: Same as above Experiment / 59: 2 hours after the start of binding C 0.1''A of sodium dihydroxide was added.

Experiment/%60: Polymerization initiation After polymerization initiation, 0.1
% addition.

In experiment A66, 0.2% sodium acetate was added before the start of polymerization, and the pl of the medium was 9.5.

Experiment A662: 0.1% Na28i0, before starting polymerization
Addition, medium pH 10.0.

Table 5 55 None 1 56 Yes 1 57 None 3 58 Yes 6 59 Yes 5 60 Yes 4 61 Yes 5 62 Yes 8

Claims (1)

[Claims] 1. An oxidizing metal of an aromatic amine compound and an electron-accepting organic compound are coated on the inner wall of a polymerization vessel, and then this coated surface is treated with an aqueous solution of a metal salt as necessary. A method for producing a polymer 2, characterized by polymerizing a saturated monomer, and a method according to claim 2, in which the aqueous medium is made alkaline with a pH of 9 or more.